CN110980741A - Tetrachlorosilane hydrogenation system and method for preparing trichlorosilane by using same - Google Patents
Tetrachlorosilane hydrogenation system and method for preparing trichlorosilane by using same Download PDFInfo
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- CN110980741A CN110980741A CN201911283979.7A CN201911283979A CN110980741A CN 110980741 A CN110980741 A CN 110980741A CN 201911283979 A CN201911283979 A CN 201911283979A CN 110980741 A CN110980741 A CN 110980741A
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- tetrachlorosilane
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 165
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 title claims abstract description 148
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 156
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 156
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 153
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 130
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 238000009834 vaporization Methods 0.000 claims abstract description 22
- 230000008016 vaporization Effects 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000009833 condensation Methods 0.000 claims abstract description 18
- 230000005494 condensation Effects 0.000 claims abstract description 18
- 239000000428 dust Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims description 102
- 239000007789 gas Substances 0.000 claims description 92
- 238000003860 storage Methods 0.000 claims description 63
- 238000005406 washing Methods 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 31
- 238000001704 evaporation Methods 0.000 claims description 24
- 239000000110 cooling liquid Substances 0.000 claims description 18
- 238000007323 disproportionation reaction Methods 0.000 claims description 18
- 238000011144 upstream manufacturing Methods 0.000 claims description 18
- 239000000112 cooling gas Substances 0.000 claims description 16
- 239000002918 waste heat Substances 0.000 claims description 16
- 239000005046 Chlorosilane Substances 0.000 claims description 15
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 15
- 239000008236 heating water Substances 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 239000006200 vaporizer Substances 0.000 claims description 12
- 239000002912 waste gas Substances 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 150000004678 hydrides Chemical class 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000005049 silicon tetrachloride Substances 0.000 description 5
- 239000000498 cooling water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
Abstract
The invention provides a system for preparing trichlorosilane by hydrogenating tetrachlorosilane, which comprises a silicon powder pretreatment unit, a tetrachlorosilane pressurizing unit, a tetrachlorosilane heat exchange unit, a hydrogen pressurizing unit, a hydrogen heat exchange unit, a vaporization heat exchange unit, a hydrogenation reaction unit, a dust removal unit and a condensation separation unit, wherein the structural units are matched with one another, so that the system has the remarkable advantages of simple and convenient operation, continuity and stability, energy conservation and consumption reduction; the trichlorosilane prepared by hydrogenating the tetrachlorosilane disclosed by the invention does not need to additionally add a catalyst, and a metal chloride byproduct generated in the hydrogenation process of the tetrachlorosilane can achieve a catalytic effect, so that the conversion rate can reach 25-28%.
Description
Technical Field
The invention relates to the technical field of silane production, in particular to a tetrachlorosilane hydrogenation system and a method for preparing trichlorosilane by using the same.
Background
The production of silane by a trichlorosilane disproportionation method produces a large amount of silicon tetrachloride, and the production of trichlorosilane by using silicon tetrachloride and the reduction of production cost become the key points of the current development. The hydrogenation system is an important component in the production process of the silane, promotes the material recycling, and has important significance in reducing the energy consumption of the silane production by improving the primary hydrogenation conversion rate.
At present, the domestic silicon tetrachloride reduction methods mainly comprise three types, namely hot hydrogenation, cold hydrogenation and chlorine hydrogenation, wherein the hot hydrogenation is easy to operate and has low technical requirements, but the energy consumption is high, the conversion rate is low, the investment cost is high, and therefore the method is basically eliminated in the practical production application; the chlorine hydrogenation is widely applied to actual production due to low energy consumption, high conversion rate and low investment cost, but still has the problems of difficult operation and high technical requirement; the cold hydrogenation also has the characteristics of low energy consumption, relatively high conversion rate and low investment cost, but has less application in actual production due to high technical requirements.
In addition, the conventional cold hydrogenation process has at least the following disadvantages: (1) the catalyst used in the main reaction has high cost and needs drying and activation (an activated hydrogen compressor and an electric heater need to be equipped); (2) the one-time conversion rate of the reactor is relatively low, and the production efficiency is low; (3) the silicon powder recovered by the dry dust removal device is incomplete, and the gas phase has more entrainment, so that the normal operation of wet dust removal is influenced, and sometimes even the device needs to be stopped for cleaning; (4) the wet dust removal device can not completely treat the silicon powder and the metal chloride in the chlorosilane mixed gas, so that subsequent equipment and pipelines are blocked.
Therefore, in view of the above-mentioned drawbacks of the prior art, it is an urgent need to solve the problems of the prior art to provide a tetrachlorosilane hydrogenation system and a method for preparing trichlorosilane therefrom.
Disclosure of Invention
In view of the above, the invention provides a system and a method for preparing trichlorosilane by hydrogenating tetrachlorosilane, which have the remarkable advantages of simple and convenient operation, continuity and stability, energy conservation and consumption reduction by combining a high-pressure production stage and a low-pressure production stage, wherein the high-pressure front-end process is a process and hardware associated with a hydrogenation reactor, a solid/heavy impurity removal device and a hydrogen recovery device, and the low-pressure rear-end process is a process consisting of purification and separation of trichlorosilane, silicon tetrachloride and dichlorosilane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a tetrachlorosilane hydrogenation system is communicated with a disproportionation reaction system and comprises a silicon powder pretreatment unit, a tetrachlorosilane pressurization unit, a tetrachlorosilane heat exchange unit, a hydrogen pressurization unit, a hydrogen heat exchange unit, a vaporization heat exchange unit, a hydrogenation reaction unit, a dust removal unit and a condensation separation unit;
the downstream of the silicon powder pretreatment unit is communicated with the hydrogenation reaction unit;
the downstream of the tetrachlorosilane pressurizing unit is communicated with the tetrachlorosilane heat exchange unit, the downstream of the hydrogen pressurizing unit is communicated with the hydrogen heat exchange unit, and the tetrachlorosilane heat exchange unit and the hydrogen heat exchange unit are respectively communicated with the vaporization heat exchange unit;
the downstream of the vaporization heat exchange unit is communicated with the hydrogenation reaction unit, and the downstream of the hydrogenation reaction unit is communicated with the dust removal unit through the vaporization heat exchange unit;
the dust removal unit is communicated with the condensation separation unit through the tetrachlorosilane heat exchange unit and the hydrogen heat exchange unit.
Preferably, the silicon powder pretreatment unit comprises a silicon powder storage tank, a silicon powder dense-phase pump, a silicon powder dryer, a silicon powder receiving tank, a silicon powder metering tank, a hydrogen heater and a silicon powder filter;
a silicon powder feeding port is formed in the top of the silicon powder storage tank, a hydrogen inlet is formed in the bottom of the silicon powder storage tank, and the bottom of the silicon powder storage tank is connected with the silicon powder dense-phase pump;
the silicon powder dense-phase pump is communicated with the hydrogen, and the downstream of the silicon powder dense-phase pump is communicated with the silicon powder dryer;
the silicon powder dryer is communicated with the silicon powder receiving tank, the bottom of the silicon powder dryer is connected with the hydrogen heater, and the hydrogen heater is communicated with hydrogen;
the bottom of the silicon powder receiving tank is communicated with the silicon powder metering tank, and the silicon powder metering tank is communicated with the hydrogenation reaction unit;
and the silicon powder dryer, the silicon powder receiving tank and the silicon powder metering tank are respectively communicated with the outside through the silicon powder filter.
Preferably, the tetrachlorosilane pressurizing unit comprises a tetrachlorosilane buffer tank and a tetrachlorosilane delivery pump;
the upper stream of the tetrachlorosilane buffer tank is connected with the disproportionation reaction system, and the lower stream of the tetrachlorosilane buffer tank is connected with the tetrachlorosilane transfer pump;
the downstream of the tetrachlorosilane transfer pump is connected with the tetrachlorosilane heat exchange unit;
the tetrachlorosilane heat exchange unit comprises a tetrachlorosilane superheater and a tetrachlorosilane preheater;
the upper stream of the tetrachlorosilane superheater is communicated with the tetrachlorosilane delivery pump, and the lower stream of the tetrachlorosilane superheater is communicated with the vaporization heat exchange unit through the tetrachlorosilane preheater.
Preferably, the hydrogen pressurizing unit comprises a hydrogen compressor and a hydrogenated compressed hydrogen buffer tank;
the hydrogen compressor is connected with the hydrogenated compressed hydrogen buffer tank, and the downstream of the hydrogenated compressed hydrogen buffer tank is communicated with the hydrogen heat exchange unit;
the hydrogen heat exchange unit comprises a hydrogen superheater and a hydrogen preheater;
the upstream of the hydrogen superheater is communicated with the hydrogenated compressed hydrogen buffer tank, and the downstream of the hydrogen superheater is communicated with the vaporization heat exchange unit through the hydrogen preheater.
Preferably, the vaporization heat exchange unit comprises a tetrachlorosilane vaporizer and a high-temperature gas-gas heat exchanger;
the upstream of the tetrachlorosilane vaporizer is respectively communicated with the tetrachlorosilane preheater and the hydrogen preheater, and the downstream of the tetrachlorosilane vaporizer is connected with the hydrogenation reaction unit through the high-temperature gas-gas heat exchanger.
Preferably, the hydrogenation reaction unit comprises an electric heater, a hydrogenation reactor and a cyclone filter, wherein the upstream of the electric heater is connected with the high-temperature gas-gas heat exchanger, and the downstream of the electric heater is connected with the hydrogenation reactor;
the bottom of the hydrogenation reactor is sequentially provided with a reaction air inlet, a feed inlet and a distribution plate from bottom to top, the reaction air inlet is connected with the electric heater through a pipeline, the feed inlet is communicated with the silicon powder metering tank, and the distribution plate is horizontally arranged in the hydrogenation reactor;
the cyclone filter is arranged on the top surface of the hydrogenation reactor and is communicated with the hydrogenation reactor, and the downstream of the cyclone filter is communicated with the dust removal unit through the high-temperature gas-gas heat exchanger.
Preferably, the dust removal unit comprises a washing tower, a raffinate evaporating pot, a solid-liquid separation condenser, a raffinate reclaimed material storage tank and a washing tower reflux pump;
the bottom of the washing tower is provided with a washing tower air inlet and a washing tower liquid outlet, the top of the washing tower is provided with a washing tower air outlet and a washing tower liquid inlet, the washing tower air inlet is communicated with the high-temperature gas-gas heat exchanger, the washing tower liquid outlet is communicated with the raffinate evaporating tank, the washing tower air outlet is communicated with the condensation separation unit sequentially through the hydrogen superheater, the hydrogen preheater, the tetrachlorosilane superheater and the tetrachlorosilane preheater, and the liquid inlet is communicated with the condensation separation unit through the washing tower reflux pump;
the residual liquid evaporating pot comprises a residual liquid pot liquid inlet, a residual liquid pot gas outlet, a steam inlet and a solid slag outlet; the residual liquid inlet and the residual liquid tank outlet are arranged at the top of the residual liquid evaporating pot, and the steam inlet is arranged on the side surface of the residual liquid evaporating pot; the solid slag outlet is arranged at the bottom of the residual liquid evaporating pot;
the chlorosilane gas outlet is communicated with the residual liquid reclaimed material storage tank through the solid-liquid separation condenser; and the residual liquid reclaimed material storage tank is communicated with the condensation separation unit.
Preferably, the condensation separation unit comprises a waste heat heating water heat exchanger, a hydrogenation evaporative condenser, a condensate storage tank, a hydrogenation gas heat exchanger, a deep cold gas-liquid separator, a hydrogenation cryogenic condenser and a hydrogenation material storage tank;
the upstream of the waste heat heating water heat exchanger is communicated with the gas outlet of the washing tower through the hydrogen superheater, the hydrogen preheater, the tetrachlorosilane superheater and the tetrachlorosilane preheater, and the downstream of the waste heat heating water heat exchanger is communicated with the hydrogenation evaporative condenser;
the hydrogenation evaporative condenser is provided with a gas outlet communicated with the hydrogenation gas heat exchanger, and a liquid outlet communicated with the condensate storage tank;
the downstream of the hydrogenation gas heat exchanger is communicated with the deep cold gas-liquid separator;
the deep cold gas-liquid separator is connected with the hydrogenation deep cold condenser, a liquid outlet of the deep cold gas-liquid separator is communicated with the hydrogenation material storage tank, and a gas outlet of the deep cold gas-liquid separator is communicated with the hydrogen compressor;
the downstream of the condensate storage tank is communicated with the hydrogenated material storage tank, and the downstream of the hydrogenated material storage tank is communicated with the disproportionation reaction system.
Preferably, the system also comprises a compressed hydrogen buffer tank, a first supplementary hydrogen buffer tank, a supplementary hydrogen compressor and a second supplementary hydrogen buffer tank;
the upper stream of the compressed hydrogen buffer tank is connected with the recovered hydrogen sequentially through the first supplementary hydrogen buffer tank, the supplementary hydrogen compressor and the second supplementary hydrogen buffer tank, the upper stream is also connected with the exhaust port of the hydrogen gas heat exchanger, the upper stream is also connected with electrolyzed water to prepare hydrogen, and the lower stream is connected with the hydrogen gas compressor.
Preferably, the system also comprises a silicon powder emergency receiving tank, an emergency discharge cooler and an emergency discharge tank;
the upper stream of the silicon powder emergency receiving tank is communicated with the hydrogenation reactor, and the silicon powder emergency receiving tank is internally connected with circulating cooling water;
the upstream of the emergency discharge cooler is respectively connected with the tetrachlorosilane vaporizer and the washing tower, the downstream of the emergency discharge cooler is connected with the emergency discharge tank, and the interior of the emergency discharge cooler is connected with circulating cooling water;
and the downstream of the emergency discharge tank is connected with the residual liquid evaporating tank.
The method for preparing trichlorosilane through hydrogenation of tetrachlorosilane is characterized by adopting the tetrachlorosilane hydrogenation system, and specifically comprises the following steps:
(1) the silicon powder is dried by the silicon powder dryer and then enters the silicon powder receiving tank, and then is put into the silicon powder metering tank for metering, and the metering is carried out through H2Pressurizing to 1.0-3.2MPaG, and conveying to a hydrogenation reactor;
(2) the tetrachlorosilane is pressurized to 1.0-3.2MPaG after passing through a tetrachlorosilane transfer pump, is introduced into a tetrachlorosilane superheater and heated to 160 ℃ for 100-;
pressurizing hydrogen to 1.0-3.2MPaG through a hydrogen compressor and a hydrogenation compressed hydrogen buffer tank, then introducing into a hydrogen superheater and heating to 160 ℃ of temperature of 100-;
controlling H in mixed gas2The molar ratio of the tetrachlorosilane to the tetrachlorosilane is (1.5-3.5): 1, heating the mixed gas to 450 ℃ in a high-temperature gas-gas heat exchanger, heating to 600 ℃ in 450 ℃ by using an electric heater, and then feeding the mixed gas into a hydrogenation reactor;
(3) the mixed gas and the silicon powder continuously react in the hydrogenation reactor, the temperature of the hydrogenation reactor is controlled to be 480-580 ℃, the pressure is controlled to be 1.0-3.2MPaG, and the gas flow velocity in the hydrogenation reactor is controlled to be 0.4-0.8 m/S; the obtained high-temperature gas hydrogenation product is output after passing through a cyclone separator;
(4) the high-temperature gas hydrogenation product exchanges heat with the mixed gas of hydrogen and tetrachlorosilane through a high-temperature gas-gas heat exchanger, is cooled to 360 ℃ and is introduced into a washing tower;
washing the high-temperature gas product in a washing tower by using a chlorosilane solution, and cooling the washed gas to 100-200 ℃ through heat exchange with hydrogen and tetrachlorosilane respectively by using a hydrogen preheater, a hydrogen superheater, a tetrachlorosilane preheater and a tetrachlorosilane superheater;
then the waste heat heating water enters a hydrogenation evaporative condenser after passing through a waste heat heating water heat exchanger, and is cooled to 50-65 ℃ to respectively obtain cooling liquid and cooling gas;
cooling liquid enters a condensate storage tank, 10-25% of the cooling liquid in the condensate storage tank is introduced into a washing tower for circulation through a washing tower circulating pump, and the rest cooling liquid is conveyed to a hydrogenation material storage tank;
introducing the cooling gas into a hydrogenation gas heat exchanger for heat exchange, then introducing the cooling gas into a deep cold gas-liquid separator, and cooling the cooling gas to-20 to-50 ℃ by matching with a hydrogenation deep cooling condenser to obtain deep cooling liquid and deep cooling gas respectively, wherein the deep cooling liquid is introduced into a hydrogenation material storage tank, and the deep cooling gas is introduced into a hydrogen compressor for recycling;
introducing a condensate and a cryogenic liquid in the hydrogenated material storage tank into a disproportionation reaction system to prepare silane;
(5) and (2) feeding the residual liquid in the washing tower into a residual liquid evaporating pot, controlling the temperature of the residual liquid evaporating pot to be 50-200 ℃, carrying out heating separation to obtain solid slag and waste gas, recycling the solid slag, cooling the waste gas by a solid-liquid separation condenser to obtain condensed waste liquid and cooled waste gas, recycling the cooled waste gas, and introducing the obtained condensed waste liquid into a disproportionation reaction system to prepare the silane.
Preferably, the condensed residual liquid enters a residual liquid recovery storage tank and then enters a disproportionation reaction system through a hydrogenation material storage tank to prepare the silane.
Preferably, the silicon powder in the step (1) is mixed with waste slag, and the waste slag is collected from the bottom of the hydrogenation reactor.
Compared with the prior art, the invention discloses a tetrachlorosilane hydrogenation system and a method for preparing trichlorosilane, and the method has the following beneficial effects:
(1) according to the invention, the catalytic effect can be achieved by utilizing the metal chloride byproduct generated in the hydrogenation process of tetrachlorosilane, no additional catalyst is needed, the conversion rate can reach 25-28%, silicon powder is heated by hot hydrogen, the heated hydrogen is directly exhausted, and the process of uniformly mixing the silicon powder and the catalyst is omitted, so that the conversion rate of silicon tetrachloride and the quality of the product are improved, the expensive cost of the catalyst is saved, and the investment of equipment is reduced;
(2) according to the invention, the distribution plate in the hydrogenation reactor is utilized to uniformly distribute the mixed gas to the cross section of the whole reactor, and the metallurgical-grade silicon powder is kept in a fluidized state, so that the mixed gas can be fully contacted with the metallurgical-grade silicon powder, and the reaction efficiency is improved; and avoids the air current carrying silicon powder particles, reduces the erosion corrosion to the equipment cylinder and internal parts, and ensures that the primary conversion rate of the system is stabilized at 25-28% in the operation process;
(3) the invention sets up the cyclone separator on the hydrogenation reactor, the vapour gas mixture that entrains silicon powder and metal chloride from hydrogenation reactor enters the cyclone separator, the silicon powder of the larger granule in the gas is separated, store in the bottom of dust-collecting equipment of dry process, the bottom of cyclone separator is equipped with the communicating pipe leading to the middle part of hydrogenation reactor, equipped with the valve on the communicating pipe, the communicating pipe enters the middle part of reactor vertically, after the pressure equilibrium of the silicon powder collected in the dust-collecting equipment of dry process, enter the hydrogenation reactor directly through gravity and recycle; the large-particle silicon powder recovered from the cyclone separator directly enters the hydrogenation reactor and participates in the reaction, and the continuous and stable operation of the system is ensured;
(4) according to the invention, the chlorosilane mixed gas containing fine particle silicon powder and metal chloride, which is treated by the cyclone separator, is firstly introduced into the high-temperature gas-gas heat exchanger, and the high-temperature gas-gas heat exchanger is utilized to carry out heat exchange to heat the reaction raw material gas, so that the energy utilization efficiency can be improved; the gas is sent to the middle lower part of the scrubber, the chlorosilane mixed gas is depressurized and cooled, the chlorosilane mixed gas moves from bottom to top in the scrubber, the chlorosilane liquid is sprayed from top to bottom, the chlorosilane spraying liquid completely removes metal chlorides and fine silicon powder in the chlorosilane mixed gas when the temperature of the chlorosilane mixed gas is reduced, and a small amount of residual liquid containing solid matters generated in the scrubber is sent to a residual liquid treatment device; the scrubber makes full use of the jet principle, so that the temperature and pressure of the chlorosilane mixed gas are reduced to 175 ℃ below zero at 150 ℃ and 2.0-2.7MPa, and the reduction of the temperature and the pressure directly determines the precipitation of fine silicon powder and metal chloride.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic structural diagram provided by the present invention.
In the figure: 10 is a silicon powder storage tank, 11 is a silicon powder dense-phase pump, 12 is a silicon powder dryer, 13 is a silicon powder receiving tank, 14 is a silicon powder metering tank, 15 is a hydrogen heater, 16 is a tetrachlorosilane buffer tank, 17 is a silicon powder filter, 18 is a tetrachlorosilane transfer pump, 19 is a hydrogen compressor, 20 is a hydrogenated compressed hydrogen buffer tank, 21 is a tetrachlorosilane vaporizer, 22 is a high-temperature gas-gas heat exchanger, 23 is an electric heater, 24 is a hydrogenation reactor, 25 is a cyclone filter, 26 is a washing tower, 27 is a raffinate evaporator tank, 28 is a solid-liquid separation condenser, 29 is a raffinate recovery material storage tank, 30 is a washing tower reflux pump, 31 is a waste heat heating water heat exchanger, 32 is a hydrogenated condenser, 33 is a condensate storage tank, 34 is a hydrogenated gas heat exchanger, 35 is a deep cold gas-liquid separator, 36 is a hydrogenated cryogenic condenser, 37 is a hydrogenated material storage tank, 38 is a tetrachlorosilane superheater, 39 is a tetrachlorosilane preheater, 40 is a hydrogen superheater, 41 is a hydrogen preheater, 42 is a compressed hydrogen buffer tank, 43 is a first supplementary hydrogen buffer tank, 44 is a supplementary hydrogen compressor, 45 is a second supplementary hydrogen buffer tank, 46 is a silicon powder emergency receiving tank, 47 is an emergency discharge cooler, and 48 is an emergency discharge tank.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment 1 of the invention discloses a tetrachlorosilane hydrogenation system which is communicated with a disproportionation reaction system and comprises a silicon powder pretreatment unit, a tetrachlorosilane pressurization unit, a tetrachlorosilane heat exchange unit, a hydrogen pressurization unit, a hydrogen heat exchange unit, a vaporization heat exchange unit, a hydrogenation reaction unit, a dust removal unit and a condensation separation unit;
the downstream of the silicon powder pretreatment unit is communicated with a hydrogenation reaction unit;
the downstream of the tetrachlorosilane pressurizing unit is communicated with a tetrachlorosilane heat exchange unit, the downstream of the hydrogen pressurizing unit is communicated with a hydrogen heat exchange unit, and the tetrachlorosilane heat exchange unit and the hydrogen heat exchange unit are respectively communicated with the vaporization heat exchange unit;
the downstream of the vaporization heat exchange unit is communicated with the hydrogenation reaction unit, and the downstream of the hydrogenation reaction unit is communicated with the dust removal unit through the vaporization heat exchange unit;
the dust removal unit is communicated with the condensation separation unit through a tetrachlorosilane heat exchange unit and a hydrogen heat exchange unit.
For further optimizing the technical scheme, the silicon powder pretreatment unit comprises a silicon powder storage tank 1, a silicon powder dense-phase pump 2, a silicon powder dryer 12, a silicon powder receiving tank 13, a silicon powder metering tank 14, a hydrogen heater 15 and a silicon powder filter 17;
the top of the silicon powder storage tank 1 is provided with a silicon powder feeding port, the bottom of the silicon powder storage tank 1 is provided with a hydrogen inlet, and the bottom of the silicon powder storage tank 1 is connected with a silicon powder dense-phase pump 2;
the silicon powder dense-phase pump 2 is communicated with hydrogen, and the downstream of the silicon powder dense-phase pump 2 is communicated with a silicon powder dryer 12;
the silicon powder dryer 12 is communicated with the silicon powder receiving tank 13, the bottom of the silicon powder dryer 12 is connected with the hydrogen heater 15, and the hydrogen heater 15 is communicated with hydrogen;
the bottom of the silicon powder receiving tank 13 is communicated with a silicon powder metering tank 14, and the silicon powder metering tank 14 is communicated with the hydrogenation reaction unit;
the silicon powder dryer 12, the silicon powder receiving tank 13, and the silicon powder measuring tank 14 are respectively communicated with the outside through a silicon powder filter 17.
In order to further optimize the technical scheme, the tetrachlorosilane pressurizing unit comprises a tetrachlorosilane buffer tank 16 and a tetrachlorosilane conveying pump 18;
the upper stream of the tetrachlorosilane buffer tank 16 is connected with a disproportionation reaction system, and the lower stream is connected with a tetrachlorosilane transfer pump 18;
the downstream of the tetrachlorosilane delivery pump 18 is connected with a tetrachlorosilane heat exchange unit for communication;
the tetrachlorosilane heat exchange unit comprises a tetrachlorosilane superheater 38 and a tetrachlorosilane preheater 39;
the tetrachlorosilane superheater 38 is communicated with the tetrachlorosilane transfer pump 18 at the upstream and is communicated with the vaporization heat exchange unit at the downstream through a tetrachlorosilane preheater 39.
For further optimization, the hydrogen pressurizing unit comprises a hydrogen compressor 19 and a hydrogenated compressed hydrogen buffer tank 20;
the hydrogen compressor 19 is connected with the hydrogenated compressed hydrogen buffer tank 20, and the downstream of the hydrogenated compressed hydrogen buffer tank is communicated with the hydrogen heat exchange unit;
the hydrogen heat exchange unit comprises a hydrogen superheater 40 and a hydrogen preheater 41;
the hydrogen superheater 40 is communicated with the hydrogenated compressed hydrogen buffer tank 20 at the upstream and is communicated with the vaporization heat exchange unit at the downstream through a hydrogen preheater 41.
In order to further optimize the technical scheme, the vaporization heat exchange unit comprises a tetrachlorosilane vaporizer 21 and a high-temperature gas-gas heat exchanger 22;
the upstream of the tetrachlorosilane vaporizer 21 is respectively communicated with a tetrachlorosilane preheater 39 and a hydrogen preheater 41, and the downstream of the tetrachlorosilane vaporizer 21 is connected with the hydrogenation reaction unit through a high-temperature gas-gas heat exchanger 22.
In order to further optimize the technical scheme, the hydrogenation reaction unit comprises an electric heater 23, a hydrogenation reactor 24 and a cyclone filter 25, wherein the upstream of the electric heater 23 is connected with a high-temperature gas-gas heat exchanger 22, and the downstream of the electric heater is connected with the hydrogenation reactor 24;
the bottom of the hydrogenation reactor 24 is sequentially provided with a reaction air inlet, a feed inlet and a distribution plate from bottom to top, the reaction air inlet is connected with the electric heater 23 through a pipeline, the feed inlet is communicated with the silicon powder metering tank 14, and the distribution plate is horizontally arranged in the hydrogenation reactor 24;
the cyclone filter 25 is arranged on the top surface of the hydrogenation reactor 24 and is communicated with the hydrogenation reactor 24, and the downstream of the cyclone filter 25 is communicated with the dust removal unit through the high-temperature gas-gas heat exchanger 22.
For further optimizing the technical scheme, the dust removal unit comprises a washing tower 26, a raffinate evaporating tank 27, a solid-liquid separation condenser 28, a raffinate reclaimed material storage tank 29 and a washing tower reflux pump 30;
the bottom of the washing tower 26 is provided with a washing tower 26 air inlet and a washing tower 26 liquid outlet, the top of the washing tower 26 is provided with a washing tower 26 air outlet and a washing tower 26 liquid inlet, the washing tower 26 air inlet is communicated with the high-temperature gas-gas heat exchanger 22, the washing tower 26 liquid outlet is communicated with the raffinate evaporating tank 27, the washing tower 26 air outlet is communicated with the condensation separation unit sequentially through a hydrogen superheater 40, a hydrogen preheater 41, a tetrachlorosilane superheater 38 and a tetrachlorosilane preheater 39, and the liquid inlet is communicated with the condensation separation unit through a washing tower reflux pump 30;
the residual liquid evaporating pot 27 comprises a residual liquid pot liquid inlet, a residual liquid pot gas outlet, a steam inlet and a solid slag outlet; a residual liquid inlet and a residual liquid tank outlet are arranged at the top of the residual liquid evaporating pot 27, and a steam inlet is arranged on the side surface of the residual liquid evaporating pot 27; the solid slag outlet is arranged at the bottom of the residual liquid evaporating pot 27;
the chlorosilane gas outlet is communicated with a residual liquid reclaimed material storage tank 29 through a solid-liquid separation condenser 28; the raffinate recovery tank 29 is in communication with the condensate separation unit.
For further optimization of the technical scheme, the condensation separation unit comprises a waste heat heating water heat exchanger 31, a hydrogenation evaporative condenser 32, a condensate storage tank 33, a hydrogenation gas heat exchanger 34, a deep cold gas-liquid separator 35, a hydrogenation deep cold condenser 36 and a hydrogenation material storage tank 37;
the upstream of the waste heat heating water heat exchanger 31 is communicated with the air outlet of the washing tower 26 through a hydrogen superheater 40, a hydrogen preheater 41, a tetrachlorosilane superheater 38 and a tetrachlorosilane preheater 39, and the downstream of the waste heat heating water heat exchanger 31 is communicated with the hydrogenation evaporative condenser 32;
the hydrogenation evaporative condenser 32 is provided with an air outlet communicated with the hydrogen gas heat exchanger 34, and the hydrogenation evaporative condenser 32 is provided with a liquid outlet communicated with the condensate storage tank 33;
the downstream of the hydrogenation gas heat exchanger 34 is communicated with a deep cold gas-liquid separator 35;
the deep cold gas-liquid separator 35 is connected with a hydrogenation deep cold condenser 36, the liquid outlet of the deep cold gas-liquid separator 35 is communicated with a hydrogenation material storage tank 37, and the gas outlet of the deep cold gas-liquid separator 35 is communicated with the hydrogen compressor 19;
the downstream of the condensate storage tank 33 is communicated with a hydrogenation material storage tank 37, and the downstream of the hydrogenation material storage tank 37 is communicated with a disproportionation reaction system.
For further optimization, the system further comprises a compressed hydrogen buffer tank 42, a first supplementary hydrogen buffer tank 43, a supplementary hydrogen compressor 44 and a second supplementary hydrogen buffer tank 45;
the compressed hydrogen buffer tank 42 is connected with the recovered hydrogen at the upstream in sequence through a first supplementary hydrogen buffer tank 43, a supplementary hydrogen compressor 44 and a second supplementary hydrogen buffer tank 45, the vent of the hydrogenation gas heat exchanger 34 is connected at the upstream, the electrolyzed water is connected at the upstream to prepare hydrogen, and the hydrogen compressor 19 is connected at the downstream.
For further optimizing the technical scheme, the system also comprises a silicon powder emergency receiving tank 46, an emergency discharge cooler 47 and an emergency discharge tank 48;
the upper stream of the silicon powder emergency receiving tank 46 is communicated with the hydrogenation reactor 24, and the inside of the silicon powder emergency receiving tank 46 is connected with circulating cooling water;
the upstream of the emergency discharge cooler 47 is respectively connected with the tetrachlorosilane vaporizer 21 and the washing tower 26, the downstream is connected with the emergency discharge tank 48, and the inside of the emergency discharge cooler 47 is connected with circulating cooling water;
the downstream of the emergency discharge tank 48 is connected to a raffinate evaporating tank 27.
Examples 2 to 4
Embodiments 2 to 4 of the present invention provide a method for preparing trichlorosilane through hydrogenation of tetrachlorosilane, which employs the tetrachlorosilane hydrogenation system of embodiment 1, and specifically includes the following steps:
(1) the silicon powder is dried by the silicon powder dryer and then enters the silicon powder receiving tank, and then is put into the silicon powder metering tank for metering, and the metering is carried out through H2Pressurizing to 1.0-3.2MPaG and conveying to a hydrogenation reactor;
(2) the tetrachlorosilane is pressurized to 1.0-3.2MPaG after passing through a tetrachlorosilane transfer pump, is introduced into a tetrachlorosilane superheater and heated to 160 ℃ for 100-;
pressurizing hydrogen to 1.0-3.2MPaG through a hydrogen compressor and a hydrogenation compressed hydrogen buffer tank, then introducing into a hydrogen superheater and heating to 160 ℃ of temperature of 100-;
controlling H in mixed gas2And tetrachloroThe molar ratio of the silane is (1.5-3.5): 1, heating the mixed gas to 450 ℃ in a high-temperature gas-gas heat exchanger, heating to 600 ℃ in 450 ℃ by using an electric heater, and then feeding the mixed gas into a hydrogenation reactor;
(3) the mixed gas and the silicon powder continuously react in the hydrogenation reactor, the temperature of the hydrogenation reactor is controlled to be 480-580 ℃, the pressure is controlled to be 1.0-3.2MPaG, and the gas flow velocity in the hydrogenation reactor is controlled to be 0.4-0.8 m/S; the obtained high-temperature gas hydrogenation product is output after passing through a cyclone separator;
(4) the high-temperature gas hydrogenation product exchanges heat with the mixed gas of hydrogen and tetrachlorosilane through a high-temperature gas-gas heat exchanger, is cooled to 360 ℃ and is introduced into a washing tower;
washing the high-temperature gas product in a washing tower by using a chlorosilane solution, and cooling the washed gas to 100-200 ℃ through heat exchange with hydrogen and tetrachlorosilane respectively by using a hydrogen preheater, a hydrogen superheater, a tetrachlorosilane preheater and a tetrachlorosilane superheater;
then the waste heat heating water enters a hydrogenation evaporative condenser after passing through a waste heat heating water heat exchanger, and is cooled to 50-65 ℃ to respectively obtain cooling liquid and cooling gas;
cooling liquid enters a condensate storage tank, 10-25% of the cooling liquid in the condensate storage tank is introduced into a washing tower for circulation through a washing tower circulating pump, and the rest cooling liquid is conveyed to a hydrogenation material storage tank;
introducing the cooling gas into a hydrogenation gas heat exchanger for heat exchange, then introducing the cooling gas into a deep cold gas-liquid separator, and cooling the cooling gas to-20 to-50 ℃ by matching with a hydrogenation deep cooling condenser to obtain deep cooling liquid and deep cooling gas respectively, wherein the deep cooling liquid is introduced into a hydrogenation material storage tank, and the deep cooling gas is introduced into a hydrogen compressor for recycling;
introducing a condensate and a cryogenic liquid in the hydrogenated material storage tank into a disproportionation reaction system to prepare silane;
(5) and (2) feeding the residual liquid in the washing tower into a residual liquid evaporating pot, controlling the temperature of the residual liquid evaporating pot to be 50-200 ℃, carrying out heating separation to obtain solid slag and waste gas, recycling the solid slag, cooling the waste gas by a solid-liquid separation condenser to obtain condensed waste liquid and cooled waste gas, recycling the cooled waste gas, and introducing the obtained condensed waste liquid into a disproportionation reaction system to prepare the silane.
And the condensed residual liquid enters a residual liquid recovery storage tank and then enters a disproportionation reaction system through a hydrogenation material storage tank to prepare silane.
And (2) mixing the silicon powder with waste residues in the step (1), and collecting the waste residues from the bottom of the hydrogenation reactor.
The specific technical parameters of the implementation processes of the examples 2 to 4 are shown in the following table 1.
TABLE 1
The tetrachlorosilane hydrogenation system disclosed in example 1 adopts the methods disclosed in examples 2 to 4 to perform statistical operation on raw materials and products, and calculates the conversion rate of the raw materials, wherein the statistical time is shown in the following table 2.
TABLE 2
| Example 2 | Example 3 | Example 4 | |
| Feeding amount (Kg) of silica powder | 10368 | 31680 | 45849 |
| Tetrachlorosilane feed (Kg) | 754320 | 2262960 | 3128650 |
| Hydrogen gas feed quantity (Kg) | 1441 | 4510 | 6490 |
| Hydrogenation product (Kg) | 765600 | 2298000 | 3179520 |
| Trichlorosilane content (Kg) | 191400 | 602064 | 861645.6 |
| |
25％ | 26.2％ | 27.1％ |
The cost and energy consumption of preparing trichlorosilane from tetrachlorosilane by using the tetrachlorosilane hydrogenation system disclosed in example 1 and the methods disclosed in examples 2 to 4 are counted, and compared with the existing method, the results are shown in table 3 below.
TABLE 3
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A tetrachlorosilane hydrogenation system is communicated with a disproportionation reaction system and is characterized by comprising a silicon powder pretreatment unit, a tetrachlorosilane pressurization unit, a tetrachlorosilane heat exchange unit, a hydrogen pressurization unit, a hydrogen heat exchange unit, a vaporization heat exchange unit, a hydrogenation reaction unit, a dust removal unit and a condensation separation unit;
the downstream of the silicon powder pretreatment unit is communicated with the hydrogenation reaction unit;
the downstream of the tetrachlorosilane pressurizing unit is communicated with the tetrachlorosilane heat exchange unit, the downstream of the hydrogen pressurizing unit is communicated with the hydrogen heat exchange unit, and the tetrachlorosilane heat exchange unit and the hydrogen heat exchange unit are respectively communicated with the vaporization heat exchange unit;
the downstream of the vaporization heat exchange unit is communicated with the hydrogenation reaction unit, and the downstream of the hydrogenation reaction unit is communicated with the dust removal unit through the vaporization heat exchange unit;
the dust removal unit is communicated with the condensation separation unit through the tetrachlorosilane heat exchange unit and the hydrogen heat exchange unit.
2. The tetrachlorosilane hydrogenation system according to claim 1, wherein the silicon powder pretreatment unit comprises a silicon powder storage tank (1), a silicon powder dense-phase pump (2), a silicon powder dryer (12), a silicon powder receiving tank (13), a silicon powder metering tank (14), a hydrogen heater (15) and a silicon powder filter (17);
a silicon powder feeding port is formed in the top of the silicon powder storage tank (1), a hydrogen inlet is formed in the bottom of the silicon powder storage tank (1), and the bottom of the silicon powder storage tank (1) is connected with the silicon powder dense-phase pump (2);
the silicon powder dense-phase pump (2) is communicated with the hydrogen, and the downstream of the silicon powder dense-phase pump (2) is communicated with the silicon powder dryer (12);
the silicon powder dryer (12) is communicated with the silicon powder receiving tank (13), the bottom of the silicon powder dryer (12) is connected with the hydrogen heater (15), and the hydrogen heater (15) is communicated with hydrogen;
the bottom of the silicon powder receiving tank (13) is communicated with the silicon powder metering tank (14), and the silicon powder metering tank (14) is communicated with the hydrogenation reaction unit;
the silicon powder dryer (12), the silicon powder receiving tank (13) and the silicon powder metering tank (14) are respectively communicated with the outside through the silicon powder filter (17).
3. The tetrachlorosilane hydrogenation system of claim 2, wherein the tetrachlorosilane pressurization unit comprises a tetrachlorosilane buffer tank (16) and a tetrachlorosilane transfer pump (18);
the upper stream of the tetrachlorosilane buffer tank (16) is connected with the disproportionation reaction system, and the lower stream is connected with the tetrachlorosilane transfer pump (18);
the downstream of the tetrachlorosilane conveying pump (18) is connected with the tetrachlorosilane heat exchange unit for communication;
the tetrachlorosilane heat exchange unit comprises a tetrachlorosilane superheater (38) and a tetrachlorosilane preheater (39);
the tetrachlorosilane superheater (38) is communicated with the tetrachlorosilane conveying pump (18) at the upstream and is communicated with the vaporization heat exchange unit at the downstream through the tetrachlorosilane preheater (39).
4. The tetrachlorosilane hydrogenation system according to claim 3, wherein said hydrogen pressurization unit comprises a hydrogen compressor (19) and a hydrogenated compressed hydrogen buffer tank (20);
the hydrogen compressor (19) is connected with the hydrogenated compressed hydrogen buffer tank (20), and the downstream of the hydrogen compressor is communicated with the hydrogen heat exchange unit;
the hydrogen heat exchange unit comprises a hydrogen superheater (40) and a hydrogen preheater (41);
the hydrogen superheater (40) is communicated with the hydrogenated compressed hydrogen buffer tank (20) at the upstream and is communicated with the vaporization heat exchange unit at the downstream through the hydrogen preheater (41).
5. The tetrachlorosilane hydrogenation system of claim 4, wherein said vaporization heat exchange unit comprises a tetrachlorosilane vaporizer (21) and a high temperature gas-gas heat exchanger (22);
the upper stream of the tetrachlorosilane vaporizer (21) is respectively communicated with the tetrachlorosilane preheater (39) and the hydrogen preheater (41), and the lower stream of the tetrachlorosilane vaporizer (21) is connected with the hydrogenation reaction unit through the high-temperature gas-gas heat exchanger (22).
6. The tetrachlorosilane hydrogenation system according to claim 5, wherein the hydrogenation reaction unit comprises an electric heater (23), a hydrogenation reactor (24) and a cyclone filter (25), the electric heater (23) is connected with the high temperature gas-gas heat exchanger (22) at the upstream and the hydrogenation reactor (24) at the downstream;
the bottom of the hydrogenation reactor (24) is sequentially provided with a reaction air inlet, a feed inlet and a distribution plate from bottom to top, the reaction air inlet is connected with the electric heater (23) through a pipeline, the feed inlet is communicated with the silicon powder metering tank (14), and the distribution plate is horizontally arranged in the hydrogenation reactor (24);
the cyclone filter (25) is arranged on the top surface of the hydrogenation reactor (24) and is communicated with the hydrogenation reactor (24), and the downstream of the cyclone filter (25) is communicated with the dust removal unit through the high-temperature gas-gas heat exchanger (22).
7. The tetrachlorosilane hydrogenation system according to claim 6, wherein said dust-removing unit comprises a washing column (26), a raffinate evaporating tank (27), a solid-liquid separation condenser (28), a raffinate recovering tank (29) and a washing column reflux pump (30);
the bottom of the washing tower (26) is provided with a washing tower (26) air inlet and a washing tower (26) liquid outlet, the top of the washing tower (26) is provided with a washing tower (26) air outlet and a washing tower (26) liquid inlet, the washing tower (26) air inlet is communicated with the high-temperature gas-gas heat exchanger (22), the washing tower (26) liquid outlet is communicated with the raffinate evaporating tank (27), the washing tower (26) air outlet is communicated with the condensation separation unit through the hydrogen superheater (40), the hydrogen preheater (41), the tetrachlorosilane superheater (38) and the tetrachlorosilane preheater (39) in sequence, and the liquid inlet is communicated with the condensation separation unit through the washing tower reflux pump (30);
the residual liquid evaporating pot (27) comprises a residual liquid pot liquid inlet, a residual liquid pot gas outlet, a steam inlet and a solid slag outlet; the raffinate inlet and the raffinate outlet are arranged at the top of the raffinate evaporator (27), and the steam inlet is arranged on the side surface of the raffinate evaporator (27); the solid slag outlet is arranged at the bottom of the residual liquid evaporating pot (27);
the chlorosilane gas outlet is communicated with the residual liquid reclaimed material storage tank (29) through the solid-liquid separation condenser (28); and the residual liquid reclaimed material storage tank (29) is communicated with the condensation separation unit.
8. The tetrachlorosilane hydrogenation system according to claim 7, wherein said condensation separation unit comprises a waste heat warm water heat exchanger (31), a hydrogenation evaporative condenser (32), a condensate storage tank (33), a hydrogenation gas heat exchanger (34), a deep cold gas liquid separator (35), a hydrogenation cryogenic condenser (36) and a hydrogenation charge storage tank (37);
the upstream of the waste heat heating water heat exchanger (31) is communicated with the air outlet of the washing tower (26) through the hydrogen superheater (40), the hydrogen preheater (41), the tetrachlorosilane superheater (38) and the tetrachlorosilane preheater (39), and the downstream of the waste heat heating water heat exchanger (31) is communicated with the hydrogenation evaporative condenser (32);
the hydrogenation evaporative condenser (32) is provided with an air outlet communicated with the hydrogenation gas heat exchanger (34), and the hydrogenation evaporative condenser (32) is provided with a liquid outlet communicated with the condensate storage tank (33);
the hydrogenation gas heat exchanger (34) is communicated with the deep cold gas-liquid separator (35) at the downstream;
the deep cold gas-liquid separator (35) is connected with the hydrogenation deep cold condenser (36), a liquid outlet of the deep cold gas-liquid separator (35) is communicated with the hydrogenation material storage tank (37), and a gas outlet of the deep cold gas-liquid separator (35) is communicated with the hydrogen compressor (19);
the downstream of the condensate storage tank (33) is communicated with the hydrogenation material storage tank (37), and the downstream of the hydrogenation material storage tank (37) is communicated with the disproportionation reaction system.
9. A method for preparing trichlorosilane through hydrogenation of tetrachlorosilane, which is characterized by adopting the tetrachlorosilane hydrogenation system of any one of claims 1 to 8, and specifically comprises the following steps:
(1) the silicon powder is dried by a silicon powder dryer (12), enters a silicon powder receiving tank (13), is then put into a silicon powder metering tank (14) for metering, and passes through H2Pressurizing to 1.0-3.2MPaG, and conveying to a hydrogenation reactor (24);
(2) tetrachlorosilane is pressurized to 1.0 to 3.2MPaG after passing through a tetrachlorosilane transfer pump (18), is introduced into a tetrachlorosilane superheater (38) and heated to 160 ℃ of temperature of 100-;
the hydrogen is pressurized to 1.0-3.2MPaG through a hydrogen compressor (19) and a hydrogenation compression hydrogen buffer tank (20), then is introduced into a hydrogen superheater (40) and heated to 160 ℃ of temperature of 100-;
controlling H in mixed gas2The molar ratio of the tetrachlorosilane to the tetrachlorosilane is (1.5-3.5): 1, the mixed gas enters a high-temperature gas-gas heat exchanger (22) to be heated to the temperature of 250-The mixture is heated to 450-600 ℃ by an electric heater (23) and enters a hydrogenation reactor (24);
(3) the mixed gas and the silicon powder continuously react in the hydrogenation reactor (24), the temperature of the hydrogenation reactor (24) is controlled to be 480-580 ℃, the pressure is controlled to be 1.0-3.2MPaG, and the gas flow velocity in the hydrogenation reactor (24) is controlled to be 0.4-0.8 m/S; the obtained high-temperature gas hydrogenation product is output after passing through a cyclone separator;
(4) the high-temperature gas hydrogenation product exchanges heat with the mixed gas of hydrogen and tetrachlorosilane through a high-temperature gas-gas heat exchanger (22), is cooled to 250-360 ℃, and is introduced into a washing tower (26);
washing the high-temperature gas product with a chlorosilane solution in a washing tower (26), and cooling the washed gas to 100-200 ℃ through heat exchange with hydrogen and tetrachlorosilane respectively through a hydrogen preheater (41), a hydrogen superheater (40), a tetrachlorosilane preheater (39) and a tetrachlorosilane superheater (38);
then the waste heat heating water enters a hydrogenation evaporative condenser (32) after passing through a waste heat heating water heat exchanger (31) and is cooled to 50-65 ℃ to respectively obtain cooling liquid and cooling gas;
cooling liquid enters a condensate storage tank (33), 10-25% of the cooling liquid in the condensate storage tank (33) is introduced into a washing tower (26) through a circulating pump of the washing tower (26) for circulation, and the rest of the cooling liquid is conveyed to a hydrogenated material storage tank (37);
the cooling gas is introduced into a hydrogenation gas heat exchanger (34) for heat exchange, and then is introduced into a deep cold gas-liquid separator (35), and is cooled to-20 to-50 ℃ by matching with a hydrogenation deep cooling condenser (36) to respectively obtain deep cooling liquid and deep cooling gas, the deep cooling liquid is introduced into a hydrogenation material storage tank (37), and the deep cooling gas is introduced into a hydrogen compressor (19) for recycling;
introducing a condensate and a cryogenic liquid in the hydride storage tank (37) into a disproportionation reaction system to prepare silane;
(5) and (2) feeding the residual liquid in the washing tower (26) into a residual liquid evaporating pot (27), controlling the temperature of the residual liquid evaporating pot (27) to be 50-200 ℃, carrying out heating separation to obtain solid slag and waste gas, recycling the solid slag, cooling the waste gas by a solid-liquid separation condenser (28) to obtain condensed waste liquid and cooled waste gas, recycling the cooled waste gas, and introducing the obtained condensed waste liquid into a disproportionation reaction system to prepare the silane.
10. The method for preparing trichlorosilane through hydrogenation of tetrachlorosilane according to claim 9, wherein the silicon powder is mixed with the waste residue in step (1), and the waste residue is collected from the bottom of the hydrogenation reactor (24).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112158848A (en) * | 2020-08-24 | 2021-01-01 | 中国恩菲工程技术有限公司 | Silicon tetrachloride cold hydrogenation system |
| WO2022041699A1 (en) * | 2020-08-24 | 2022-03-03 | 中国恩菲工程技术有限公司 | Silicon tetrachloride cold hydrogenation system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730691A (en) * | 2012-07-10 | 2012-10-17 | 内蒙古盾安光伏科技有限公司 | Energy utilization in polysilicon hydrogenation process |
| KR20150108735A (en) * | 2013-01-27 | 2015-09-30 | 시 추 | The method and system for production of silicon and devicies |
| CN106629740A (en) * | 2016-12-29 | 2017-05-10 | 内蒙古盾安光伏科技有限公司 | Trichlorosilane cold hydrogenation production system and process |
| CN211496957U (en) * | 2019-12-13 | 2020-09-15 | 内蒙古兴洋科技有限公司 | Tetrachlorosilane hydrogenation system |
-
2019
- 2019-12-13 CN CN201911283979.7A patent/CN110980741A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730691A (en) * | 2012-07-10 | 2012-10-17 | 内蒙古盾安光伏科技有限公司 | Energy utilization in polysilicon hydrogenation process |
| KR20150108735A (en) * | 2013-01-27 | 2015-09-30 | 시 추 | The method and system for production of silicon and devicies |
| CN106629740A (en) * | 2016-12-29 | 2017-05-10 | 内蒙古盾安光伏科技有限公司 | Trichlorosilane cold hydrogenation production system and process |
| CN211496957U (en) * | 2019-12-13 | 2020-09-15 | 内蒙古兴洋科技有限公司 | Tetrachlorosilane hydrogenation system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112158848A (en) * | 2020-08-24 | 2021-01-01 | 中国恩菲工程技术有限公司 | Silicon tetrachloride cold hydrogenation system |
| WO2022041699A1 (en) * | 2020-08-24 | 2022-03-03 | 中国恩菲工程技术有限公司 | Silicon tetrachloride cold hydrogenation system |
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