CN102633262B - Method for preparing silane - Google Patents
Method for preparing silane Download PDFInfo
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- CN102633262B CN102633262B CN201210097153.3A CN201210097153A CN102633262B CN 102633262 B CN102633262 B CN 102633262B CN 201210097153 A CN201210097153 A CN 201210097153A CN 102633262 B CN102633262 B CN 102633262B
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- hydrogen fluoride
- silicomethane
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- magnesium
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Abstract
The invention discloses a method for preparing silane. The method comprises the following steps of: carrying out a reaction on magnesium silicide and excessive anhydrous hydrogen fluoride; and removing hydrogen fluoride in reacted gas by condensing and removing impurities through absorption of a molecular sieve, so as to obtain the silane. The method for preparing the silane provided by the invention uses normal chemical raw materials of the anhydrous hydrogen fluoride and the magnesium silicide. The method for preparing the silane provided by the invention has the advantages that: 1, the source of raw materials is wide and the price is low; and 2, the reacted magnesium silicide does not react with the anhydrous hydrogen fluoride, so that the by-product of magnesium fluoride is obtained by a normal separation means, and the use ratio of the anhydrous hydrogen fluoride is high. According to the by-product in the production process provided by the invention, on one hand, condensed hydrogen fluoride can be reused; and on the other hand, the magnesium silicide obtained by separating can be used as high-end fluoride for direct sale. Therefore, the economic benefits can be enhanced.
Description
Technical field
The present invention relates to a kind of preparation method of silicomethane, belong to inorganic synthesis technical field.
Background technology
Silane is a kind of important Chemicals, the ultra-pure electronic gas obtaining after purifying, very important intermediates in silicon product industrial chain, be the main raw material of preparing the products such as electronic-grade polycrystalline silicon, amorphous silicon film battery, silicon chip extension, peritonaeum glass, nano silicon material, the development of information industry and New Energy Industry is had to very important effect.
The silane Jin U.S., Japan and other countries minority enterprise have realized industrialization production at present.Its method mainly contains the chlorosilane discrimination method of U.S. UCC company employing and the tetrafluoride reduced method of sodium aluminum hydride that MEMC company adopts.These two kinds of methods are applicable to the successful case of large-scale production existing kiloton scale production of silane line, but the threshold height such as investment, technology, equipment have limited its popularization; Japan adopts little Song method to take ammonium chloride and magnesium silicide to prepare process for producing silicane as raw material, although invest little its by product magnesium chloride hex-ammoniate crystallization, has easily stopped up its development of having reclaimed the drawbacks limit such as difficulty, production cost are high of reactor, ammonia.Therefore, developing low-cost, invest process for producing silicane little, easy large-scale production and become a kind of active demand.
Summary of the invention
The object of this invention is to provide that a kind of purity is high, side reaction is few, eco-friendly silicomethane preparation method, and reduce cost prepared by silicomethane.
In order to realize above object, the technical solution adopted in the present invention is: a kind of preparation method of silicomethane, and magnesium silicide and excessive anhydrous hydrogen fluoride reaction, reacted gas except hydrogen fluoride, obtains silicomethane through condensation.
The gas that condensation is removed after hydrogen fluoride carries out molecular sieve adsorption removal of impurities.
Described temperature of reaction is-20～100 ℃.
The temperature of reaction of optimized choice is-20 ℃～20 ℃, and reaction process is followed and continued to stir.
Described reaction process adopts protection of inert gas.
The described reaction times is 0.5～5 hour.
The mol ratio of described anhydrous hydrogen fluoride and magnesium silicide is 4～20: 1.
After reaction, from reaction system, separation obtains solid, and drying obtains magnesium fluoride.
Chemical reaction of the present invention is as follows:
Mg
2Si+4HF→2MgF
2+SiH
4↑
In reaction process, magnesium silicide and excessive anhydrous hydrogen fluoride reaction, generate magnesium fluoride and silicomethane gas.Wherein anhydrous hydrogen fluoride can be also gaseous state for liquid state, and liquid anhydrous hydrogen fluoride and magnesium silicide are solid-liquid reaction, and the solid-liquid reaction container of employing is not specifically limited, and can adopt with the reactor that continues whipping appts and carry out solid-liquid reaction; The anhydrous hydrogen fluoride of gaseous state and magnesium silicide are gas-solid reaction, and the gas-solid reaction container of employing is not specifically limited, and can adopt fluidized-bed to carry out gas-solid reaction.The silicomethane gas that reaction generates overflows, and wherein can carry a small amount of anhydrous hydrogen fluoride secretly, removes the hydrogen fluoride of deentrainment through the condensation of condenser, can obtain high-purity silicomethane, and the hydrogen fluoride of wherein removing can reuse.The by-product magnesium fluoride that reaction produces can be widely used in the high-tech areas such as aerospace, instrument.
The preparation method of silicomethane of the present invention, adopts conventional chemical feedstocks anhydrous hydrogen fluoride and magnesium silicide, and the one, raw material sources are extensive, cheap; The 2nd, reacted magnesium fluoride can not produce and react with anhydrous hydrogen fluoride, can obtain by conventional separation means by-product magnesium fluoride, and the utilization ratio of anhydrous hydrogen fluoride is high.By product in production process of the present invention, on the one hand condensed hydrogen fluoride can recycle, and the separated magnesium fluoride obtaining can be used as directly outer selling of high-end fluorochemical on the other hand, increases economic benefit.Reacting phase of the present invention is for traditional technology, and reaction process is gentle, has increased safety coefficient, has promoted the sound development speed of domestic silane industry, is easy to large-scale production.Three-waste free discharge of the present invention, belongs to the process for cleanly preparing that country advocates.
In the preparation method of silicomethane of the present invention, during reaction, can relate to liquid anhydrous hydrogen fluoride and the solid-liquid reaction of magnesium silicide, and anhydrous hydrogen fluoride condensation is recycled and also can be related to liquid anhydrous hydrogen fluoride, in actual production activity, foreign gas oxygen and the carbonic acid gas of meeting solution minute quantity in liquid anhydrous hydrogen fluoride, these foreign gases can enter in the silicomethane gas of generation along with reaction, the present invention removes after hydrogen fluoride in condensation, adopt these foreign gases of molecular sieve adsorption, reach the object of further raising silicomethane purity.If but the anhydrous hydrogen fluoride material purity adopting is high, maybe can avoid oxygen or carbonic acid gas in dissolved air, can not adopt molecular sieve adsorption step.
In sum: the present invention is better than traditional technology from aspects such as production technique, quality product, safety and environmental protections, be that polysilicon industry and silane are prepared the direction of industry development from now on.In a word, the present invention has good economic benefit, social benefit and environmental benefit.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the embodiment of the present invention 1,2,3.
Embodiment
Embodiment 1
The silicomethane preparation method of the present embodiment is as follows: by anhydrous hydrogen fluoride and magnesium silicide raw material 2: 1 in molar ratio under protection of inert gas, join in stirred autoclave continuous uniform, under-20 ℃ of conditions, react 5 hours, the thick silicomethane that reaction generates enters condenser from reactor top, by cryogenic condensation (temperature is lower than hydrogen fluoride boiling point), remove hydrogen fluoride, through molecular sieve adsorption removal of impurities, obtain high-purity silicomethane, storage and transportation for the ease of silicomethane, silicomethane after compressing and liquefying, membrane compressor is bottled, obtain high purity silane finished product, concrete technical process is referring to Fig. 1.The main content 99.9999% of gained silane, silane yield is 95% (in magnesium silicide).Reacted system is filtered and is obtained magnesium fluoride solid, dry under present 40～100 ℃ (the present embodiment adopts 40～50 ℃) conditions, more logical hot nitrogen can obtain magnesium fluoride product, and the main content of magnesium fluoride is 99.95%.
Embodiment 2
The silicomethane preparation method of the present embodiment is as follows: by anhydrous hydrogen fluoride and magnesium silicide raw material 5: 1 in molar ratio under protection of inert gas; join in stirred autoclave continuous uniform; under 10 ℃ of conditions, react 3 hours; the thick silicomethane that reaction generates enters condenser from reactor top; by cryogenic condensation (temperature is lower than hydrogen fluoride boiling point), remove hydrogen fluoride; through molecular sieve adsorption removal of impurities; obtain high-purity silicomethane; storage and transportation for the ease of silicomethane; silicomethane is bottled after membrane compressor compresses and liquefies, obtain high purity silane finished product.The main content 99.9995% of gained silane, silane yield is 97% (in magnesium silicide).Reacted system is filtered and is obtained magnesium fluoride solid, dry under present 40～100 ℃ (the present embodiment adopts 70～80 ℃) conditions, more logical hot nitrogen can obtain magnesium fluoride product, and the main content of magnesium fluoride is 99.98%.
Embodiment 3
The silicomethane preparation method of the present embodiment is as follows: by anhydrous hydrogen fluoride and magnesium silicide raw material 10: 1 in molar ratio under protection of inert gas; join in stirred autoclave continuous uniform; under 0 ℃ of condition, react 1 hour; the thick silicomethane that reaction generates enters condenser from reactor top; by cryogenic condensation (temperature is lower than hydrogen fluoride boiling point), remove hydrogen fluoride; through molecular sieve adsorption removal of impurities; obtain high-purity silicomethane; storage and transportation for the ease of silicomethane; silicomethane is bottled after membrane compressor compresses and liquefies, obtain high purity silane finished product.The main content 99.99999% of gained silane, silane yield is 98% (in magnesium silicide).Reacted system is filtered and is obtained magnesium fluoride solid, dry under present 40～100 ℃ (the present embodiment adopts 70～80 ℃) conditions, more logical hot nitrogen can obtain magnesium fluoride product, and the main content of magnesium fluoride is 99.99%.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, difference is just that temperature of reaction is 100 ℃, and anhydrous hydrogen fluoride is gaseous state, and reaction vessel adopts fluidized-bed, after generating silicomethane, equally gas is carried out to condensation except hydrogen fluoride, the hydrogen fluoride of removing returns and is heated to 100 ℃ and becomes gaseous state and pass in fluidized-bed.The main content 99.99999% of gained silane, silane yield is 98% (in magnesium silicide).After reaction, in fluidized-bed, can stay remaining magnesium fluoride solid, pass into hot nitrogen and can obtain magnesium fluoride product, the main content of magnesium fluoride is 99.99%.
Claims (4)
1. a preparation method for silicomethane, is characterized in that: magnesium silicide and excessive anhydrous hydrogen fluoride reaction, and reacted gas except hydrogen fluoride, except the gas after hydrogen fluoride carries out molecular sieve adsorption removal of impurities, obtains silicomethane to condensation through condensation; Described temperature of reaction is-20 ℃～20 ℃; The described reaction times is 0.5～5 hour; The mol ratio of described anhydrous hydrogen fluoride and magnesium silicide is 4～20:1.
2. the preparation method of silicomethane according to claim 1, is characterized in that: described reaction process is followed and continued to stir.
3. the preparation method of silicomethane according to claim 1, is characterized in that: described reaction process adopts protection of inert gas.
4. the preparation method of silicomethane according to claim 1, is characterized in that: after reaction, from reaction system, separation obtains solid, and drying obtains magnesium fluoride.
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| CN201210097153.3A CN102633262B (en) | 2012-04-01 | 2012-04-01 | Method for preparing silane |
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| CN201210097153.3A CN102633262B (en) | 2012-04-01 | 2012-04-01 | Method for preparing silane |
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| CN102633262A CN102633262A (en) | 2012-08-15 |
| CN102633262B true CN102633262B (en) | 2014-03-26 |
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| TW201412379A (en) * | 2012-09-20 | 2014-04-01 | Taiwan Special Chemicals Corp | Purification method of disilane |
| TW201412378A (en) * | 2012-09-20 | 2014-04-01 | Taiwan Special Chemicals Corp | Purification method for silane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4632816A (en) * | 1982-12-13 | 1986-12-30 | Ethyl Corporation | Process for production of silane |
| CN101511732A (en) * | 2006-09-27 | 2009-08-19 | 电气化学工业株式会社 | Process for continuously producing monosilane |
| CN102203104A (en) * | 2008-10-31 | 2011-09-28 | 昭和电工株式会社 | Method for producing monosilane and tetraalkoxysilane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7972584B2 (en) * | 2008-08-25 | 2011-07-05 | Orion Laboratories, Llc | Magnesiothermic methods of producing high-purity silicon |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4632816A (en) * | 1982-12-13 | 1986-12-30 | Ethyl Corporation | Process for production of silane |
| CN101511732A (en) * | 2006-09-27 | 2009-08-19 | 电气化学工业株式会社 | Process for continuously producing monosilane |
| CN102203104A (en) * | 2008-10-31 | 2011-09-28 | 昭和电工株式会社 | Method for producing monosilane and tetraalkoxysilane |
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Effective date of registration: 20190412 Address after: 650300 Xia Luzhen Village, Luzhen Town, Anning City, Kunming City, Yunnan Province Patentee after: Duofuduo (Kunming) Technology Development Co. Ltd. Address before: 454191, Feng County, Henan Province, Jiaozuo Feng Feng Chemical Industry Zone Patentee before: Duo-fluoride Chemicals Co., Ltd. |
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