CN101798085B - Process for preparing silane by magnesium silicide method - Google Patents
Process for preparing silane by magnesium silicide method Download PDFInfo
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- CN101798085B CN101798085B CN201010151496A CN201010151496A CN101798085B CN 101798085 B CN101798085 B CN 101798085B CN 201010151496 A CN201010151496 A CN 201010151496A CN 201010151496 A CN201010151496 A CN 201010151496A CN 101798085 B CN101798085 B CN 101798085B
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Abstract
The invention discloses a continuous production method for silane by a magnesium silicide method, which comprises the following steps of: preparing solid ammonium chloride and liquid ammonia into an ammonium chloride-liquid ammonia solution; carrying out addition or grading limit continuous addition of the solution and a magnesium silicide solid from the first stage of a multistage series connection silane generator; stirring and cooling all stages of the silane generator; leading the silane which is continuously generated by all stages of the silane generator to enter a silane buffer tank by all stages of washing tower and condensers for collecting; and returning the liquid ammonia formed by condensing the ammonia carried by a silane gas through a condenser to all stages of the silane generator by the washing towers and simultaneously washing impurities, such as borane in the silane and the like, by the returned liquid ammonia. The method continuously generates the silane at multiple stages by adopting continuous feed, and the reaction temperature at each stage is subjected to stepped type adjustment and control, therefore, the invention has stable silane gas quantity, mild reaction condition, high safety, high yield, few impurity and low cost and meets the requirement of green manufacturing.
Description
Technical field
The invention belongs to field of polysilicon technology, relate to a kind of preparation technology of silane, relating in particular to a kind of is the improvement technology of the preparation silane of raw material with the magnesium silicide.
Background technology
Silane (SiH
4) be widely used in the epitaxial deposition monocrystalline silicon membrane and produce polysilicon film, make the photosensitive part of non-crystal silicon solar cell and duplicating machine, replace traditional toner cartridge with the silicon drum, and in glass industry, be used to produce cranberry glass.In high-tech area, silane and ethene can generate the silicon carbide super powder under laser active, and silane and ammonia can generate the ultrafine powder of silicon nitride end under laser active.Along with the fast development of photovoltaic industry, domestic silane demand increases rapidly simultaneously.
Producing silane method at present mainly contains: magnesium silicide ammonolysis process (abbreviation magnesium silicide method), chlorosilane discrimination method (also claiming the UCC method) and silicon fluoride hydride process (also claiming the ETHYL method).The method that magnesium silicide prepares silane is early stage a kind of working method of commonplace employing in the world, is replaced by additive method gradually afterwards.In domestic generation nineteen sixty, succeeded in developing magnesium silicide method and technology route, and domestic present still magnesium silicide method is occupied an leading position.The ultimate principle that magnesium silicide method is produced silane is: with magnesium silicide and ammonium chloride is raw material, is reaction medium with the liquid ammonia, and reaction generates silane and magnesium chloride hex-ammoniate.This method has that the silane productive rate is high, reaction raw materials is easy to get, simple to operate, advantage such as the temperature and pressure processing condition reach easily.There is the obvious deficiency of following several respects in the preparation method of existing silane by magnesium silicide method because many-sided factors such as technology and safety adopt periodical operation on a small scale basically:
1) air output is unstable in the silane generating process, and is high to operator and equipment requirements, poor stability;
2) the rhythmic reaction time is generally 24h, and productive rate has only 70%, and production capacity is low, has increased production cost;
3) temperature of reaction of silane generation is generally selected-40～-80 ℃, and so the cooling of coldcondition reaction pair refrigerant requires height, has increased energy consumption;
4) directly entering silane refining step of back takes place in silane, and it is big to carry the liquefied ammonia amount secretly, has increased the purification difficulty;
5) leakage of periodical operation liquefied ammonia is more, and environmental pollution is serious.
Summary of the invention
The objective of the invention is deficiencies such as the existing labour intensity of existing magnesium silicide method small-scale batch production silane is big, poor stability, productive rate is low, energy consumption is high, environmental pollution is serious in order to solve; A kind of method of magnesium silicide method continuous production silane is provided, and it comprises the steps:
It is 1%～40% ammonium chloride solution ammonia solution that solid ammonium chloride and liquefied ammonia are mixed with massfraction; The ammonium chloride solution ammonia solution for preparing and magnesium silicide solid are added by the first step of plural serial stage silane generator or classification addings of limiting the quantity of continuously, and magnesium silicide and ammonium chloride raw material totally mol ratio are 1: 1～8; Silane generators at different levels are stirred and cool off, and the temperature of reaction of silane generators at different levels is-60～30 ℃, and reaction pressure is 0.1～1.5MPa, and the reaction mass residence time is 1～12h; The silane that silane generators at different levels recur gets into the silane surge tank and collects via washing tower, condensing surface; The liquefied ammonia of the ammonia that silane gas is taken out of after condenser condenses returns silane generator by washing tower, and the liquefied ammonia that returns washs the impurity such as borine in the silane simultaneously.
Preferred 2～4 grades of described plural serial stage silane generator, preferably 3 grades or 4 grades.When being less than 3 grades, the reaction times prolongs, and productive rate descends, and during more than 4 grades, though operation more tends to safety, stable, has the shortcoming that plant investment is big, floor space is big, energy consumption is high.The form of silane generator is generally reaction kettle.
The massfraction of said preparation ammonium chloride solution ammonia solution is 1%～40%, preferred 10%～30%.Ammonium chloride concentration is low excessively, and speed of response is slow, is unfavorable for the raising of production capacity; And excessive concentration, the contact of solid-liquid material is bad, and speed of response is also had very big influence.
In the reaction process, magnesium silicide and ammonium chloride raw material accumulative total mol ratio is generally 1: 1～and 8, be 1: 4～6 to feed intake preferably by the accumulative total mol ratio.The stoichiometric of magnesium silicide and ammonium chloride reaction is 1: 4, and the ammonium chloride proportioning is low excessively, and the magnesium silicide reaction not exclusively; Proportioning is too high, and the ammonium chloride raw materials cost obviously increases.
In a kind of preferred embodiment, ammonium chloride solution ammonia solution for preparing and magnesium silicide add silane generator with pump and screw feeder metering respectively continuously.
When adopting 3 grade silane producer operate continuouslys, along with the continuous adding of reaction raw materials, the material in the first step silane generator is imported second, third grade silane producer successively through pump, carries out successive silane and reacts.The 3 grade silane producer reaction mass residence time were 1～12h, preferred 3～8h.
Placed in-line silane generator at different levels can adopt the uniform operation temperature and pressure, also can adopt different temperature and pressure; The preferred productive rate of operating method that adopts temperature of reaction to improve step by step to guarantee that silane takes place.
When adopting 3 grades to operate continuously; Come fast reaction speed through the differential responses temperature controlling; Guarantee the complete of magnesium silicide reaction; First, second and third grade silane generator temperature is controlled at respectively in-60～-10 ℃ ,-40～10 ℃ ,-20～30 ℃ scopes, preferred-50～-20 ℃ ,-30～0 ℃ ,-10～20 ℃.The concentration of raw material is higher in the first step producer, and speed of response is very fast, controls lower temperature and helps controlling steadily carrying out that silane reacts, along with the carrying out of reaction progressively improved temperature of reaction and make raw material complete reaction fast.The pressure of silane generators at different levels is 0.1～1.5MPa, preferred 0.3～1.0MPa, this mainly be because ammonia under existing temperature condition, 0.3～1.0MPa relative volatility is less, can effectively reduce the area of condensing surface, thereby reduces investment cost.
When liquefied ammonia returns silane generator by washing tower, can the impurity such as borine in the silane be washed, reduce the content of impurity in the silane, can reduce silane purified difficulty.
The continuous extraction of magnesium chloride hex-ammoniate suspension-s of last step silane generator is pending to the buffer suspension jar.
Foregoing invention is based on such thinking proposition: the serialization preparation of ammonium chloride solution ammonia solution can reduce labour intensity greatly, increases work efficiency, and has reduced the pollution of batching simultaneously; Magnesium silicide adds the silane generator reaction simultaneously with ammonium chloride solution can make the solid-liquid material better contact, thereby has improved speed of response, has improved working efficiency and production capacity.
In addition, SV has been installed in many places in this tooling, has further strengthened safe safety.Particularly, guarantee the safe operation that silane takes place through SV all being installed at silane generators at different levels.
The inventive method has following advantage:
1) adopt continuously feeding, multistagely recur silane, and every grade temperature of reaction is carried out the staged regulation and control; Therefore silane tolerance is stable, and not high to operator and equipment requirements, security is good; SV has been installed in many places in this tooling simultaneously, has further strengthened safe safety;
2) adopt continous batching, reinforced, silane takes place, silane is collected and the extraction of magnesium chloride hex-ammoniate suspension-s, productive rate can reach 95%, has improved production capacity, has reduced production cost;
3) temperature of reaction of silane generation is controlled at-60～30 ℃, reaction pressure 0.1～1.5MPa, and reaction conditions comparatively relaxes, and is less demanding to the refrigerant cooling;
4) silane takes place impurity such as borine wherein effectively to be removed after washed by the liquefied ammonia washing tower, and condensing surface can reduce impurity and the liquefied ammonia in the silane with returning in the silane generator after most ammonia condensations simultaneously, greatly reduces the purification difficulty;
5) silane takes place to adopt continuous operation, does not have liquefied ammonia to leak basically, meets the requirement of green manufacturing.
Description of drawings
Fig. 1 is the process flow sheet of the preferred 3 grade silane producers series connection of the present invention serialization silane preparation.
1-ammonium chloride header tank; 2-ammonium chloride feeder; 3-ammonium chloride batching still; 4-cold liquid ammonia condenser; 5-ammonium chloride solution transferpump; 6-magnesium silicide header tank; 7-magnesium silicide feeder; 8,12,16-silane generator; 9,13,17-silane generation condensing surface; 10,14,18-washing tower; 11,15,19-suspension-s extraction pump; 20,21,22-SV.
Embodiment
Mode below in conjunction with accompanying drawing and embodiment is further explained the present invention, but the present invention is not limited to these embodiment.Except as otherwise noted, wherein " part " or " % " is " mass parts " or " quality % ".
The preparation of embodiment 13 grade silane producers series connection serialization silane
Silane carries out gas displacement with nitrogen to whole reaction system before taking place, and the replacement of oxygen in the reaction system is clean;
Replacement of oxygen is finished; With liquefied ammonia with per hour 80 parts by surge tank squeeze into the batching still 3 in; The ammonia of vaporization returns batching still 3 after via condensing surface 4 condensations, ammonium chloride with per hour 20 parts add in the batching stills 3 through screw feeder 2 by header tank 1, be mixed with 20% ammonium chloride solution ammonia solution;
The ammonium chloride solution ammonia solution for preparing through pump 5 with 100 parts of input first step silane generators 8 per hour; Simultaneously the magnesium silicide in the magnesium silicide header tank 6 is continuously added reaction in the first step silane generator 8 with per hour 6.9 parts (mol ratio of magnesium silicide and ammonium chloride is 1: 4.1) through magnesium silicide screw feeder 7; Wherein temperature is-30 ℃; Pressure is 0.6MPa, and the silane of generation gets into the silane surge tank through washing tower 10, condensing surface 9;
The feed liquid of complete reaction is not via the 12 continuation reactions of pump 11 input second stage silane generators in the first step silane generator 8, and wherein temperature is-10 ℃, and pressure is 0.6MPa, and the silane of generation gets into the silane surge tanks through washing tower 14, condensing surface 13;
In the second stage silane generator 12 not the feed liquid of complete reaction continue reaction via pump 15 input third stage silane generators 16; Wherein temperature is 10 ℃; Pressure is 0.6MPa; The silane that takes place gets into the silane surge tank through washing tower 18, condensing surface 17, and the magnesium chloride hex-ammoniate liquefied ammonia suspension-s that reacts completely is via pump 19 input suspension-s surge tanks.
The productive rate of the relative magnesium silicide of the finished product silane is 93.1%.
Embodiment 2
Technical process is with embodiment 1, just with liquefied ammonia among the embodiment 1 per hour add-on change 106.7 parts (are mixed with 15% ammonium chloride solution ammonia solution) into by 80 parts, other conditions are constant.The productive rate of the relative magnesium silicide of the finished product silane is 92.6%.
Embodiment 3
Technical process is with embodiment 1, just with liquefied ammonia among the embodiment 1 per hour add-on change 64 parts (are mixed with 25% ammonium chloride solution ammonia solution) into by 80 parts, other conditions are constant.The productive rate of the relative magnesium silicide of the finished product silane is 95.2%.
Embodiment 4
Technical process is with embodiment 1, just with magnesium silicide among the embodiment 1 per hour add-on change 6.3 parts (mol ratio of magnesium silicide and ammonium chloride is 1: 4.5) into by 6.9 parts, other conditions are constant.The productive rate of the relative magnesium silicide of the finished product silane is 94.0%.
Embodiment 5
Technical process is with embodiment 1, just with magnesium silicide among the embodiment 1 per hour add-on change 5.7 parts (mol ratio of magnesium silicide and ammonium chloride is 1: 5) into by 6.9 parts, other conditions are constant.The productive rate of the relative magnesium silicide of the finished product silane is 94.9%.
Embodiment 6
Technical process is just changed into-40 ℃ ,-20 ℃, 0 ℃ respectively with 3 grade silane generator temperatures among the embodiment 1 with embodiment 1, and other conditions are constant.The productive rate of the relative magnesium silicide of the finished product silane is 90.1%.
Embodiment 7
Technical process is just changed into 0.5MPa with 3 grade silane producer reaction pressures among the embodiment 1 with embodiment 1, and other conditions are constant.The productive rate of the relative magnesium silicide of the finished product silane is 93.9%.
Embodiment 8
Technical process is just changed into 0.7MPa with 3 grade silane producer reaction pressures among the embodiment 1 with embodiment 1, and other conditions are constant.The productive rate of the relative magnesium silicide of the finished product silane is 91.9%.
Embodiment 9
Technical process is just changed into first step 0.7MPa, second stage 0.6MPa and third stage 0.5MPa respectively with 3 grade silane producer reaction pressures among the embodiment 1 with embodiment 1, and other conditions are constant.The productive rate of the relative magnesium silicide of the finished product silane is 94.9%.
The preparation of embodiment 10 2 grade silane producers series connection serialization silane
Third stage reactor drum cancellation with in the generation of 3 grade silanes among the embodiment 1 changes 2 grade silanes into and takes place, and other reaction conditionss are constant.The productive rate of the relative magnesium silicide of the finished product silane is 89.9%.
The preparation of embodiment 11 3 grade silane producers series connection serialization silane
Change 3 grade silane producers among the embodiment 1 into 4 grade silane producers, wherein fourth stage silane generator temperature of reaction is 20 ℃, and pressure is 0.6MPa, and other reaction conditionss are constant.The productive rate of the relative magnesium silicide of the finished product silane is 93.9%.
The reinforced serialization silane preparation of embodiment 12 3 grade silane producer classifications
With the per hour 6.9 parts of all adding first step silane generator reactions of per hour 100 parts of the ammonium chloride solution ammonia solutions for preparing among the embodiment 1, magnesium silicide; Change into to first step silane generator and per hour add 70 parts of ammonium chloride solutions, 4.5 parts of magnesium silicides; Per hour add per hour 2.4 parts of 30 parts of ammonium chloride solutions, magnesium silicides to second stage silane generator simultaneously, other reaction conditionss are constant.The productive rate of the relative magnesium silicide of the finished product silane is 94.2%.
The reinforced serialization silane preparation of embodiment 13 3 grade silane producer classifications
With the per hour 6.9 parts of all adding first step silane generator reactions of per hour 100 parts of the ammonium chloride solution ammonia solutions for preparing among the embodiment 1, magnesium silicide; Change into to first step silane generator and per hour add 60 parts of ammonium chloride solutions, 4 parts of magnesium silicides; Per hour add per hour 2 parts of 30 parts of ammonium chloride solutions, magnesium silicides to second stage silane generator; Per hour add per hour 0.9 part of 10 parts of ammonium chloride solutions, magnesium silicide to third stage silane generator; Fourth stage temperature of reaction is 20 ℃ simultaneously, and pressure is 0.6MPa, and other reaction conditionss are constant.The productive rate of the relative magnesium silicide of the finished product silane is 95.0%.
Claims (8)
1. a magnesium silicide method is produced the method for silane, adopts continuous production method, comprises the steps: that it is 1%～40% ammonium chloride solution ammonia solution that solid ammonium chloride and liquefied ammonia are mixed with massfraction; The ammonium chloride solution ammonia solution for preparing and magnesium silicide solid are added by the first step of plural serial stage silane generator or classification addings of limiting the quantity of continuously, and magnesium silicide and ammonium chloride raw material totally mol ratio are 1: 5～8; Silane generators at different levels are stirred and cool off, and the temperature of reaction of silane generators at different levels is-60～30 ℃ and improves step by step that reaction pressure is 0.1～1.5MPa, and the reaction mass residence time is 1～12h; The silane that silane generators at different levels recur gets into the silane surge tank and collects via washing tower, condensing surface; The liquefied ammonia of the ammonia that silane gas is taken out of after condenser condenses returns silane generator by washing tower, and the liquefied ammonia that returns washs the borine impurity in the silane simultaneously.
2. method according to claim 1, described plural serial stage silane generator is 2～4 grades.
3. method according to claim 1 and 2, the massfraction of said ammonium chloride solution ammonia solution are 10%～30%.
4. method according to claim 1 and 2, said magnesium silicide and ammonium chloride raw material accumulative total mol ratio are 1: 5～6.
5. method according to claim 1 and 2, the temperature of reaction of silane generators at different levels are-50～20 ℃, and reaction pressure is 0.3～1.0MPa, and the reaction mass residence time is 3～8h.
6. method according to claim 1 and 2, when adopting 3 grades to operate continuously, first, second and third grade silane generator temperature is controlled at-60～-10 ℃ ,-40～10 ℃ ,-20～30 ℃ respectively.
7. method according to claim 6, described first, second and third grade silane generator temperature are controlled at-50～-20 ℃ ,-30～0 ℃ ,-10～20 ℃ respectively.
8. method according to claim 1 and 2 further, is installed SV on silane generators at different levels.
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| CN101249313A (en) * | 2008-04-01 | 2008-08-27 | 南京特种气体厂有限公司 | Recovery cyclic utilization method and apparatus for recovering discharged alkaline air in process of production of silicone hydride with magnesium silicide method |
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| JPS61191513A (en) * | 1985-02-19 | 1986-08-26 | Denki Kagaku Kogyo Kk | Continuous production of silane compounds |
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| CN101249313A (en) * | 2008-04-01 | 2008-08-27 | 南京特种气体厂有限公司 | Recovery cyclic utilization method and apparatus for recovering discharged alkaline air in process of production of silicone hydride with magnesium silicide method |
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| Title |
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| JP昭61-191513A 1986.08.26 |
| 王季陶等.高纯硅烷气的制取.《半导体技术》.1981,第8页"1.具体工艺流程"以及图1. |
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