CN102557041B - Method and device for continuous production of silicochloroform - Google Patents
Method and device for continuous production of silicochloroform Download PDFInfo
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- CN102557041B CN102557041B CN201010603418.3A CN201010603418A CN102557041B CN 102557041 B CN102557041 B CN 102557041B CN 201010603418 A CN201010603418 A CN 201010603418A CN 102557041 B CN102557041 B CN 102557041B
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Abstract
The invention discloses a method and a device for producing gaseous monosilane by reacting liquid silicon tetrachloride with hydrogen under high pressure. The method comprises the following steps of: under certain pressure, controlling the temperature to be above the boiling point of the silicon tetrachloride and below the boiling point of silicochloroform and reach a temperature suitable for reaction, reacting the hydrogen with the liquid silicon tetrachloride to produce gaseous silicochloroform, and continuously discharging the gaseous silicochloroform from a reactor. According to the method and the device, disclosed by the invention, the continuous operation of a process that the silicon tetrachloride is continuously converted into the silicochloroform at a lower temperature under normal pressure is achieved, the reaction temperature is lower, the conversion rate is higher, the energy consumption in production is little, no solid particles exist in a system, the damage to equipment is little, and the production cost of polycrystalline silicon and the maintenance cost of the equipment can be remarkably lowered.
Description
Technical field
The present invention relates to a kind of method and the device that utilize silicon tetrachloride production Trichloromonosilane, more particularly relate to a kind of method and the device that under elevated pressure conditions liquid silicon tetrachloride continuous hydrogenation are converted into Trichloromonosilane.
Background technology
At present, most method for preparing polysilicon is improvement Siemens process.The main drawback that this technique exists is: adopt Trichloromonosilane to be that raw material carries out polysilicon deposition, in reaction process, generate a large amount of silicon tetrachloride as by-product, if not recycle in addition, harm environment is caused great wastage of material, has a strong impact on production cost.The silicon tetrachloride recycle utilization of heavy industrialization is mainly cold hydrogenation and hot hydrogenation at present, and be approach silicon tetrachloride being converted into again raw material Trichloromonosilane, reaction equation is as follows.
Hot hydrogenation technology is using graphite or carbon composite as electric heating part in hot hydrogenation furnace, and pressure is 0.4 ~ 0.8MPa, and temperature is make hydrogen and silicon tetrachloride react the process generating Trichloromonosilane under the condition of 1200 ~ 1300 DEG C.The technical process of hot hydrogenation and equipment are all comparatively simple, scale of investment is less, but hot hydrogenation energy consumption is high, the current consumption of average production every kilogram Trichloromonosilane is generally not less than 3kWh, production of polysilicon total cost is made to be difficult to control, and very easily depositing silicon on electric heating part in hot hydrogenation furnace, cause heats to reduce, there is spark discharge damage equipment time more serious, reduce plant factor and add maintenance cost.Cold hydrogenation technology is that passing into hydrogen and silicon tetrachloride, is 2 ~ 4MPa at pressure using metallurgical grade silica flour as bed raw material in fluidized-bed reactor, and temperature is carry out reaction under the condition of 500 ~ 550 DEG C to generate Trichloromonosilane.Cold hydrogenation is produced Trichloromonosilane unit power consumption and is only 0.6 ~ 0.8kWh/kg, and single device treatment scale is comparatively large, and silicon tetrachloride per pass conversion can more than 25%.But cold hydrogenation process scheme is complicated, and facility investment is larger, and relate to the solid silica flour conveying under High Temperature High Pressure in system, due to silica flour extreme hardness, therefore very easily denude equipment, production line maintenance cost is higher and be difficult to ensure that long period is run continuously.
No matter prior art is hot hydrogenation or cold hydrogenation, is mainly the hydrogenation of silicon tetrachloride in gas phase.The reaction of hot hydrogenation and cold hydrogenation is reversible reaction, and reaction equilibrium constant is not high, and in gas-phase reaction, reactant is not separated with product, the product generated will affect the further reaction of reactant, and in gas phase, density of gas molecules is lower, and speed of reaction is difficult to improve.
On the reaction mechanism basis that have studied silicon tetrachloride and hydrogen, the present invention proposes and utilize hydrogen and liquid silicon tetrachloride to react the method generating Trichloromonosilane.Can under the temperature condition of forward movement at hydrogenation of silicon tetrachloride molecular balance, utilize suitable pressure, make silicon tetrachloride be in liquid state and ensure the boiling point of temperature lower than Trichloromonosilane under this pressure, hydrogen and silicon tetrachloride react the Trichloromonosilane generated and constantly vaporize and leave reactive system, impel reaction to carry out to the positive reaction direction generating trichlorosilane all the time.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of by liquid silicon tetrachloride continuously and hydrogen reaction
Produce the method for Trichloromonosilane, by hydrogen being passed into liquid silicon tetrachloride under high pressure and certain temperature condition, the method is undertaken reacting that the mode generating gaseous state Trichloromonosilane realizes on a large scale, low cost, energy-efficient hydrogenation of silicon tetrachloride conversion production Trichloromonosilane.
The technical problem that the present invention also will solve is to provide the device realizing aforesaid method.
For solving the problems of the technologies described above, the present invention adopts technical scheme as follows:
A kind of method of continuous production of silicochloroform, what be included in sealing is equipped with in the reactor of liquid silicon tetrachloride, under certain temperature and pressure, pure hydrogen is passed into liquid silicon tetrachloride reaction to generate Trichloromonosilane and hydrogen chloride gas and discharge reactor, and constantly in reactor, supplement liquid silicon tetrachloride, reaction is carried out continuously.
Wherein, described closed reactor internal pressure is 20 ~ 35MPa, is preferably 23 ~ 28MPa.
Wherein, in described closed reactor, temperature is 380 ~ 550 DEG C, is preferably 400 ~ 450 DEG C.
Wherein, described hydrogen is 2 ~ 5: 1 with the reaction volume ratio of silicon tetrachloride unstripped gas.
Wherein, described hydrogen is heated to 300 ~ 600 DEG C and passes into reactor.
Wherein, described liquid silicon tetrachloride is heated to 300 ~ 500 DEG C and passes into reactor.
Wherein, catalyzer can be added in described closed reactor.Further, described catalyzer is one or more in metal chloride and ionic liquid, is preferably alkaline earth metal chloride and ionic liquid, particularly preferably bariumchloride and Repone K is dissolved in ionic liquid and makes catalyzer.
In a preferred production method, be under 23 ~ 25MPa by pressure and the liquid silicon tetrachloride being heated to 300 ~ 350 DEG C to pass in reactor from described silicon tetrachloride feeding pipe and passes in reactor by described catalyzer by described catalyst addition tube; The hydrogen being heated to 300 ~ 400 DEG C is passed in reactor by Hydrogen distribution device described in described hydrogen gas Guan Jing, after for some time, the heating unit of reactor is started after stablizing until pressure reduction between hydrogen gas pipe and products export, be warming up to 400 ~ 450 DEG C, pass into hydrogen continuously, and the mixed gas of product Trichloromonosilane and hydrogen, hydrogenchloride and a small amount of silicon tetrachloride is discharged by products export, can continuous seepage.
The invention still further relates to a kind of device of continuous production of silicochloroform, comprise housing 1, Hydrogen distribution device 3, hydrogen gas pipe 4, silicon tetrachloride feeding pipe 5, products export 6 and catalyst addition tube 7; Housing 1 is closed pressure vessel, housing 1 top connects hydrogen gas pipe 4, silicon tetrachloride feeding pipe 5, products export 6 and catalyst addition tube 7, it is inner that silicon tetrachloride feeding pipe 5 stretches into housing 1, it is characterized in that housing 1 inside is also provided with Hydrogen distribution parts, and described Hydrogen distribution parts are connected with described hydrogen gas pipe 4.In this device, described housing preferably has liner, and material is high hardness alloy.
Wherein, described Hydrogen distribution parts are Hydrogen distribution device 3, and its surface is provided with uniform some pores 301.Further, described Hydrogen distribution device 3 has the diameter of expansion, and the pore direction of described Hydrogen distribution device down.Further, the bottom surface of described Hydrogen distribution device 3 bottom expanding reach is preferably located in reactor height overall 1/3rd and sentences down.
Wherein, described Hydrogen distribution parts are hydrogen nozzle 8.
Wherein, described housing 1 bottom also comprises magnetic stirrer 9.
Wherein, described housing is high pressure vessel, and is provided with electric heating part or heat-conducting oil heating chuck.
Wherein, described closed reactor is preferably cylindrical structural, and liquid silicon tetrachloride filling liquid level is no more than reactor 2/3rds height.
Beneficial effect
According to the method for continuous production of silicochloroform of the present invention, temperature of reaction all lower than existing hydrogenation technology, reduces energy consumption of reaction.
According to the method for continuous production of silicochloroform of the present invention, change the reactive mode of hydrogenation of silicon tetrachloride, become liquid phase reaction from gas-phase reaction, and product Trichloromonosilane leaves reactive system after generating immediately, advances molecular balance and moves to positive reaction direction and accelerate speed of reaction.
According to the method for continuous production of silicochloroform of the present invention, without solid particulate in system, reduce the risk of equipment damage.
Accompanying drawing explanation
Fig. 1 is a kind of device schematic diagram that Trichloromonosilane is produced in liquid silicon tetrachloride hydrogenation of the present invention.Wherein, 1 housing, 2 liquid silicon tetrachlorides, 3 Hydrogen distribution devices, 4 hydrogen gas pipes, 5 silicon tetrachloride feeding pipes, 6 products exports, 7 catalyst addition tube.
Fig. 2 is the another kind of device schematic diagram that Trichloromonosilane is produced in liquid silicon tetrachloride hydrogenation of the present invention.Wherein, 8 hydrogen nozzles, 9 magnetic stirrers.
Embodiment
Also by reference to the accompanying drawings the production method in the present invention and device are described in detail below by way of specific embodiment, but these embodiments are only illustrative objects, are not intended to carry out any restriction to scope of the present invention.
Embodiment 1:
It is the schematic diagram of the process of a kind of optimization of liquid silicon tetrachloride hydrogenation of the present invention production Trichloromonosilane see Fig. 1, Fig. 1.It comprises housing 1, liquid silicon tetrachloride 2, Hydrogen distribution device 3, hydrogen gas pipe 4, silicon tetrachloride feeding pipe 5, products export 6 and catalyst addition tube 7.
Housing 1 top connects hydrogen gas pipe 4, silicon tetrachloride feeding pipe 5, products export 6 and catalyst addition tube 7; Hydrogen gas pipe 4 connects Hydrogen distribution device 3, and it is inner that Hydrogen distribution device 3 is located at housing 1.Nitrogen pressure being about 25MPa is filled with in housing 1 and carries out reactor displacement, after having replaced, pressure is not less than 25MPa and the liquid silicon tetrachloride 2 being heated to 350 ~ 380 DEG C passes in housing 1 by silicon tetrachloride feeding pipe 5, until liquid level reaches about 2/3rds places of housing 1 height, bariumchloride will be adopted, the catalyzer of Repone K and ionic liquid synthesis passes in housing 1 by catalyst addition tube 7, pressure is about 25MPa, the pure hydrogen being heated to about 400 DEG C by hydrogen gas pipe 4 via Hydrogen distribution device 3, spray into downwards below liquid silicon tetrachloride 2 liquid level in liquid silicon tetrachloride 2, after stable to pressure reduction between hydrogen gas pipe 4 import and products export 6, electric heating part is adopted to heat housing 1, also holding temperature is stable to make liquid silicon tetrachloride 2 be warming up to 410 DEG C, keep pressure-stabilisation at 25MPa, continue to pass into quantitative pure hydrogen, liquid silicon tetrachloride 2 liquid level decline 5% time by silicon tetrachloride feeding pipe 5 in housing 1 supplement liquid silicon tetrachloride 2 to initial level, the mixed gas got rid of by products export 6 comprises product Trichloromonosilane gas, hydrogen, hydrogenchloride and micro-silicon tetrachloride gas, can obtain product Trichloromonosilane, hydrogen reusable edible through being separated.
Employing diameter is 0.5m, the cylindrical reactor housing of high 1.2m, and the electric heater unit configuring that rated output is 50kW, reaction parameter is as follows:
1) hydrogen flowing quantity is about 26kg/h;
2) silicon tetrachloride magnitude of recruitment is about 45kg/h
3) continuous seepage 100 hours, consume silicon tetrachloride and be about 4500kg, separation obtains product Trichloromonosilane and is about 3300kg, and total power consumption is about 3000kWh, and the mean unit power consumption producing trichlorosilane is about 0.91kWh/kg.
Embodiment 2
See Fig. 2, with enforcement 1 unlike the Hydrogen distribution device replaced with hydrogen nozzle in embodiment 1, and adopt magnetic stirrer fully to be stirred, final separation obtains product Trichloromonosilane and is about 3235kg, total power consumption is about 3397kWh, and the mean unit power consumption producing trichlorosilane is about 1.05kWh/kg.
In above-described embodiment, utilize silicon tetrachloride to generate Trichloromonosilane with hydrogen reaction under high-pressure liquid condition, temperature of reaction is lower, energy consumption is lower, and equipment is simple and separate unit reaction unit treatment capacity is large, and medium is without solid particulate, can ensure long period continuous seepage, comprehensive cost significantly reduces.
Although give detailed description and explanation to the specific embodiment of the present invention above; but what should indicate is; various equivalence can be carried out according to conception of the present invention to above-mentioned embodiment to change and amendment; its function produced do not exceed that specification sheets and accompanying drawing contain yet spiritual time, all should within protection scope of the present invention.
Claims (14)
1. the method for a continuous production of silicochloroform, what be included in sealing is equipped with in the reactor of liquid silicon tetrachloride, under certain temperature and pressure, pure hydrogen is passed into liquid silicon tetrachloride and reacts, reaction generates Trichloromonosilane and hydrogen chloride gas discharges reactor, and constantly in reactor, supplement liquid silicon tetrachloride, make the step that reaction is carried out continuously, wherein:
Closed reactor internal pressure is 20 ~ 35MPa;
In closed reactor, temperature is 380 ~ 550 DEG C;
Described hydrogen is 2 ~ 5:1 with the reaction volume ratio of silicon tetrachloride.
2. the method for production Trichloromonosilane according to claim 1, is characterized in that closed reactor internal pressure is 23 ~ 28MPa.
3. the method for production Trichloromonosilane according to claim 1, is characterized in that in closed reactor, temperature is 400 ~ 450 DEG C.
4. the method for production Trichloromonosilane according to claim 1, is characterized in that described hydrogen is heated to 300 ~ 600 DEG C and passes into reactor.
5. the method for production Trichloromonosilane according to claim 1, is characterized in that described liquid silicon tetrachloride is heated to 300 ~ 500 DEG C and passes into reactor.
6. the method for production Trichloromonosilane according to claim 1, is characterized in that adding catalyzer in described closed reactor.
7. method according to claim 6, is characterized in that described catalyzer is one or more in metal chloride and ionic liquid.
8. method according to claim 7, is characterized in that described catalyzer is alkaline earth metal chloride and ionic liquid.
9. realize a device for the method for any one of claim 1-8 continuous production of silicochloroform, comprise housing (1), hydrogen gas pipe (4), silicon tetrachloride feeding pipe (5), products export (6) and catalyst addition tube (7); Housing (1) is closed pressure vessel, housing (1) top connects hydrogen gas pipe (4), silicon tetrachloride feeding pipe (5), products export (6) and catalyst addition tube (7), it is inner that silicon tetrachloride feeding pipe (5) stretches into housing (1), it is characterized in that housing (1) inside is also provided with Hydrogen distribution parts, and described Hydrogen distribution parts are connected with described hydrogen gas pipe (4).
10. device according to claim 9, it is characterized in that described Hydrogen distribution parts are Hydrogen distribution device (3), its surface is provided with uniform some pores (301).
11. devices according to claim 10, it is characterized in that described Hydrogen distribution device (3) has the diameter of expansion, the pore direction of described Hydrogen distribution device down.
12. devices according to claim 9, is characterized in that described Hydrogen distribution parts are hydrogen nozzle (8).
13. according to claim 9-11 the device of any one, it is characterized in that described housing (1) bottom also comprises magnetic stirrer (9).
14. devices according to claim 9, is characterized in that described housing is high pressure vessel, and are provided with electric heating part or heat-conducting oil heating chuck.
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| CN201010603418.3A CN102557041B (en) | 2010-12-24 | 2010-12-24 | Method and device for continuous production of silicochloroform |
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| CN201010603418.3A CN102557041B (en) | 2010-12-24 | 2010-12-24 | Method and device for continuous production of silicochloroform |
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| CN106276917B (en) * | 2015-05-28 | 2019-01-22 | 内蒙古盾安光伏科技有限公司 | Polysilicon production process and system |
| CN106276918A (en) * | 2015-05-28 | 2017-01-04 | 内蒙古盾安光伏科技有限公司 | Polysilicon production process and system |
| CN105000564B (en) * | 2015-07-17 | 2020-05-26 | 江苏中能硅业科技发展有限公司 | Production method of dichlorosilane for preparing silane |
| CN105060297B (en) * | 2015-07-28 | 2017-09-12 | 吴联凯 | A kind of method and device for producing silicochloroform |
| CN113387362B (en) * | 2021-05-08 | 2022-11-29 | 内蒙古新特硅材料有限公司 | Improved method and device for synthesizing trichlorosilane by cold hydrogenation |
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| CN201372206Y (en) * | 2009-02-27 | 2009-12-30 | 比亚迪股份有限公司 | Facility for preparing trichlorosilane by silicon tetrachloride |
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| CN201372206Y (en) * | 2009-02-27 | 2009-12-30 | 比亚迪股份有限公司 | Facility for preparing trichlorosilane by silicon tetrachloride |
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Effective date of registration: 20170803 Address after: 831800 the Xinjiang Uygur Autonomous Region Hui Autonomous Prefecture of Changji economic and Technological Development Zone East Red Sand Springs North Industrial Zone, four Cross Road East Patentee after: Xinjiang GCL new energy Mstar Technology Ltd Address before: 221004 Xuzhou Economic Development Zone, Jiangsu, Yang Road, No. 66 Patentee before: Jiangsu Zhongneng Polysilicon Technology Development Co., Ltd. |
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