CN205099363U - System for production silicon nitride - Google Patents
System for production silicon nitride Download PDFInfo
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- CN205099363U CN205099363U CN201520897686.9U CN201520897686U CN205099363U CN 205099363 U CN205099363 U CN 205099363U CN 201520897686 U CN201520897686 U CN 201520897686U CN 205099363 U CN205099363 U CN 205099363U
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Abstract
The utility model discloses a system for production silicon nitride, include: the initial response ware, heating device, this heating device with the initial response ware is connected, the drip washing tower, the first feed inlet of this drip washing tower with heating device connects. This system can recycle the reaction with dichlorosilane with the ammonia of preparing the in -process formation, has rebuild the required nitrogenous silane compound of midbody second of preparation silicon nitride to the cost has been practiced thrift.
Description
Technical field
The utility model belongs to silicon nitride production technical field, is specifically related to a kind of system of producing silicon nitride.
Background technology
Silicon nitride has that physical strength is high, Heat stability is good, good chemical stability, for the high temperature often run in modern technologies, at a high speed, the Working environment of strong corrosive medium and high wearing and tearing, there is special purposes.Silicon nitride having many uses industrially is general, can be applicable to metallurgy, machinery, chemical industry, semi-conductor, aerospace and auto industry field, as turbine blade, high-temperature bearing, high speed cutting instrument, heat-resistant part, abrasion-proof corrosion-proof parts etc.Along with the continuous expansion of silicon nitride range of application and improving constantly silicon nitride quality requirements, the preparation of beta-silicon nitride powder more and more comes into one's own.
The silicon nitride technology of preparing of commercial applications has four kinds: (1) silica flour direct nitridation method, comprises low-voltage high-temperature nitrogenize and the nitrogenize of high pressure self-propagating; (2), in nitrogen, there is redox reaction by silicon-dioxide and carbon dust and generate silicon nitride in carbothermic method; (3) low temperature silane thermal decomposition process, generates intermediate product nitrogenated silicon hydride compounds Si (NH) by silicon tetrachloride and ammonia
2, and then pyrolysis is silicon nitride; (4) high temperature silane thermal decomposition process, by silicon tetrachloride or silicomethane at high temperature directly and ammonia to react generation silicon nitride.In the above-mentioned methods, low temperature silane thermal decomposition process and high temperature silane thermal decomposition process easily realize, to raw-material purification, being suitable for the preparation of high purity silicon nitride silicon powder.But in high temperature silane thermal decomposition process, silicomethane is inflammable and explosive, dangerous high, and during using silicon tetrachloride as raw material, need the technology such as using plasma, laser to carry out reaction strengthening, investment is large, and productive rate is low, and cost is high.
Silicon nitride prepared by low temperature silane thermal decomposition process is generally accepted by people with its high quality, but the rapid reaction synthesizing strong heat release of nitrogenated silicon hydride compounds in low temperature silane thermal decomposition process, chlorine element is easily carried secretly in nitrogenated silicon hydride compounds, therefore its liquid-liquid interface reaction of producing general employing silicon tetrachloride and ammonia controls speed of response at present, and then obtaining pure nitrogenated silicon hydride compounds by the method that a large amount of liquefied ammonia washes away ammonium chloride by-product, last reheating is decomposed into silicon nitride.Liquid-liquid interface speed of reaction is slow, and complex process, production capacity is low, causes its cost can not to be in any more always.
Utility model content
Technical problem to be solved in the utility model is for above shortcomings in prior art, a kind of system of producing silicon nitride is provided, the ammonia generated in preparation process recycling can be reacted with the second chlorosilane by this system, regenerate the intermediate second nitrogenated silicon hydride compounds prepared needed for silicon nitride, thus save cost.
The technical scheme that solution the utility model technical problem adopts is to provide a kind of system of producing silicon nitride, comprising:
First reactor, for carrier gas Raw first chlorosilane and raw material first ammonia gas react, obtain the first solid mixture and the first gaseous mixture, wherein, described first solid mixture comprises the first nitrogenated silicon hydride compounds and the first ammonium chloride that described first chlorosilane and described first ammonia gas react generate, and described first gaseous mixture comprises carrier gas and the first ammonia;
Heating unit, be connected with described first reactor, described first solid mixture in described first reactor enters described heating unit, described heating unit is for heating described first solid mixture reaction, obtain the second solid matter and the second gaseous mixture, wherein, described second gaseous mixture comprises described first ammonium chloride through heating the ammonia and hydrogenchloride that generate, and described second solid matter comprises described first nitrogenated silicon hydride compounds through heating the silicon nitride of the high α phase content generated;
Eluting column, be connected with described heating unit, described second gaseous mixture enters described eluting column, described eluting column is used for passing into the second chlorosilane and carries out drip washing to described second gaseous mixture, obtain the 3rd solid mixture and the 3rd gaseous matter, wherein, described 3rd solid mixture comprises the second nitrogenated silicon hydride compounds and the second ammonium chloride that the ammonia gas react in described second chlorosilane and described second gaseous mixture generates, and described 3rd gaseous matter comprises hydrogenchloride.
The ammonia generated in preparation process recycling can be reacted with the second chlorosilane by the system of production silicon nitride of the present utility model, has regenerated the intermediate second nitrogenated silicon hydride compounds prepared needed for silicon nitride, thus has saved cost.
Reaction in first reactor is gas solid/liquid/gas reactions, and the flow of unstripped gas and reaction are all easy to control.
Nitrogenated silicon hydride compounds of the present utility model, generally also referred to as silicon diimine, easily absorbs or exists with Si-N-H based compound form after releasing ammonia, the most available Si (NH) of nitrogenated silicon hydride compounds
2formula represents, Si (NH)
2be not a concrete material, this compounds can be Si
6n
13h
15, Si
6n
12h
12, Si
6n
11h
9deng.
Carrier gas in described first reactor is the one in nitrogen, ammonia, rare gas element, is diluted reaction raw material used by carrier gas.
Chlorosilane carrier gas passes into, and preferred carrier gas is nitrogen, and the flow controlling nitrogen is more than 2 times of the first chlorosilane, to control speed of response and to prevent the system of producing silicon nitride from occurring line clogging.
Preferably, described first chlorosilane is one or more in silicon tetrachloride, trichlorosilane, dichlorosilane.
Raw material first chlorosilane adopted and raw material first ammonia purity all 99.99% and more than, other first ammonia and carrier gas all will carry out processed.
Preferably, in described first reactor, the temperature of described heating carrier gas Raw first chlorosilane and raw material first ammonia gas react is 10 ~ 100 DEG C, and pressure is 0 ~ 1MPa.
Preferably, in described first reactor, the mol ratio of described first chlorosilane and described first ammonia is 1:(6 ~ 30).The excessive chlorosilane that can make of ammonia reacts completely.
Preferably, the tower reactor of described eluting column is connected with the entrance of described heating unit, enters described heating unit for described 3rd solid mixture.Then described 3rd solid mixture mixes with described first solid mixture, the reaction in heating unit described in recirculation.
Preferably, described heating unit comprises:
Primary heater, comprise the entrance of primary heater, first outlet of primary heater, second outlet of primary heater, the entrance of described primary heater is connected with described first reactor, described primary heater is entered for described first solid mixture in described first reactor, under non-oxidizing atmosphere, heat described first solid mixture reaction, obtain the 4th solid mixture and the 4th gaseous mixture, described 4th gaseous mixture comprises the gas of the described non-oxidizing atmosphere in described primary heater, the ammonia that described first ammonium chloride generation thermolysis generates and hydrogenchloride, described 4th solid mixture comprises described first nitrogenated silicon hydride compounds, by product first ammonium chloride is eliminated by this step, first outlet of described primary heater is connected with described eluting column, described 4th gaseous mixture enters described eluting column through the first outlet of described primary heater,
Secondary heater, comprise the entrance of secondary heater, first outlet of secondary heater, second outlet of secondary heater, the entrance of described secondary heater and second of described primary heater exports and is connected, enter in described secondary heater for described 4th solid mixture in described primary heater, under ammonia atmosphere, heat described 4th solid mixture, obtain the 5th solid mixture and the 5th gaseous mixture, described 5th solid mixture comprises described first nitrogenated silicon hydride compounds generation thermolysis and generates unbodied silicon nitride, described 5th gaseous mixture comprises the gas of ammonia atmosphere, hydrogenchloride, the ammonia that described first nitrogenated silicon hydride compounds generation thermolysis generates, first outlet of described secondary heater is connected with described eluting column, described 5th gaseous mixture enters described eluting column through the first outlet of described secondary heater, the ammonia that described first nitrogenated silicon hydride compounds generation thermolysis generates enters the inside of the first nitrogenated silicon hydride compounds, the chlorine element that removing is wherein inner, avoid liquefied ammonia washing in prior art and, except the method for dechlorination element, greatly simplify the Production Flow Chart of silicon nitride.First outlet of primary heater, the first outlet of secondary heater are all connected with eluting column, can reclaim the ammonia in the 4th gaseous mixture and the 5th gaseous mixture simultaneously, reduce processing cost.
3rd well heater, export with second of described secondary heater and be connected, described 5th solid mixture in described secondary heater enters in described 3rd well heater, for under non-oxidizing atmosphere, heat described 5th solid mixture, obtain described second solid matter and described second gaseous mixture, described unbodied silicon nitride generates the silicon nitride of high α phase content through heating.
Preferably, in described primary heater, the temperature of the described first solid mixture reaction of described heating is 500 ~ 600 DEG C, and heat-up time is 1 ~ 2 hour;
In described secondary heater, the temperature of described 4th solid mixture of described heating is 650 ~ 1200 DEG C, and heat-up time is 2 ~ 8 hours;
In described 3rd well heater, the temperature of described 5th solid mixture of described heating is 1250 ~ 1700 DEG C, and heat-up time is 2 ~ 8 hours.
Preferably, in described 3rd well heater, the temperature of described 5th solid mixture of described heating is 1350 ~ 1600 DEG C, and temperature is too low, then the phase in version time is long, and temperature is too high, then easily promote the content of β phase in silicon nitride.
Preferably, the system of described production silicon nitride also comprises:
Second reactor, comprise the entrance of the second reactor and the outlet of the second reactor, the entrance of described second reactor is connected with the tower top of described eluting column, described second reactor is entered by the tower top of described eluting column for described 3rd gaseous matter, described second reactor is used for passing into silica flour and described 3rd gaseous matter reacting by heating obtains trichlorosilane, the outlet of described second reactor is connected with the entrance of the first reactor, and described trichlorosilane enters in described first reactor.Then described trichlorosilane mixes with described first chlorosilane, repeats the reaction in described first reactor, is reused for the production of silicon nitride.
Preferably, described second reactor is 300 ~ 500 DEG C for the temperature of reaction passing into silica flour and described 3rd gaseous matter reacting by heating and obtain trichlorosilane, more preferably, 325 ~ 400 DEG C, by controlling the temperature of reaction, each component can be regulated in the trichlorosilane product of generation as the content of silicon tetrachloride, trichlorosilane.
Product trichlorosilane in second reactor is also the raw material of production of polysilicon, and therefore this product can be incorporated in polycrystalline silicon production system, realizes the coproduction of silicon nitride and polysilicon, reduces costs further.
Preferably, the system of described production silicon nitride also comprises:
Rectifier unit, comprise the entrance of rectifier unit and the outlet of rectifier unit, the entrance of described rectifier unit is connected with the outlet of described second reactor, the outlet of described rectifier unit is connected with the entrance of the first reactor, described rectifier unit is used for carrying out rectification and purification to described trichlorosilane, and purified trichlorosilane enters described first reactor.
Preferably, the outlet of described second reactor is also connected with eluting column, enters in described eluting column for drip washing for described trichlorosilane.Then described trichlorosilane mixes with described second chlorosilane, repeats the drip washing in described eluting column.
Preferably, the system of described production silicon nitride also comprises:
Strainer, comprise the entrance of strainer, first outlet of strainer, second outlet of strainer, the entrance of described strainer is connected with the first reactor, the first gaseous mixture in described first reactor and part first solid mixture enter described strainer, described strainer is used for gas-solid filtering separation described first solid mixture of part that obtains separating and described first gaseous mixture, first outlet of described strainer is connected with described heating unit, described first solid mixture of part enters described heating unit by the first outlet of described strainer, second outlet of described strainer is connected with described first reactor, described first gaseous mixture enters described first reactor by the second outlet of described strainer.Described first solid mixture generated in first reactor is deposited in the first reactor bottom, and part is taken out of strainer by unreacted ammonia.First solid mixture of the bottom of the first reactor can be discharged continuously, also can steply discharge.
Preferably, the system of described production silicon nitride also comprises:
Water cooler, comprise the entrance of water cooler, the first outlet of water cooler, the second outlet of water cooler, the entrance of described water cooler and second of described strainer exports and is connected, enter described water cooler for described first gaseous mixture by the second outlet of described strainer, described water cooler is used for refrigerated separation and obtains liquefied ammonia and carrier gas; Temperature in described water cooler is-35 ~-50 DEG C.
Carrier gas reservoir, comprise the entrance of carrier gas reservoir and the outlet of carrier gas reservoir, the entrance of described carrier gas reservoir and first of described water cooler exports and is connected, entered into the entrance of described carrier gas reservoir by the first outlet of described water cooler for the carrier gas in described water cooler, the outlet of described carrier gas reservoir is connected with described first reactor; Carrier gas in carrier gas reservoir is reused for the carrier gas in the first reactor.
Liquid ammonia storage tank, comprise the entrance of liquid ammonia storage tank and the outlet of liquid ammonia storage tank, the entrance of described liquid ammonia storage tank and second of described water cooler exports and is connected, entered into the entrance of described liquid ammonia storage tank by the second outlet of described water cooler for the liquefied ammonia in described water cooler, the outlet of described liquid ammonia storage tank is connected with described first reactor.Certainly, the liquefied ammonia in liquid ammonia storage tank also can be used as the protective atmosphere in heating unit.
Preferably, described second chlorosilane is one or more in silicon tetrachloride, trichlorosilane, dichlorosilane.
Preferably, described trichlorosilane is one or more in silicon tetrachloride, trichlorosilane, dichlorosilane.
The system of production silicon nitride of the present utility model can realize the continuous prodution of intermediate first nitrogenated silicon hydride compounds, the production of whole silicon nitride is closed loop process, by product and unreacted reactant obtain recycling, needing the raw material supplemented for being only silica flour and ammonia, significantly can reduce the production cost of silicon nitride.
Accompanying drawing explanation
Fig. 1 is the structural representation of the system of production silicon nitride in the utility model embodiment 1,2;
Fig. 2 is the structural representation of the system of production silicon nitride in the utility model embodiment 2;
Fig. 3 is the part-structure schematic diagram of the system of production silicon nitride in the utility model embodiment 2.
In figure: 1-first reactor; 2-heating unit; 3-eluting column; The tower reactor of 31-eluting column; The tower top of 32-eluting column; First opening for feed of 33-eluting column; Second opening for feed of 34-eluting column; 4-primary heater; The entrance of 41-primary heater; First outlet of 42-primary heater; Second outlet of 43-primary heater; 5-secondary heater; The entrance of 51-secondary heater; First outlet of 52-secondary heater; Second outlet of 53-secondary heater; 6-the 3rd well heater; 7-second reactor; The entrance of 71-second reactor; The outlet of 72-second reactor; 8-rectifier unit; The entrance of 81-rectifier unit; The outlet of 82-rectifier unit; 9-strainer; The entrance of 91-strainer; First outlet of 92-strainer; Second outlet of 93-strainer; 10-water cooler; The entrance of 101-water cooler; First outlet of 102-water cooler; Second outlet of 103-water cooler; 11-carrier gas reservoir; The entrance of 111-carrier gas reservoir; The outlet of 112-carrier gas reservoir; 12-liquid ammonia storage tank; The entrance of 121-liquid ammonia storage tank; The outlet of 122-liquid ammonia storage tank.
Embodiment
For making those skilled in the art understand the technical solution of the utility model better, below in conjunction with the drawings and specific embodiments, the utility model is described in further detail.
Embodiment 1
As shown in Figure 1, the technical scheme that the present embodiment technical problem adopts is to provide a kind of system of producing silicon nitride, comprising:
First reactor 1, for heating carrier gas Raw first chlorosilane and raw material first ammonia gas react, obtain the first solid mixture and the first gaseous mixture, wherein, described first solid mixture comprises the first nitrogenated silicon hydride compounds and the first ammonium chloride that described first chlorosilane and described first ammonia gas react generate, and described first gaseous mixture comprises carrier gas and the first ammonia;
Heating unit 2, be connected with described first reactor 1, described first solid mixture in described first reactor 1 enters described heating unit 2, described heating unit 2 is for heating described first solid mixture reaction, obtain the second solid matter and the second gaseous mixture, wherein, described second gaseous mixture comprises described first ammonium chloride through heating the ammonia and hydrogenchloride that generate, and described second solid matter comprises described first nitrogenated silicon hydride compounds through heating the silicon nitride of the high α phase content generated;
Eluting column 3, be connected with described heating unit 2, described second gaseous mixture enters described eluting column 3, described eluting column 3 carries out drip washing for passing into the second chlorosilane to described second gaseous mixture, obtain the 3rd solid mixture and the 3rd gaseous matter, wherein, described 3rd solid mixture comprises the second nitrogenated silicon hydride compounds and the second ammonium chloride that the ammonia gas react in described second chlorosilane and described second gaseous mixture generates, and described 3rd gaseous matter comprises hydrogenchloride.
Reaction in first reactor 1 is gas solid/liquid/gas reactions, and the flow of unstripped gas and reaction are all easy to control.
The nitrogenated silicon hydride compounds of the present embodiment, generally also referred to as silicon diimine, easily absorbs or exists with Si-N-H based compound form after releasing ammonia, the most available Si (NH) of nitrogenated silicon hydride compounds
2formula represents, Si (NH)
2be not a concrete material, this compounds can be Si
6n
13h
15, Si
6n
12h
12, Si
6n
11h
9deng.
Carrier gas in described first reactor 1 is the one in nitrogen, ammonia, rare gas element, is diluted reaction raw material used by carrier gas.
Chlorosilane carrier gas passes into, and preferred carrier gas is nitrogen, and the flow controlling nitrogen is more than 2 times of the first chlorosilane, to control speed of response and to prevent the system of producing silicon nitride from occurring line clogging.
The ammonia generated in preparation process recycling can be reacted with the second chlorosilane by the system of the production silicon nitride of the present embodiment, has regenerated the intermediate second nitrogenated silicon hydride compounds prepared needed for silicon nitride, thus has saved cost.
Embodiment 2
As shown in Figure 1, 2, the technical scheme that the present embodiment technical problem adopts is to provide a kind of system of producing silicon nitride, comprising:
First reactor 1, for heating carrier gas Raw first chlorosilane and raw material first ammonia gas react, obtain the first solid mixture and the first gaseous mixture, wherein, described first solid mixture comprises the first nitrogenated silicon hydride compounds and the first ammonium chloride that described first chlorosilane and described first ammonia gas react generate, and described first gaseous mixture comprises carrier gas and the first ammonia;
Heating unit 2, be connected with described first reactor 1, described first solid mixture in described first reactor 1 enters described heating unit 2, described heating unit 2 is for heating described first solid mixture reaction, obtain the second solid matter and the second gaseous mixture, wherein, described second gaseous mixture comprises described first ammonium chloride through heating the ammonia and hydrogenchloride that generate, and described second solid matter comprises described first nitrogenated silicon hydride compounds generates high α phase content silicon nitride through heating;
Eluting column 3, eluting column 3 comprises the first opening for feed 33 of eluting column and the second opening for feed 34 of eluting column, first opening for feed 33 of eluting column is connected with described heating unit 2, described second gaseous mixture enters described eluting column 3, described eluting column 3 carries out drip washing for passing into the second chlorosilane to described second gaseous mixture, obtain the 3rd solid mixture and the 3rd gaseous matter, wherein, described 3rd solid mixture comprises the second nitrogenated silicon hydride compounds and the second ammonium chloride that the ammonia gas react in described second chlorosilane and described second gaseous mixture generates, described 3rd gaseous matter comprises hydrogenchloride.
The ammonia generated in preparation process recycling can be reacted with the second chlorosilane by the system of the production silicon nitride of the present embodiment, has regenerated the intermediate second nitrogenated silicon hydride compounds prepared needed for silicon nitride, thus has saved cost.
Reaction in first reactor 1 is gas solid/liquid/gas reactions, and the flow of unstripped gas and reaction are all easy to control.
The nitrogenated silicon hydride compounds of the present embodiment, generally also referred to as silicon diimine, easily absorbs or exists with Si-N-H based compound form after releasing ammonia, the most available Si (NH) of nitrogenated silicon hydride compounds
2formula represents, Si (NH)
2be not a concrete material, this compounds can be Si
6n
13h
15, Si
6n
12h
12, Si
6n
11h
9deng.
Carrier gas in described first reactor 1 is the one in nitrogen, ammonia, rare gas element, is diluted reaction raw material used by carrier gas.
Chlorosilane carrier gas passes into, and preferred carrier gas is nitrogen, and the flow controlling nitrogen is more than 2 times of the first chlorosilane, to control speed of response and to prevent the system of producing silicon nitride from occurring line clogging.
Preferably, described first chlorosilane is one or more in silicon tetrachloride, trichlorosilane, dichlorosilane.
Raw material first chlorosilane adopted and raw material first ammonia purity all 99.99% and more than, other first ammonia and carrier gas all will carry out processed.
Preferably, in described first reactor 1, the temperature of described heating carrier gas Raw first chlorosilane and raw material first ammonia gas react is 10 ~ 100 DEG C, and pressure is 0 ~ 1MPa.
Preferably, in described first reactor 1, the mol ratio of described first chlorosilane and described first ammonia is 1:(6 ~ 30).The excessive chlorosilane that can make of ammonia reacts completely.
Preferably, the tower reactor 31 of described eluting column is connected with the entrance of described heating unit 2, and described 3rd solid mixture enters described heating unit 2.Then described 3rd solid mixture mixes with described first solid mixture, the reaction in heating unit 2 described in recirculation.
Preferably, described heating unit 2 comprises:
Primary heater 4, comprise the entrance 41 of primary heater, first outlet 42 of primary heater, second outlet 43 of primary heater, the entrance 41 of primary heater is connected with described first reactor 1, described first solid mixture in described first reactor 1 enters described primary heater 4, under non-oxidizing atmosphere, heat described first solid mixture reaction, obtain the 4th solid mixture and the 4th gaseous mixture, described 4th gaseous mixture comprises the gas of the described non-oxidizing atmosphere in described primary heater 4, the ammonia that described first ammonium chloride generation thermolysis generates and hydrogenchloride, described 4th solid mixture comprises described first nitrogenated silicon hydride compounds, by product first ammonium chloride is eliminated by this step, first outlet 42 of described primary heater is connected with the first opening for feed 33 of described eluting column, and described 4th gaseous mixture exports through first of described primary heater the first opening for feed 33 that 42 enter described eluting column.
Secondary heater 5, comprise the entrance 51 of secondary heater, first outlet 52 of secondary heater, second outlet 53 of secondary heater, the entrance 51 of described secondary heater and second of described primary heater exports 43 and is connected, described 4th solid mixture in described primary heater 4 enters in described secondary heater 5, under ammonia atmosphere, heat described 4th solid mixture, obtain the 5th solid mixture and the 5th gaseous mixture, described 5th solid mixture comprises described first nitrogenated silicon hydride compounds generation thermolysis and generates unbodied silicon nitride, described 5th gaseous mixture comprises the gas of ammonia atmosphere, hydrogenchloride, the ammonia that described first nitrogenated silicon hydride compounds generation thermolysis generates, first outlet 52 of described secondary heater is connected with the first opening for feed 33 of described eluting column, described 5th gaseous mixture exports through first of described secondary heater the first opening for feed 33 that 52 enter described eluting column, described ammonia atmosphere can enter the inside of described 4th solid mixture or the 5th solid mixture, the chlorine element that removing is wherein inner, avoids liquefied ammonia washing in prior art and, except the method for dechlorination element, greatly simplify the Production Flow Chart of silicon nitride.First outlet 42 of primary heater, the first outlet 52 of secondary heater are all connected with the first opening for feed 33 of eluting column, can reclaim the ammonia in the 4th gaseous mixture and the 5th gaseous mixture simultaneously, reduce processing cost.
3rd well heater 6, export 53 with second of described secondary heater to be connected, described 5th solid mixture in described secondary heater 5 enters in described 3rd well heater 6, under non-oxidizing atmosphere, heat described 5th solid mixture, obtain described second solid matter and described second gaseous mixture, described unbodied silicon nitride generates the silicon nitride of high α phase content through heating.
Preferably, in described primary heater 4, the temperature of the described first solid mixture reaction of described heating is 500 ~ 600 DEG C, and heat-up time is 1 ~ 2 hour;
In described secondary heater 5, the temperature of described 4th solid mixture of described heating is 650 ~ 1200 DEG C, and heat-up time is 2 ~ 8 hours;
In described 3rd well heater 6, the temperature of described 5th solid mixture of described heating is 1250 ~ 1700 DEG C, and heat-up time is 2 ~ 8 hours.
Preferably, in described 3rd well heater 6, the temperature of described 5th solid mixture of described heating is 1350 ~ 1600 DEG C, and temperature is too low, then the phase in version time is long, and temperature is too high, then easily promote the content of β phase in silicon nitride.
Preferably, the system of described production silicon nitride also comprises:
Second reactor 7, comprise the entrance 71 of the second reactor and the outlet 72 of the second reactor, the entrance 71 of described second reactor is connected with the tower top 32 of described eluting column, described 3rd gaseous matter enters described second reactor 7 by the tower top 32 of described eluting column, described second reactor 7 is for passing into silica flour and described 3rd gaseous matter reacting by heating obtains trichlorosilane, the outlet 72 of described second reactor is connected with the entrance of described first reactor 1, and described trichlorosilane enters in described first reactor 1.Then described trichlorosilane mixes with described first chlorosilane, repeats the reaction in described first reactor 1, is reused for the production of silicon nitride.
Preferably, described second reactor 7 is 300 ~ 500 DEG C for the temperature of reaction passing into silica flour and described 3rd gaseous matter reacting by heating and obtain trichlorosilane, more preferably, 325 ~ 400 DEG C, by controlling the temperature of reaction, each component can be regulated in the trichlorosilane product of generation as the content of silicon tetrachloride, trichlorosilane.
Product trichlorosilane in second reactor 7 is also the raw material of production of polysilicon, and therefore this product can be incorporated in polycrystalline silicon production system, realizes the coproduction of silicon nitride and polysilicon, reduces costs further.
Preferably, the system of described production silicon nitride also comprises:
Rectifier unit 8, comprise the entrance 81 of rectifier unit and the outlet 82 of rectifier unit, the entrance 81 of described rectifier unit is connected with the outlet 72 of described second reactor, the outlet 82 of described rectifier unit is connected with the entrance 13 of described first reactor, and described rectifier unit 8 is for carrying out rectification and purification to described trichlorosilane.
Preferably, the outlet 72 of described second reactor is also connected with the second opening for feed 34 of eluting column, and described trichlorosilane enters in described eluting column 3 for drip washing.Then described trichlorosilane mixes with described second chlorosilane, repeats the drip washing in described eluting column 3.
As shown in Figure 3, preferably, the system of described production silicon nitride also comprises:
Strainer 9, comprise the entrance 91 of strainer, first outlet 92 of strainer, second outlet 93 of strainer, the entrance 91 of described strainer is connected with the first reactor 1, the first gaseous mixture in described first reactor 1 and part first solid mixture enter described strainer 9, described first solid mixture of part that described strainer 9 obtains separating for gas-solid filtering separation and described first gaseous mixture, first outlet 92 of described strainer is connected with described heating unit 2, described first solid mixture of part enters described heating unit 2 by the first outlet 92 of described strainer, second outlet 93 of described strainer is connected with described first reactor 1, described first gaseous mixture enters described first reactor 1 by the second outlet 93 of described strainer.Described first solid mixture generated in first reactor 1 is deposited in the bottom of the first reactor 1, and part is taken out of strainer 9 by unreacted ammonia.First solid mixture of the bottom of the first reactor 1 can be discharged continuously, also can steply discharge.
Preferably, the system of described production silicon nitride also comprises:
Water cooler 10, comprise the entrance 101 of water cooler, the first outlet 102 of water cooler, the second outlet 103 of water cooler, the entrance 101 of described water cooler and second of described strainer exports 93 and is connected, described first gaseous mixture enters described water cooler 10 by the second outlet 93 of described strainer, and described water cooler 10 cools the liquefied ammonia and carrier gas that obtain for the first ammonia that gas gas refrigerated separation obtains separating; Temperature in described water cooler 10 is-35 ~-50 DEG C.
Carrier gas reservoir 11, comprise the entrance 111 of carrier gas reservoir and the outlet 112 of carrier gas reservoir, the entrance 111 of described carrier gas reservoir and first of described water cooler exports 102 and is connected, carrier gas in described water cooler 10 enters into the entrance 111 of described carrier gas reservoir by the first outlet 102 of described water cooler, and the outlet 112 of described carrier gas reservoir is connected with described first reactor 1; Carrier gas in carrier gas reservoir 11 is reused for the carrier gas in the first reactor 1.
Liquid ammonia storage tank 12, comprise the entrance 121 of liquid ammonia storage tank and the outlet 122 of liquid ammonia storage tank, the entrance 121 of described liquid ammonia storage tank and second of described water cooler exports 103 and is connected, liquefied ammonia in described water cooler 10 enters into the entrance 121 of described liquid ammonia storage tank by the second outlet 103 of described water cooler, and the outlet 122 of described liquid ammonia storage tank is connected with described first reactor 1.Certainly, the liquefied ammonia in liquid ammonia storage tank 12 also can be used as the protective atmosphere in heating unit 2.
Preferably, described second chlorosilane is one or more in silicon tetrachloride, trichlorosilane, dichlorosilane.
Preferably, described trichlorosilane is one or more in silicon tetrachloride, trichlorosilane, dichlorosilane.
The system of the production silicon nitride of the present embodiment can realize the continuous prodution of intermediate first nitrogenated silicon hydride compounds, the production of whole silicon nitride is closed loop process, by product and unreacted reactant obtain recycling, needing the raw material supplemented for being only silica flour and ammonia, significantly can reduce the production cost of silicon nitride.
Embodiment 3
The present embodiment provides a kind of system of the production silicon nitride used in embodiment 2 to prepare the method for silicon nitride, comprises the following steps:
(1) at volume be 4L reactor in be first full of the ammonia of 0.1MPa.Controlling ammonia flow velocity is 320mL/min, adds the silicon tetrachloride gas of 40mL/min in reactor.By the constant pressure in back pressure valve control reactor at 0.1MPa, controlling internal temperature by thermoswitch is 100 DEG C.Lower pass into gas speed under, the silicon diimine of generation is substantially all deposited in the bottom of reactor.After reaction 1h, obtain loose silicon diimine that weight is 28.3g and ammonium chloride mixed powder in the bottom of reactor.
(2) the silicon diimine pressed powder obtained is placed in tube furnace and heat-treats 1h, thermal treatment temp is 550 DEG C, and protective atmosphere is ammonia, to remove the ammonium chloride on silicon diimine surface.After thermal treatment, obtain thick silicon diimine pressed powder 6.1g, Cl content is wherein 200ppm.
(3), after thick silicon diimine powder simply being ground, put into tube furnace and carry out high temperature pyrolysis process.During thermal treatment, heat up from 650 DEG C, after 1h is warming up to 1100 DEG C, be incubated 4h again, whole process is using ammonia as protective atmosphere.After pyrolysis processing, obtain unbodied alpha-silicon nitride powders.After testing, the cl content in silicon nitride is down to 45ppm.
(4) finally unbodied alpha-silicon nitride powders is carried out high-temperature phase-transitional process, 4h is incubated at the temperature of 1400 DEG C, obtain silicon nitride product, after grinding, α phase silicon nitride content in silicon nitride product is 96.5wt%, metals content impurity <30ppm, cl content is 45ppm, and oxygen level is 0.8wt%.
Collect tail gas during silicon diimine thermal treatment, and keep the temperature of tail gas at 550 DEG C.Then in tail gas, spray into the silicon tetrachloride of exhaust gas volumes than 2 times and trichlorosilane mixture, wherein the mol ratio of silicon tetrachloride and trichlorosilane is 1:1, make the ammonia in tail gas completely and chlorosilane react and generate silicon diimine.By gas chromatographic detection, only containing HCl in reacted gas, ammonia level does not detect.Adopt the silicon diimine obtained and originally execute heat treatment step same in example, finally obtain silicon nitride product, after grinding, its α phase content is 92.7wt%, metals content impurity <35ppm, and cl content is 140ppm, and oxygen level is 0.6wt%.
Collect the HCl tail gas after chlorosilane drip washing, react with silica flour generation chlorosilane in a fluidized bed reactor, and the temperature controlling reactor is 350 DEG C, after reaction, in the chlorosilane of generation, silicon tetrachloride accounts for 14.4wt%, and trichlorosilane accounts for 85.0wt%,, dichlorosilane accounts for 0.6wt%.
Collect the HCl tail gas after chlorosilane drip washing, react with silica flour generation chlorosilane in a fluidized bed reactor, and the temperature controlling reactor is 450 DEG C, after reaction, in the chlorosilane generated, silicon tetrachloride accounts for 57.6wt%, and trichlorosilane accounts for 41.4wt%, and dichlorosilane accounts for 1.0wt%.
Be understandable that, the illustrative embodiments that above embodiment is only used to principle of the present utility model is described and adopts, but the utility model is not limited thereto.For those skilled in the art, when not departing from spirit of the present utility model and essence, can make various modification and improvement, these modification and improvement are also considered as protection domain of the present utility model.
Claims (10)
1. produce a system for silicon nitride, it is characterized in that, comprising:
First reactor, for carrier gas Raw first chlorosilane and raw material first ammonia gas react, obtain the first solid mixture and the first gaseous mixture, wherein, described first solid mixture comprises the first nitrogenated silicon hydride compounds and the first ammonium chloride that described first chlorosilane and described first ammonia gas react generate, and described first gaseous mixture comprises carrier gas and the first ammonia;
Heating unit, be connected with described first reactor, described first solid mixture in described first reactor enters described heating unit, described heating unit is for heating described first solid mixture reaction, obtain the second solid matter and the second gaseous mixture, wherein, described second gaseous mixture comprises described first ammonium chloride through heating the ammonia and hydrogenchloride that generate, and described second solid matter comprises described first nitrogenated silicon hydride compounds through heating the silicon nitride of the high α phase content generated;
Eluting column, be connected with described heating unit, described second gaseous mixture enters described eluting column, described eluting column is used for passing into the second chlorosilane and carries out drip washing to described second gaseous mixture, obtain the 3rd solid mixture and the 3rd gaseous matter, wherein, described 3rd solid mixture comprises the second nitrogenated silicon hydride compounds and the second ammonium chloride that the ammonia gas react in described second chlorosilane and described second gaseous mixture generates, and described 3rd gaseous matter comprises hydrogenchloride.
2. the system of production silicon nitride according to claim 1, is characterized in that, the tower reactor of described eluting column is connected with the entrance of described heating unit, enters described heating unit for described 3rd solid mixture.
3. the system of production silicon nitride according to claim 1, is characterized in that, described heating unit comprises:
Primary heater, comprise the entrance of primary heater, first outlet of primary heater, second outlet of primary heater, the entrance of described primary heater is connected with described first reactor, described primary heater is entered for described first solid mixture in described first reactor, under non-oxidizing atmosphere, heat described first solid mixture reaction, obtain the 4th solid mixture and the 4th gaseous mixture, described 4th gaseous mixture comprises the gas of the described non-oxidizing atmosphere in described primary heater, the ammonia that described first ammonium chloride generation thermolysis generates and hydrogenchloride, described 4th solid mixture comprises described first nitrogenated silicon hydride compounds, first outlet of described primary heater is connected with described eluting column, described 4th gaseous mixture enters described eluting column through the first outlet of described primary heater,
Secondary heater, comprise the entrance of secondary heater, first outlet of secondary heater, second outlet of secondary heater, the entrance of described secondary heater and second of described primary heater exports and is connected, enter in described secondary heater for described 4th solid mixture in described primary heater, under ammonia atmosphere, heat described 4th solid mixture, obtain the 5th solid mixture and the 5th gaseous mixture, described 5th solid mixture comprises described first nitrogenated silicon hydride compounds generation thermolysis and generates unbodied silicon nitride, described 5th gaseous mixture comprises the gas of ammonia atmosphere, hydrogenchloride, the ammonia that described first nitrogenated silicon hydride compounds generation thermolysis generates, first outlet of described secondary heater is connected with described eluting column, described 5th gaseous mixture enters described eluting column through the first outlet of described secondary heater,
3rd well heater, export with second of described secondary heater and be connected, described 5th solid mixture in described secondary heater enters in described 3rd well heater, for under non-oxidizing atmosphere, heat described 5th solid mixture, obtain described second solid matter and described second gaseous mixture, described unbodied silicon nitride generates the silicon nitride of high α phase content through heating.
4. the system of production silicon nitride according to claim 1, is characterized in that, also comprise:
Second reactor, comprise the entrance of the second reactor and the outlet of the second reactor, the entrance of described second reactor is connected with the tower top of described eluting column, described second reactor is entered by the tower top of described eluting column for described 3rd gaseous matter, described second reactor is used for passing into silica flour and described 3rd gaseous matter reacting by heating obtains trichlorosilane, the outlet of described second reactor is connected with described first reactor, and described trichlorosilane enters in described first reactor.
5. the system of production silicon nitride according to claim 4, is characterized in that, also comprise:
Rectifier unit, comprise the entrance of rectifier unit and the outlet of rectifier unit, the entrance of described rectifier unit is connected with the outlet of described second reactor, the outlet of described rectifier unit is connected with described first reactor, described rectifier unit is used for carrying out rectification and purification to described trichlorosilane, and purified trichlorosilane enters described first reactor.
6. the system of production silicon nitride according to claim 4, is characterized in that, the outlet of described second reactor is also connected with described eluting column, enters in described eluting column for drip washing for described trichlorosilane.
7. the system of production silicon nitride according to claim 1, is characterized in that, also comprise:
Strainer, comprise the entrance of strainer, first outlet of strainer, second outlet of strainer, the entrance of described strainer is connected with described first reactor, the first gaseous mixture in described first reactor and part first solid mixture enter described strainer, described strainer is used for gas-solid filtering separation described first solid mixture of part that obtains separating and described first gaseous mixture, first outlet of described strainer is connected with described heating unit, described first solid mixture of part enters described heating unit by the first outlet of described strainer, second outlet of described strainer is connected with described first reactor, described first gaseous mixture enters described first reactor by the second outlet of described strainer.
8. the system of production silicon nitride according to claim 7, is characterized in that, also comprise:
Water cooler, comprise the entrance of water cooler, the first outlet of water cooler, the second outlet of water cooler, the entrance of described water cooler and second of described strainer exports and is connected, enter described water cooler for described first gaseous mixture by the second outlet of described strainer, described water cooler is used for refrigerated separation and obtains liquefied ammonia and carrier gas.
9. the system of production silicon nitride according to claim 8, is characterized in that, also comprise:
Carrier gas reservoir, comprise the entrance of carrier gas reservoir and the outlet of carrier gas reservoir, the entrance of described carrier gas reservoir and first of described water cooler exports and is connected, entered into the entrance of described carrier gas reservoir by the first outlet of described water cooler for the carrier gas in described water cooler, the outlet of described carrier gas reservoir is connected with described first reactor.
10. the system of production silicon nitride according to claim 8, is characterized in that, also comprise:
Liquid ammonia storage tank, comprise the entrance of liquid ammonia storage tank and the outlet of liquid ammonia storage tank, the entrance of described liquid ammonia storage tank and second of described water cooler exports and is connected, entered into the entrance of described liquid ammonia storage tank by the second outlet of described water cooler for the liquefied ammonia in described water cooler, the outlet of described liquid ammonia storage tank is connected with described first reactor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672922A (en) * | 2015-11-11 | 2017-05-17 | 新特能源股份有限公司 | System for producing silicon nitride |
| CN113148965A (en) * | 2021-04-20 | 2021-07-23 | 安徽工业大学 | Suspension reactor for synthesizing silicon nitride powder |
-
2015
- 2015-11-11 CN CN201520897686.9U patent/CN205099363U/en not_active Withdrawn - After Issue
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672922A (en) * | 2015-11-11 | 2017-05-17 | 新特能源股份有限公司 | System for producing silicon nitride |
| CN106672922B (en) * | 2015-11-11 | 2019-01-22 | 新疆晶硕新材料有限公司 | A kind of system producing silicon nitride |
| CN113148965A (en) * | 2021-04-20 | 2021-07-23 | 安徽工业大学 | Suspension reactor for synthesizing silicon nitride powder |
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