CN107473230A - The preparation technology of silane by magnesium silicide method - Google Patents
The preparation technology of silane by magnesium silicide method Download PDFInfo
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- CN107473230A CN107473230A CN201710735881.5A CN201710735881A CN107473230A CN 107473230 A CN107473230 A CN 107473230A CN 201710735881 A CN201710735881 A CN 201710735881A CN 107473230 A CN107473230 A CN 107473230A
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- silane
- ammonium chloride
- generator
- magnesium silicide
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- 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
- C01B33/04—Hydrides of silicon
- C01B33/043—Monosilane
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of continuous production method with silane by magnesium silicide method, comprise the following steps：Solid ammonium chloride and liquefied ammonia are configured to ammonium chloride solution ammonia solution；Solution and the magnesium silicide solid is added by the first order of plural serial stage silane generator or grading limit continuous adds, silane generators at different levels are stirred and cooled down, the silane that silane generators at different levels recur is collected via scrubbing towers at different levels, condenser into silane surge tank, the condensed liquefied ammonia of the condensed device of ammonia that silane gas is taken out of returns to silane generators at different levels by scrubbing tower, and the liquefied ammonia of return washs to impurity such as the borines in silane simultaneously.This method uses continuous feed, and multistage recurs silane, and every grade of reaction temperature carries out staged regulation and control, therefore silane tolerance is stable, and reaction condition is gentle, and security is good, and yield is high, and impurity is few, and cost is low, meets the requirement of green manufacturing.
Description
Technical field
The invention belongs to field of polysilicon technology, is related to a kind of preparation technology of silane, more particularly to one kind with magnesium silicide
For the modified technique for preparing silane of raw material.
Background technology
Silane (SiH4) epitaxial deposition monocrystalline silicon membrane and production polysilicon film are widely used in, manufacture non-crystal silicon solar cell
With the photosensitive part of duplicator, roused with silicon and replace traditional toner cartridge, and for producing dark-brown glass in glass industry.In height
In sciemtifec and technical sphere, silane and ethene can generate silicon carbide super powder, silane and ammonia under laser active can under laser active
Generate ultrafine powder of silicon nitride end.Simultaneously as the fast development of photovoltaic industry, domestic silane demand rapidly increase.
Production silane method mainly has at present：Magnesium silicide ammonolysis process (abbreviation magnesium silicide method), chlorosilane discrimination method are (also referred to as
UCC methods) and silicon fluoride hydrogenization method (also referred to as ETHYL methods).The method that magnesium silicide prepares silane is commonplace in the world in early days adopts
A kind of production method, was gradually substituted by other method later.In domestic generation nineteen sixty, succeeds in developing magnesium silicide method and technology
Route, domestic still magnesium silicide method is occupied an leading position at present.Magnesium silicide method production silane general principle be：With magnesium silicide and chlorine
Change ammonium is raw material, using liquid ammonia as reaction medium, reaction generation silane and magnesium chloride hexammoniate.This method have silane yield it is high,
The advantages that reaction raw materials are easy to get, are simple to operate, temperature and pressure process conditions easily reach.The preparation of existing silane by magnesium silicide method
, substantially using small-scale intermittently operated, the obvious of following several respects be present due to many factors such as technology and safety in method
Deficiency：
1) gas output is unstable in silane generating process, high to operating personnel and equipment requirement, and security is poor；
2) the intermittent reaction time is generally 24h, and yield only has 70%, and production capacity is low, adds production cost；
3) reaction temperature that silane occurs is typically chosen -40~-80 DEG C, and such cryogenic conditions reaction cools to refrigerant requires high,
Add energy consumption；
4) silane is directly entered silane refining step after occurring, and entrainment liquefied ammonia amount is big, adds purification difficulty；
5) intermittently operated A leak of liquefied ammonia is more, and environmental pollution is serious.
The content of the invention
The invention aims to solve the labor intensity present in the small-scale Batch Process silane of existing magnesium silicide method
Greatly, security is poor, low yield, high energy consumption, serious environmental pollution the deficiencies of, there is provided a kind of side of magnesium silicide method continuous production silane
Method, it comprises the following steps：
Solid ammonium chloride and liquefied ammonia are configured to the ammonium chloride solution ammonia solution that mass fraction is 1%~40%；The chlorine that will be prepared
Change ammonium liquid ammonia solution and magnesium silicide solid and continuously add or be classified limitation addition by the first order of plural serial stage silane generator,
It is 1: 1~8 that magnesium silicide adds up mol ratio with ammonium chloride raw material；Silane generators at different levels are stirred and cooled down, each grade silane
The reaction temperature of generator is -60~30 DEG C, and reaction pressure is 0.1~1.5MPa, and the reaction mass residence time is 1~12h；Respectively
The silane that grade silane generator recurs is collected via scrubbing tower, condenser into silane surge tank, what silane gas was taken out of
The condensed liquefied ammonia of the condensed device of ammonia returns to silane generator by scrubbing tower, and the liquefied ammonia of return is simultaneously to borine in silane etc.
Impurity is washed.
Preferably 2~4 grades, preferably 3 grades or 4 grades of described plural serial stage silane generator.During less than 3 grades, the reaction time
Extending, yield declines, during more than 4 grades, although operation more towards safe and stable, is present, plant investment is big, floor space is big,
The shortcomings that high energy consumption.The form of silane generator is usually reactor.
The mass fraction for preparing ammonium chloride solution ammonia solution is 1%~40%, preferably 10%~30%.Ammonium chloride concentration
Too low, reaction speed is slow, is unfavorable for the raising of production capacity；And excessive concentration, the contact of solid-liquid material are bad, also have very to reaction speed
Big influence.
In course of reaction, it is usually 1: 1~8 that magnesium silicide adds up mol ratio with ammonium chloride raw material, preferably by accumulative mol ratio
Fed intake for 1: 4~6.Magnesium silicide and the stoichiometric of ammonium chloride reaction are 1: 4, and ammonium chloride matches too low, silication reactive magnesium
Not exclusively；Match too high, ammonium chloride cost of material substantially increases.
In a kind of preferred embodiment, the ammonium chloride solution ammonia solution and magnesium silicide that prepare use pump and screw feeder respectively
Metering is continuously added to silane generator.
When being operated continuously using 3 grade silane generators, with being continuously added for reaction raw materials, in first order silane generator
Material sequentially input second, third grade silane generator through pump, carry out continuous silane and react.3 grade silane generators
The reaction mass residence time is 1~12h, preferably 3~8h.
The silane generators at different levels of series connection can use consistent operation temperature and pressure, can also use different temperature
And pressure；It is preferred that the mode of operation that reaction temperature improves step by step is used to ensure the yield of silane generation.
When using 3 grades of continuous operations, reaction speed is accelerated by the control of differential responses temperature, it is ensured that magnesium silicide is anti-
That answers is complete, and first, second and third grade silane generator temperature controls in -60~-10 DEG C, -40~10 DEG C, -20~30 DEG C of models respectively
In enclosing, preferably -50~-20 DEG C, -30~0 DEG C, -10~20 DEG C.The concentration of raw material is higher in first order generator, reaction speed
Comparatively fast, control relatively low temperature to be advantageous to the steady progress for controlling silane to react, step up instead with reaction
Answer temperature that raw material is quickly reacted completely.The pressure of silane generators at different levels is 0.1~1.5MPa, preferably 0.3~
1.0MPa, this is primarily due to ammonia under existing temperature conditionss, and 0.3~1.0MPa relative volatilities are smaller, can effectively subtract
The area of few condenser, so as to reduce investment cost.
When liquefied ammonia returns to silane generator by scrubbing tower, the impurity such as the borine in silane can be washed, reduce silicon
The content of impurity in alkane, the refined difficulty of silane can be reduced.
Continuously extraction is pending to buffer suspension tank for the magnesium chloride hexammoniate suspension of afterbody silane generator.
Foregoing invention is proposed based on such thinking：The serialization of ammonium chloride solution ammonia solution, which is prepared, greatly to be subtracted
Few labor intensity, improves operating efficiency, while reduce the pollution of dispensing；Magnesium silicide adds silane hair with ammonium chloride solution simultaneously
Raw device reaction can enable solid-liquid material preferably contact, and so as to improve reaction speed, improve operating efficiency and production capacity.
In addition, many places are mounted with safety valve in this technological equipment, safe reliability further enhancing.Especially by
Safety valve is respectively mounted in silane generators at different levels, it is ensured that the safe operation that silane occurs.
The inventive method has the following advantages that：
1) continuous feed is used, multistage recurs silane, and every grade of reaction temperature carries out staged regulation and control, therefore silane gas
Amount is stable, and not high to operating personnel and equipment requirement, security is good, while many places are mounted with safety valve in this technological equipment, enters
One step enhances safe reliability；
2) collected using continuous batching, charging, silane generation, silane and the extraction of magnesium chloride hexammoniate suspension, yield can reach
95%, production capacity is improved, reduces production cost；
3) reaction temperature that silane occurs is controlled at -60~30 DEG C, and 0.1~1.5MPa of reaction pressure, reaction condition more relaxes,
Refrigerant is cooled less demanding；
4) pass through after silane occurs and washed by liquefied ammonia scrubbing tower, the impurity such as borine therein are effectively removed, while condenser
It can will be returned after most ammonia condensations in silane generator, reduce the impurity and liquefied ammonia in silane, greatly reduce and carry
Pure difficulty；
5) silane occurs to use continuous operation, substantially without A leak of liquefied ammonia, meets the requirement of green manufacturing.
Brief description of the drawings
Fig. 1 is process chart prepared by currently preferred 3 grade silane generator series connection serialization silane.
1- ammonium chloride head tanks；2- ammonium chloride feeders；3- ammonium chloride batching kettles；4- liquefied ammonia condensers；5- ammonium chlorides are molten
Liquid delivery pump；6- magnesium silicide head tanks；7- magnesium silicide feeders；8th, 12,16- silane generators；9th, 13,17- silane occurs cold
Condenser；10th, 14,18- scrubbing towers；11st, 15,19- suspension extraction pump；20th, 21,22- safety valves.
Embodiment
The present invention is explained further in mode with reference to the accompanying drawings and examples, but the present invention is not limited to these implementations
Example.Unless otherwise indicated, " part " therein or " % " are " mass parts " or " quality % ".
It is prepared by the grade silane generator of embodiment 13 series connection serialization silane
Gas displacement is carried out to whole reaction system with nitrogen before silane generation, the replacement of oxygen in reaction system is clean；
Replacement of oxygen is finished, and liquefied ammonia is squeezed into batching kettle 3 with 80 parts per hour by surge tank, the ammonia of vaporization is via condenser 4
Back ingredient kettle 3 after condensation, ammonium chloride are added in batching kettle 3 through screw feeder 2 by head tank 1 with 20 parts per hour, are configured to
20% ammonium chloride solution ammonia solution；
The ammonium chloride solution ammonia solution prepared through pump 5 with 100 parts per hour input first order silane generators 8, while by silication
Magnesium silicide in magnesium head tank 6 is added using 6.9 parts per hour (mol ratio of magnesium silicide and ammonium chloride is 1: 4.1) siliconized magnesium spirals
Glassware 7, which is continuously added in first order silane generator 8, to react, and wherein temperature is -30 DEG C, pressure 0.6MPa, is occurred
The scrubbed tower 10 of silane, condenser 9 enter silane surge tank；
The feed liquid do not reacted completely in first order silane generator 8 inputs second level silane generator 12 via pump 11 and continued instead
Should, wherein temperature is -10 DEG C, pressure 0.6MPa, and the scrubbed tower 14 of silane, the condenser 13 of generation enter silane surge tank；
The feed liquid do not reacted completely in second level silane generator 12 inputs third level silane generator 16 via pump 15 and continued instead
Should, wherein temperature is 10 DEG C, pressure 0.6MPa, and the scrubbed tower 18 of silane, the condenser 17 of generation enter silane surge tank, instead
Complete magnesium chloride hexammoniate liquefied ammonia suspension is answered to input suspension surge tank via pump 19.
Final products silane is 93.1% with respect to the yield of magnesium silicide.
Embodiment 2
Technological process is with embodiment 1, and simply by liquefied ammonia in embodiment 1, addition is changed to 106.7 parts by 80 parts and (is configured to per hour
15% ammonium chloride solution ammonia solution), other conditions are constant.Final products silane is 92.6% with respect to the yield of magnesium silicide.
Embodiment 3
Technological process is with embodiment 1, and simply by liquefied ammonia in embodiment 1, addition is changed to 64 parts by 80 parts and (is configured to per hour
25% ammonium chloride solution ammonia solution), other conditions are constant.Final products silane is 95.2% with respect to the yield of magnesium silicide.
Embodiment 4
Technological process is with embodiment 1, and simply by magnesium silicide in embodiment 1, addition is changed to 6.3 parts of (silication by 6.9 parts per hour
The mol ratio of magnesium and ammonium chloride is 1: 4.5), other conditions are constant.Final products silane is 94.0% with respect to the yield of magnesium silicide.
Embodiment 5
Technological process is with embodiment 1, and simply by magnesium silicide in embodiment 1, addition is changed to 5.7 parts of (silication by 6.9 parts per hour
The mol ratio of magnesium and ammonium chloride is 1: 5), other conditions are constant.Final products silane is 94.9% with respect to the yield of magnesium silicide.
Embodiment 6
Technological process with embodiment 1, simply by 3 grade silane generator temperatures in embodiment 1 change into respectively -40 DEG C, -20 DEG C, 0
DEG C, other conditions are constant.Final products silane is 90.1% with respect to the yield of magnesium silicide.
Embodiment 7
3 grade silane generator reaction pressures in embodiment 1 are simply changed into 0.5MPa with embodiment 1 by technological process, other
Part is constant.Final products silane is 93.9% with respect to the yield of magnesium silicide.
Embodiment 8
3 grade silane generator reaction pressures in embodiment 1 are simply changed into 0.7MPa with embodiment 1 by technological process, other
Part is constant.Final products silane is 91.9% with respect to the yield of magnesium silicide.
Embodiment 9
3 grade silane generator reaction pressures in embodiment 1 are simply changed into the first order by technological process respectively with embodiment 1
0.7MPa, second level 0.6MPa and third level 0.5MPa, other conditions are constant.Final products silane is with respect to the yield of magnesium silicide
94.9%.
It is prepared by the grade silane generator of embodiment 10 2 series connection serialization silane
Third level reactor during 3 grade silanes in embodiment 1 are occurred is cancelled, and is changed to the generation of 2 grade silanes, other reaction conditions
It is constant.Final products silane is 89.9% with respect to the yield of magnesium silicide.
It is prepared by the grade silane generator of embodiment 11 3 series connection serialization silane
3 grade silane generators in embodiment 1 are changed to 4 grade silane generators, wherein fourth stage silane generator reaction temperature
For 20 DEG C, pressure 0.6MPa, other reaction conditions are constant.Final products silane is 93.9% with respect to the yield of magnesium silicide.
It is prepared by the grade silane generator of embodiment 12 3 classification charging serialization silane
100 parts per hour of the ammonium chloride solution ammonia solution prepared in embodiment 1, magnesium silicide are all added for 6.9 parts per hour
First order silane generator reacts, and is changed to add 70 parts of ammonium chloride solution, magnesium silicide 4.5 per hour to first order silane generator
Part, while 2.4 parts per hour of 30 parts of ammonium chloride solution, magnesium silicide are added per hour to second level silane generator, other reactions
Condition is constant.Final products silane is 94.2% with respect to the yield of magnesium silicide.
It is prepared by the grade silane generator of embodiment 13 3 classification charging serialization silane
100 parts per hour of the ammonium chloride solution ammonia solution prepared in embodiment 1, magnesium silicide are all added for 6.9 parts per hour
First order silane generator reacts, and is changed to add 60 parts of ammonium chloride solution, magnesium silicide 4 per hour to first order silane generator
Part, 2 parts per hour of 30 parts of ammonium chloride solution, magnesium silicide are added per hour to second level silane generator, are sent out to third level silane
Raw device adds 0.9 part per hour of 10 parts of ammonium chloride solution, magnesium silicide per hour, while fourth stage reaction temperature is 20 DEG C, pressure
It is constant for 0.6MPa, other reaction conditions.Final products silane is 95.0% with respect to the yield of magnesium silicide.
Claims (9)
1. a kind of method of magnesium silicide method production silane, using continuous producing method, comprises the following steps：By solid ammonium chloride with
Liquefied ammonia is configured to the ammonium chloride solution ammonia solution that mass fraction is 1%~40%；By the ammonium chloride solution ammonia solution prepared and silication
Magnesium solid is continuously added by the first order of plural serial stage silane generator or classification limitation adds, magnesium silicide and ammonium chloride raw material
Accumulative mol ratio is 1: 1~8；Silane generators at different levels are stirred and cooled down, the reaction temperatures of silane generators at different levels for-
60~30 DEG C, reaction pressure is 0.1~1.5MPa, and the reaction mass residence time is 1~12h；Silane generators at different levels are continuously sent out
Raw silane is collected via scrubbing tower, condenser into silane surge tank, after the condensed device condensation of the ammonia that silane gas is taken out of
Liquefied ammonia silane generator is returned to by scrubbing tower, the liquefied ammonia of return washs to impurity such as the borines in silane simultaneously.
2. according to the method for claim 1, described plural serial stage silane generator is 2~4 grades.
3. method according to claim 1 or 2, the mass fraction of the ammonium chloride solution ammonia solution is 10%~30%.
4. method according to claim 1 or 2, it is 1: 4~6 that the magnesium silicide adds up mol ratio with ammonium chloride raw material.
5. method according to claim 1 or 2, the reaction temperature of silane generators at different levels is -50~20 DEG C, reaction pressure
For 0.3~1.0MPa, the reaction mass residence time is 3~8h.
6. method according to claim 1 or 2, described plural serial stage silane generator is improved step by step using reaction temperature
Mode of operation.
7. according to the method for claim 6, operated continuously using 3 grades, first, second and third grade silane generator temperature point
Do not control at -60~-10 DEG C, -40~10 DEG C, -20~30 DEG C.
8. according to the method for claim 7, first, second and third described grade silane generator temperature controls -50 respectively
~-20 DEG C, -30~0 DEG C, -10~20 DEG C.
9. method according to claim 1 or 2, further, safety valve is installed on silane generators at different levels.
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| CN201710735881.5A CN107473230A (en) | 2017-08-24 | 2017-08-24 | The preparation technology of silane by magnesium silicide method |
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| CN201710735881.5A CN107473230A (en) | 2017-08-24 | 2017-08-24 | The preparation technology of silane by magnesium silicide method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694091A (en) * | 2021-02-25 | 2021-04-23 | 刘振宇 | Electronic gas preparation system and method based on chip and intelligent manufacturing |
-
2017
- 2017-08-24 CN CN201710735881.5A patent/CN107473230A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694091A (en) * | 2021-02-25 | 2021-04-23 | 刘振宇 | Electronic gas preparation system and method based on chip and intelligent manufacturing |
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| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20171215 |
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