CN106672922B - A kind of system producing silicon nitride - Google Patents
A kind of system producing silicon nitride Download PDFInfo
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- CN106672922B CN106672922B CN201510768516.5A CN201510768516A CN106672922B CN 106672922 B CN106672922 B CN 106672922B CN 201510768516 A CN201510768516 A CN 201510768516A CN 106672922 B CN106672922 B CN 106672922B
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Abstract
The invention discloses a kind of systems for producing silicon nitride, comprising: first reactor；Heating device, the heating device are connect with the first reactor；Eluting column, the first charging aperture of the eluting column are connect with the heating device.The system can recycle the ammonia generated in preparation process reacts with the second chlorosilane, the nitrogenous silane compound of intermediate second needed for preparing silicon nitride has been regenerated, to save cost.
Description
Technical field
The invention belongs to silicon nitride production technical fields, and in particular to a kind of system for producing silicon nitride.
Background technique
Silicon nitride has that high mechanical strength, thermal stability be good, good chemical stability, in modern technologies often
High temperature, high speed, strong corrosive medium and the high working environment worn encountered, has special purposes.Silicon nitride is industrially
Have many uses general, can be applied to metallurgy, machinery, chemical industry, semiconductor, aerospace and auto industry field, as turbo blade,
High-temperature bearing, high-speed cutting tool, heat-resistant part, abrasion-proof corrosion-proof component etc..With silicon nitride application range it is continuous expansion and
The preparation of continuous improvement to silicon nitride quality requirements, beta-silicon nitride powder is increasingly taken seriously.
There are four types of the silicon nitride technologies of preparing of commercial applications: (1) silicon powder direct nitridation method, including low-voltage high-temperature nitrogen
Change and high pressure self- propagating nitrogenizes；(2) redox reaction generation is occurred in nitrogen by silica and carbon dust for carbothermic method
Silicon nitride；(3) low temperature silane thermal decomposition process generates the nitrogenous silane compound Si (NH) of intermediate product by silicon tetrachloride and ammonia2, then again
Pyrolysis is silicon nitride；(4) high temperature silane thermal decomposition process is directly reacted with ammonia at high temperature by silicon tetrachloride or monosilane and generates nitrogen
SiClx.In the above-mentioned methods, low temperature silane thermal decomposition process and the purification easy to accomplish to raw material of high temperature silane thermal decomposition process, are suitable for high purity silicon nitride
The preparation of silicon powder.But in high temperature silane thermal decomposition process, monosilane is inflammable and explosive, and risk is high, and when using silicon tetrachloride as raw material, need
The technologies such as using plasma, laser are wanted to carry out reaction reinforcing, investment is big, and low yield is at high cost.
Silicon nitride prepared by low temperature silane thermal decomposition process is generally received with its high quality by people, but nitrogenated silicon in low temperature silane thermal decomposition process
Hydride compounds synthesize strongly exothermic fast reaction, and entrainment chlorine element is easy in nitrogenous silane compound, therefore its life at present
It produces and is generally reacted using the liquid-liquid interface of silicon tetrachloride and ammonia to control reaction speed, then wash away ammonium chloride with a large amount of liquefied ammonia again
The method of by-product obtains pure nitrogenous silane compound, and last reheating is decomposed into silicon nitride.Liquid-liquid interface reaction rate is slow,
Complex process, production capacity is low, its cost is caused to remain high always.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of production nitrogen
The system of SiClx, which can recycle the ammonia generated in preparation process reacts with the second chlorosilane, regenerates
The nitrogenous silane compound of intermediate second needed for preparing silicon nitride, to save cost.
It solves technical solution used by present invention problem and is to provide a kind of system for producing silicon nitride, comprising:
First reactor is reacted for the first chlorosilane of raw material in carrier gas with the first ammonia of raw material, and it is mixed to obtain the first solid
Close object and first gas mixture, wherein first solid mixture includes first chlorosilane and first ammonia
The the first nitrogenous silane compound and the first ammonium chloride generated is reacted, the first gas mixture includes carrier gas and the first ammonia
Gas；
Heating device is connect with the first reactor, first solid mixture in the first reactor into
Enter the heating device, the heating device for heating the first solid mixture reaction, obtain the second solid matter and
Second gas mixture, wherein ammonia that the second gas mixture, which includes first ammonium chloride, to be generated by heating and
Hydrogen chloride, second solid matter include the nitrogen for the high α phase content that the described first nitrogenous silane compound is generated by heating
SiClx；
Eluting column is connect with the heating device, and the second gas mixture enters the eluting column, the eluting column
The second gas mixture is eluted for being passed through the second chlorosilane, obtains third solid mixture and third gas object
Matter, wherein the third solid mixture includes that second chlorosilane is reacted with the ammonia in the second gas mixture
The the second nitrogenous silane compound and the second ammonium chloride generated, the third gas substance includes hydrogen chloride.
The system of production silicon nitride of the invention can recycle the ammonia generated in preparation process and the second chlorosilane
Reaction, has regenerated the nitrogenous silane compound of intermediate second needed for preparing silicon nitride, to save cost.
Reaction in first reactor is gas solid/liquid/gas reactions, and the flow of unstripped gas and reaction are easily controlled.
Nitrogenous silane compound of the invention is also commonly referred to as silicon diimine, is easy after absorption or releasing ammonia with Si-N-H
Based compound form exists, and nitrogenous silane compound majority can use Si (NH)2Formula expression, Si (NH)2It is not a specific object
Matter, such compound can be Si6N13H15、Si6N12H12、Si6N11H9Deng.
Carrier gas in the first reactor is one of nitrogen, ammonia, inert gas, by carrier gas to used in reaction
Raw material be diluted.
Chlorosilane is passed through with carrier gas, and preferred carrier gas is nitrogen, and the flow for controlling nitrogen be 2 times of the first chlorosilane with
On, to control reaction speed and prevent the system for producing silicon nitride from line clogging occur.
Preferably, first chlorosilane is one or more of silicon tetrachloride, trichlorosilane, dichlorosilane.
Used the first chlorosilane of raw material and the first ammonia of raw material purity are 99.99% or more, other the first ammonia
Gas and carrier gas are intended to be carried out dehydrating.
Preferably, in the first reactor, the first chlorosilane of raw material and the first ammonia of raw material in the heating carrier gas
The temperature of reaction is 10~100 DEG C, and pressure is 0~1MPa.
Preferably, in the first reactor, the molar ratio of first chlorosilane and first ammonia is 1:(6
~30).Ammonia can excessively make chlorosilane fully reacting.
Preferably, the tower reactor of the eluting column is connect with the entrance of the heating device, mixed for the third solid
It closes object and enters the heating device.Then the third solid mixture is mixed with first solid mixture, repetitive cycling institute
State the reaction in heating device.
Preferably, the heating device includes:
Primary heater, the second of the first outlet of entrance, primary heater including primary heater, primary heater
Outlet, the entrance of the primary heater is connect with the first reactor, for described first in the first reactor
Solid mixture enters the primary heater, under non-oxidizing atmosphere, heats the first solid mixture reaction, obtains
4th solid mixture and the 4th admixture of gas, the 4th admixture of gas include described non-in the primary heater
The ammonia and hydrogen chloride that the gas of oxidizing atmosphere, first ammonium chloride thermally decompose to generate, the 4th solid mixing
Object includes the described first nitrogenous silane compound, eliminates the first ammonium chloride of by-product by the step, the primary heater
First outlet is connect with the eluting column, and the 4th admixture of gas enters institute by the first outlet of the primary heater
State eluting column；
Secondary heater, the second of the first outlet of entrance, secondary heater including secondary heater, secondary heater
Outlet, the entrance of the secondary heater are connect with the second outlet of the primary heater, in the primary heater
The 4th solid mixture enter in the secondary heater, under ammonia atmosphere, heat the 4th solid mixture,
The 5th solid mixture and the 5th admixture of gas are obtained, the 5th solid mixture includes that the described first nitrogenous silanization closes
Object thermally decomposes to generate unbodied silicon nitride, and the 5th admixture of gas includes the gas, hydrogen chloride, institute of ammonia atmosphere
State the ammonia that the first nitrogenous silane compound thermally decomposes to generate, the first outlet of the secondary heater and the eluting column
Connection, the 5th admixture of gas enter the eluting column by the first outlet of the secondary heater；Described first contains
The ammonia that nitrogen silane compound thermally decomposes to generate enters the inside of the first nitrogenous silane compound, removes wherein internal chlorine
Element avoids the method that liquefied ammonia washing removes chlorine element in the prior art, greatlies simplify the production procedure of silicon nitride.First
The first outlet of heater, the first outlet of secondary heater are connect with eluting column, can recycle the 4th gas mixing simultaneously
Ammonia in object and the 5th admixture of gas reduces processing cost.
Third heater is connect with the second outlet of the secondary heater, and the in the secondary heater the described 5th
Solid mixture enters in the third heater, for heating the 5th solid mixture, obtaining under non-oxidizing atmosphere
To second solid matter and the second gas mixture, the unbodied silicon nitride generates high α phase by heating and contains
The silicon nitride of amount.
Preferably, in the primary heater, the temperature of the heating first solid mixture reaction is 500~
600 DEG C, heating time is 1~2 hour；
In the secondary heater, the temperature of the heating the 4th solid mixture is 650~1200 DEG C, when heating
Between be 2~8 hours；
In the third heater, the temperature of heating the 5th solid mixture is 1250~1700 DEG C, heating
Time is 2~8 hours.
Preferably, in the third heater, the temperature of the heating the 5th solid mixture is 1350~
1600 DEG C, temperature is too low, then the phase transition time is long, and temperature is excessively high, then is easy to promote the content of β phase in silicon nitride.
Preferably, the system of the production silicon nitride further include:
Second reactor, the outlet of entrance and second reactor including second reactor, the second reactor enter
Mouth is connect with the tower top of the eluting column, enters described second instead by the tower top of the eluting column for the third gas substance
Device is answered, the second reactor reacts to obtain third chlorosilane for being passed through silicon powder with third gas substance heating, described
The outlet of second reactor and the entrance of first reactor connect, and the third chlorosilane enters in the first reactor.Then
The third chlorosilane is mixed with first chlorosilane, is repeated the reaction in the first reactor, is reused for silicon nitride
Production.
Preferably, the second reactor reacts to obtain third for being passed through silicon powder with third gas substance heating
The reaction temperature of chlorosilane is 300~500 DEG C, it is further preferred that 325~400 DEG C, by the temperature of control reaction, can adjust
Save the content of each component such as silicon tetrachloride, trichlorosilane in the third chlorosilane product generated.The chlorine that will can be generated in the process
Change hydrogen recycling reacted with silicon powder regenerate prepare silicon nitride needed for raw chlorsilane.
Product third chlorosilane in second reactor is also the raw material of production of polysilicon, therefore the product can be incorporated into
In polycrystalline silicon production system, realizes the coproduction of silicon nitride and polysilicon, further reduce the cost.
Preferably, the system of the production silicon nitride further include:
Rectifier unit, the outlet of entrance and rectifier unit including rectifier unit, the entrance of the rectifier unit with it is described
The outlet of second reactor connects, and the outlet of the rectifier unit and the entrance of first reactor connect, and the rectifier unit is used
In carrying out rectification and purification to the third chlorosilane, purified third chlorosilane enters the first reactor.
Preferably, the outlet of the second reactor is also connect with eluting column, enters institute for the third chlorosilane
It states in eluting column for eluting.Then the third chlorosilane is mixed with second chlorosilane, repeats the leaching in the eluting column
It washes.
Preferably, the system of the production silicon nitride further include:
Filter, first outlet, the second outlet of filter of entrance, filter including filter, the filter
Entrance connect with first reactor, the first solid mixture of first gas mixture and part in the first reactor
Into the filter, the filter for gas-solid be separated by filtration the part separated first solid mixture and
The first gas mixture, the first outlet of the filter are connect with the heating device, and part first solid is mixed
It closes object and the heating device is entered by the first outlet of the filter, the second outlet of the filter is anti-with described first
Device is answered to connect, the first gas mixture enters the first reactor by the second outlet of the filter.First is anti-
It answers first solid mixture generated in device to be deposited in first reactor bottom, is partially taken out of by unreacted ammonia to mistake
Filter.First solid mixture of the bottom of first reactor can continuously be discharged, discharge that can also be intermittent.
Preferably, the system of the production silicon nitride further include:
Cooler, first outlet, the second outlet of cooler of entrance, cooler including cooler, the cooler
Entrance connect with the second outlet of the filter, for the first gas mixture second going out by the filter
Mouth enters the cooler, and the cooler obtains liquefied ammonia and carrier gas for refrigerated separation；Temperature in the cooler is -35
~-50 DEG C.
Carrier gas reservoir, the outlet of entrance and carrier gas reservoir including carrier gas reservoir, the entrance of the carrier gas reservoir with it is described
The first outlet of cooler connects, entered for the carrier gas in the cooler by the first outlet of the cooler described in
The entrance of carrier gas reservoir, the outlet of the carrier gas reservoir are connect with the first reactor；Carrier gas in carrier gas reservoir is used again
In the carrier gas in first reactor.
Liquid ammonia storage tank, the outlet of entrance and liquid ammonia storage tank including liquid ammonia storage tank, the entrance of the liquid ammonia storage tank with it is described
The second outlet of cooler connects, entered for the liquefied ammonia in the cooler by the second outlet of the cooler described in
The entrance of liquid ammonia storage tank, the outlet of the liquid ammonia storage tank are connect with the first reactor.Certainly, the liquefied ammonia in liquid ammonia storage tank
It may be used as the protective atmosphere in heating device.
Preferably, second chlorosilane is one or more of silicon tetrachloride, trichlorosilane, dichlorosilane.
Preferably, the third chlorosilane is one or more of silicon tetrachloride, trichlorosilane, dichlorosilane.
The continuous production of the nitrogenous silane compound of intermediate first may be implemented in the system of production silicon nitride of the invention,
Entire silicon nitride is produced as closed loop process, and by-product and unreacted reactant are recycled, the original required supplementation with
The production cost of silicon nitride can be greatly reduced to be only silicon powder and ammonia in material.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the system of the production silicon nitride in the embodiment of the present invention 1,2；
Fig. 2 is the structural schematic diagram of the system of the production silicon nitride in the embodiment of the present invention 2；
Fig. 3 is the partial structure diagram of the system of the production silicon nitride in the embodiment of the present invention 2.
In figure: 1- first reactor；2- heating device；3- eluting column；The tower reactor of 31- eluting column；The tower of 32- eluting column
Top；The first charging aperture of 33- eluting column；The second charging aperture of 34- eluting column；4- primary heater；41- primary heater enters
Mouthful；The first outlet of 42- primary heater；The second outlet of 43- primary heater；5- secondary heater；51- secondary heater
Entrance；The first outlet of 52- secondary heater；The second outlet of 53- secondary heater；6- third heater；7- second is anti-
Answer device；The entrance of 71- second reactor；The outlet of 72- second reactor；8- rectifier unit；The entrance of 81- rectifier unit；82-
The outlet of rectifier unit；9- filter；The entrance of 91- filter；The first outlet of 92- filter；The second of 93- filter goes out
Mouthful；10- cooler；The entrance of 101- cooler；The first outlet of 102- cooler；The second outlet of 103- cooler；11- is carried
Gas storage tank；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.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing and specific embodiment party
Present invention is further described in detail for formula.
Embodiment 1
As shown in Figure 1, technical solution used by the present embodiment technical problem is to provide a kind of system for producing silicon nitride,
Include:
First reactor 1 is reacted for heating in carrier gas the first chlorosilane of raw material with the first ammonia of raw material, and it is solid to obtain first
Body mixture and first gas mixture, wherein first solid mixture includes first chlorosilane and described first
The the first nitrogenous silane compound and the first ammonium chloride that ammonia reaction generates, the first gas mixture includes carrier gas and first
Ammonia；
Heating device 2 is connect with the first reactor 1, first solid mixture in the first reactor 1
Into the heating device 2, the heating device 2 obtains the second solids for heating the first solid mixture reaction
Matter and second gas mixture, wherein the second gas mixture includes the ammonia that first ammonium chloride is generated by heating
Gas and hydrogen chloride, second solid matter include the high α phase content that the described first nitrogenous silane compound is generated by heating
Silicon nitride；
Eluting column 3 is connect with the heating device 2, and the second gas mixture enters the eluting column 3, the leaching
It washes tower 3 to elute the second gas mixture for being passed through the second chlorosilane, obtains third solid mixture and third
Gaseous matter, wherein the third solid mixture includes the ammonia in second chlorosilane and the second gas mixture
The the second nitrogenous silane compound and the second ammonium chloride that solid/liquid/gas reactions generate, the third gas substance includes hydrogen chloride.
Reaction in first reactor 1 is gas solid/liquid/gas reactions, and the flow of unstripped gas and reaction are easily controlled.
The nitrogenous silane compound of the present embodiment is also commonly referred to as silicon diimine, is easy after absorption or releasing ammonia with Si-
N-H based compound form exists, and nitrogenous silane compound majority can use Si (NH)2Formula expression, Si (NH)2It is not one specific
Substance, such compound can be Si6N13H15、Si6N12H12、Si6N11H9Deng.
Carrier gas in the first reactor 1 is one of nitrogen, ammonia, inert gas, by carrier gas to reaction institute
Raw material is diluted.
Chlorosilane is passed through with carrier gas, and preferred carrier gas is nitrogen, and the flow for controlling nitrogen be 2 times of the first chlorosilane with
On, to control reaction speed and prevent the system for producing silicon nitride from line clogging occur.
The system of the production silicon nitride of the present embodiment can recycle the ammonia generated in preparation process and the second chlorine silicon
Alkane reaction, has regenerated the nitrogenous silane compound of intermediate second needed for preparing silicon nitride, to save cost.
Embodiment 2
As shown in Figure 1, 2, technical solution used by the present embodiment technical problem be to provide it is a kind of produce silicon nitride be
System, comprising:
First reactor 1 is reacted for heating in carrier gas the first chlorosilane of raw material with the first ammonia of raw material, and it is solid to obtain first
Body mixture and first gas mixture, wherein first solid mixture includes first chlorosilane and described first
The the first nitrogenous silane compound and the first ammonium chloride that ammonia reaction generates, the first gas mixture includes carrier gas and first
Ammonia；
Heating device 2 is connect with the first reactor 1, first solid mixture in the first reactor 1
Into the heating device 2, the heating device 2 obtains the second solids for heating the first solid mixture reaction
Matter and second gas mixture, wherein the second gas mixture includes the ammonia that first ammonium chloride is generated by heating
Gas and hydrogen chloride, second solid matter include the described first nitrogenous silane compound by the high α phase content of heating generation
Silicon nitride；
Eluting column 3, eluting column 3 include the first charging aperture 33 of eluting column and the second charging aperture 34 of eluting column, eluting column
First charging aperture 33 connect with the heating device 2, the second gas mixture enter the eluting column 3, the elution
Tower 3 elutes the second gas mixture for being passed through the second chlorosilane, obtains third solid mixture and third gas
Body substance, wherein the third solid mixture includes the ammonia in second chlorosilane and the second gas mixture
The the second nitrogenous silane compound and the second ammonium chloride generated is reacted, the third gas substance includes hydrogen chloride.
The system of the production silicon nitride of the present embodiment can recycle the ammonia generated in preparation process and the second chlorine silicon
Alkane reaction, has regenerated the nitrogenous silane compound of intermediate second needed for preparing silicon nitride, to save cost.
Reaction in first reactor 1 is gas solid/liquid/gas reactions, and the flow of unstripped gas and reaction are easily controlled.
The nitrogenous silane compound of the present embodiment is also commonly referred to as silicon diimine, is easy after absorption or releasing ammonia with Si-
N-H based compound form exists, and nitrogenous silane compound majority can use Si (NH)2Formula expression, Si (NH)2It is not one specific
Substance, such compound can be Si6N13H15、Si6N12H12、Si6N11H9Deng.
Carrier gas in the first reactor 1 is one of nitrogen, ammonia, inert gas, by carrier gas to reaction institute
Raw material is diluted.
Chlorosilane is passed through with carrier gas, and preferred carrier gas is nitrogen, and the flow for controlling nitrogen be 2 times of the first chlorosilane with
On, to control reaction speed and prevent the system for producing silicon nitride from line clogging occur.
Preferably, first chlorosilane is one or more of silicon tetrachloride, trichlorosilane, dichlorosilane.
Used the first chlorosilane of raw material and the first ammonia of raw material purity are 99.99% or more, other the first ammonia
Gas and carrier gas are intended to be carried out dehydrating.
Preferably, in the first reactor 1, the first chlorosilane of raw material and the first ammonia of raw material in the heating carrier gas
The temperature of reaction is 10~100 DEG C, and pressure is 0~1MPa.
Preferably, in the first reactor 1, the molar ratio of first chlorosilane and first ammonia is 1:(6
~30).Ammonia can excessively make chlorosilane fully reacting.
Preferably, the tower reactor 31 of the eluting column is connect with the entrance of the heating device 2, the third solid mixing
Object enters the heating device 2.Then the third solid mixture is mixed with first solid mixture, described in repetitive cycling
Reaction in heating device 2.
Preferably, the heating device 2 includes:
Primary heater 4, entrance 41, the first outlet 42 of primary heater, primary heater including primary heater
Second outlet 43, the entrance 41 of primary heater is connect with the first reactor 1, described in the first reactor 1
First solid mixture enters the primary heater 4, and under non-oxidizing atmosphere, it is anti-to heat first solid mixture
It answers, obtains the 4th solid mixture and the 4th admixture of gas, the 4th admixture of gas includes in the primary heater 4
The non-oxidizing atmosphere gas, first ammonium chloride ammonia and hydrogen chloride that thermally decompose to generate, the described 4th
Solid mixture includes the described first nitrogenous silane compound；The first ammonium chloride of by-product is eliminated by the step, described first
The first outlet 42 of heater is connect with the first charging aperture 33 of the eluting column, and the 4th admixture of gas is by described the
The first outlet 42 of one heater enters the first charging aperture 33 of the eluting column.
Secondary heater 5, entrance 51, the first outlet 52 of secondary heater, secondary heater including secondary heater
Second outlet 53, the entrance 51 of the secondary heater connect with the second outlet 43 of the primary heater, described first
The 4th solid mixture in heater 4 enters in the secondary heater 5, under ammonia atmosphere, heating the described 4th
Solid mixture obtains the 5th solid mixture and the 5th admixture of gas, and the 5th solid mixture includes described first
Nitrogenous silane compound thermally decomposes to generate unbodied silicon nitride, and the 5th admixture of gas includes the gas of ammonia atmosphere
The ammonia that body, hydrogen chloride, the first nitrogenous silane compound thermally decompose to generate, the first outlet of the secondary heater
52 connect with the first charging aperture 33 of the eluting column, and the 5th admixture of gas goes out by the first of the secondary heater
Mouth 52 enters the first charging aperture 33 of the eluting column；The ammonia atmosphere can enter the 4th solid mixture or the 5th
The inside of solid mixture, this is this step using ammonia as the purpose of atmosphere, removes wherein internal chlorine element, avoids
The method that liquefied ammonia washing removes chlorine element in the prior art, greatlies simplify the production procedure of silicon nitride.The of primary heater
One first outlet 52 for exporting 42, secondary heater is connect with the first charging aperture of eluting column 33, can recycle the 4th simultaneously
Ammonia in admixture of gas and the 5th admixture of gas reduces processing cost.
Third heater 6 is connect with the second outlet 53 of the secondary heater, described in the secondary heater 5
5th solid mixture enters in the third heater 6, under non-oxidizing atmosphere, heats the 5th solid mixture,
Second solid matter and the second gas mixture are obtained, the unbodied silicon nitride generates high α phase by heating
The silicon nitride of content.
Preferably, in the primary heater 4, the temperature of heating the first solid mixture reaction is 500
~600 DEG C, heating time is 1~2 hour；
In the secondary heater 5, the temperature of heating the 4th solid mixture is 650~1200 DEG C, heating
Time is 2~8 hours；
In the third heater 6, the temperature of heating the 5th solid mixture is 1250~1700 DEG C, heating
Time is 2~8 hours.
Preferably, in the third heater 6, the temperature of the heating the 5th solid mixture is 1350~
1600 DEG C, temperature is too low, then the phase transition time is long, and temperature is excessively high, then is easy to promote the content of β phase in silicon nitride.
Preferably, the system of the production silicon nitride further include:
The outlet 72 of second reactor 7, the entrance 71 including second reactor and second reactor, the second reactor
Entrance 71 connect with the tower top 32 of the eluting column, the third gas substance as the eluting column tower top 32 enter described in
Second reactor 7, the second reactor 7 react to obtain third chlorine silicon for being passed through silicon powder with third gas substance heating
Alkane, the outlet 72 of the second reactor are connect with the entrance of the first reactor 1, and the third chlorosilane enters described the
In one reactor 1.Then the third chlorosilane is mixed with first chlorosilane, repeats the reaction in the first reactor 1,
It is reused for the production of silicon nitride.
Preferably, the second reactor 7 reacts to obtain for being passed through silicon powder and the third gas substance and heating
The reaction temperature of trichlorosilane is 300~500 DEG C,, can be with by the temperature of control reaction it is further preferred that 325~400 DEG C
Adjust the content of each component such as silicon tetrachloride, trichlorosilane in the third chlorosilane product generated.
Product third chlorosilane in second reactor 7 is also the raw material of production of polysilicon, therefore the product can be incorporated to
Into polycrystalline silicon production system, realizes the coproduction of silicon nitride and polysilicon, further reduce the cost.
Preferably, the system of the production silicon nitride further include:
Rectifier unit 8, the outlet 82 of entrance 81 and rectifier unit including rectifier unit, the entrance 81 of the rectifier unit
It is connect with the outlet 72 of the second reactor, the outlet 82 of the rectifier unit and the entrance 13 of the first reactor connect
It connects, the rectifier unit 8 is used to carry out rectification and purification to the third chlorosilane.
Preferably, the outlet 72 of the second reactor is also connect with the second charging aperture of eluting column 34, the third
Chlorosilane enters in the eluting column 3 for eluting.Then the third chlorosilane is mixed with second chlorosilane, described in repetition
Elution in eluting column 3.
As shown in Figure 3, it is preferred that the system of the production silicon nitride further include:
Filter 9, first outlet 92, the second outlet of filter 93 of entrance 91, filter including filter are described
The entrance 91 of filter is connect with first reactor 1, first gas mixture and part first in the first reactor 1
Solid mixture enters the filter 9, and the filter 9 is separated by filtration the part separated described first for gas-solid
Solid mixture and the first gas mixture, the first outlet 92 of the filter are connect with the heating device 2, part
First solid mixture enters the heating device 2 by the first outlet 92 of the filter, and the of the filter
Two outlets 93 are connect with the first reactor 1, the first gas mixture by the second outlet 93 of the filter into
Enter the first reactor 1.First solid mixture generated in first reactor 1 is deposited in the bottom of first reactor 1
Portion is partially taken out of by unreacted ammonia to filter 9.First solid mixture of the bottom of first reactor 1 can be continuous
Discharge, discharge that can also be intermittent.
Preferably, the system of the production silicon nitride further include:
Cooler 10, first outlet 102, the second outlet of cooler 103 of entrance 101, cooler including cooler,
The entrance 101 of the cooler is connect with the second outlet 93 of the filter, and the first gas mixture passes through the mistake
The second outlet 93 of filter enters the cooler 10, and the cooler 10 obtains liquefied ammonia and carrier gas for refrigerated separation；It is described
Temperature in cooler 10 is -35~-50 DEG C.
The outlet 112 of carrier gas reservoir 11, the entrance 111 including carrier gas reservoir and carrier gas reservoir, the carrier gas reservoir enter
Mouth 111 is connect with the first outlet 102 of the cooler, and the carrier gas in the cooler 10 goes out by the first of the cooler
Mouth 102 enters the entrance 111 of the carrier gas reservoir, and the outlet 112 of the carrier gas reservoir is connect with the first reactor 1；
Carrier gas in carrier gas reservoir 11 is reused for the carrier gas in first reactor 1.
Liquid ammonia storage tank 12, the outlet 122 of entrance 121 and liquid ammonia storage tank including liquid ammonia storage tank, the liquid ammonia storage tank enter
Mouth 121 is connect with the second outlet 103 of the cooler, and the liquefied ammonia in the cooler 10 goes out by the second of the cooler
Mouth 103 enters the entrance 121 of the liquid ammonia storage tank, and the outlet 122 of the liquid ammonia storage tank is connect with the first reactor 1.
Certainly, the liquefied ammonia in liquid ammonia storage tank 12 is also used as the protective atmosphere in heating device 2.
Preferably, second chlorosilane is one or more of silicon tetrachloride, trichlorosilane, dichlorosilane.
Preferably, the third chlorosilane is one or more of silicon tetrachloride, trichlorosilane, dichlorosilane.
The continuous metaplasia of the nitrogenous silane compound of intermediate first may be implemented in the system of the production silicon nitride of the present embodiment
It produces, entire silicon nitride is produced as closed loop process, and by-product and unreacted reactant are recycled, required supplementation with
The production cost of silicon nitride can be greatly reduced to be only silicon powder and ammonia in raw material.
Embodiment 3
The present embodiment provides a kind of methods that the system using the production silicon nitride in embodiment 2 prepares silicon nitride, including
Following steps:
(1) ammonia of 0.1MPa is first full of in the reactor that volume is 4L.Control ammonia flow velocity is 320mL/min, to
The silicon tetrachloride gas of 40mL/min is added in reactor.It is constant in 0.1MPa that the pressure in reactor is controlled by counterbalance valve,
Controlling internal temperature by thermoregulator is 100 DEG C.It is lower be passed through gas velocity under, the silicon diimine of generation all settles substantially
In the bottom of reactor.After reacting 1h, the loose silicon diimine that weight is 28.3g is obtained in the bottom of reactor and ammonium chloride is mixed
Close powder.
(2) obtained silicon diimine solid powder is placed in tube furnace and carries out heat treatment 1h, heat treatment temperature 550
DEG C, protective atmosphere is ammonia, to remove the ammonium chloride on silicon diimine surface.After heat treatment, thick silicon diimine solid powder is obtained
6.1g, Cl content therein are 200ppm.
(3) thick silicon diimine powder is carried out after simply grinding, is put into progress high temperature pyrolysis processing in tube furnace.At heat
It when reason, is started to warm up from 650 DEG C, keeps the temperature 4h again after 1h is warming up to 1100 DEG C, whole process is using ammonia as protective atmosphere.Heat
After solution processing, unbodied alpha-silicon nitride powders are obtained.Through detecting, the chlorinity in silicon nitride is down to 45ppm.
(4) finally by unbodied alpha-silicon nitride powders carry out high-temperature phase-transitional processing, 1400 DEG C at a temperature of keep the temperature 4h,
Silicon nitride product is obtained, after grinding, α phase silicon nitride content in silicon nitride product is 96.5wt%, metals content impurity <
30ppm, chlorinity 45ppm, oxygen content 0.8wt%.
Embodiment 4
The present embodiment provides a kind of methods that the system using the production silicon nitride in embodiment 2 prepares silicon nitride, including
Following steps:
(1) using the reactor in embodiment 1, control ammonia flow velocity is 1L/min, and 300mL/min is added into reactor
Nitrogen and trichlorosilane mixed gas, wherein the molar ratio of nitrogen and silicon tetrachloride be 2:1.It is controlled and is reacted by counterbalance valve
Pressure in device is constant in 0.5MPa, and controlling internal temperature by thermoregulator is 50 DEG C.After reacting 1h, altogether from reactor bottom
The millipore filter that portion and reactor outlet go out obtains the loose silicon diimine and ammonium chloride mixed-powder of 69.0g.
(2) obtained silicon diimine solid powder is placed in tube furnace and carries out heat treatment 2h, heat treatment temperature 500
DEG C, protective atmosphere is ammonia, to remove the ammonium chloride on silicon diimine surface.After heat treatment, thick silicon diimine solid powder is obtained
14.7g, Cl content therein are 240ppm.
(3) thick silicon diimine powder is carried out after simply grinding, is put into progress high temperature pyrolysis processing in tube furnace.At heat
It when reason, is started to warm up from 650 DEG C, keeps the temperature 4h again after 1h is warming up to 1200 DEG C, whole process is using ammonia as protective atmosphere.Heat
After solution processing, unbodied alpha-silicon nitride powders are obtained.Through detecting, the chlorinity in silicon nitride is down to 50ppm.
(4) finally by unbodied alpha-silicon nitride powders carry out high-temperature phase-transitional processing, 1650 DEG C at a temperature of keep the temperature 3h,
High-purity silicon nitride product is obtained, after grinding, the α phase silicon nitride content in silicon nitride product is 97.3wt%, and metal impurities contain
Amount < 30ppm, chlorinity 50ppm, oxygen content 0.9wt%.
Embodiment 5
The present embodiment provides a kind of methods that the system using the production silicon nitride in embodiment 2 prepares silicon nitride, including
Following steps:
(1) with the reactor of embodiment 1.Control ammonia flow velocity is 3L/min, and the nitrogen of 1.2L/min is added into reactor
Gas and silicon tetrachloride, trichlorosilane, dichlorosilane mixed gas, wherein mole of nitrogen and silicon tetrachloride, trichlorosilane
Than for 6:1:1:0.5.It is constant in 1.0MPa by the pressure in counterbalance valve control reactor, pass through thermoregulator and controls inside
Temperature is 60 DEG C.After reacting 1h, the loose of 206.8g is obtained from the millipore filter that reactor bottom and reactor outlet go out altogether
Silicon diimine and ammonium chloride mixed-powder.
(2) obtained silicon diimine solid powder is placed in tube furnace and carries out heat treatment 1h, heat treatment temperature 600
DEG C, protective atmosphere is ammonia, to remove the ammonium chloride on silicon diimine surface.After heat treatment, thick silicon diimine solid powder is obtained
43.2g, Cl content therein are 350ppm.
(3) thick silicon diimine powder is carried out after simply grinding, is put into progress high temperature pyrolysis processing in tube furnace.At heat
It when reason, is started to warm up from 650 DEG C, keeps the temperature 8h again after 1h is warming up to 1000 DEG C, whole process is using ammonia as protective atmosphere.Heat
After solution processing, unbodied alpha-silicon nitride powders are obtained.Through detecting, the chlorinity in silicon nitride is down to 63ppm.
(4) finally by unbodied alpha-silicon nitride powders carry out high-temperature phase-transitional processing, 1300 DEG C at a temperature of keep the temperature 8h,
High-purity silicon nitride product is obtained, after grinding, α phase content is 95.4wt%, and metals content impurity < 30ppm, chlorinity is
63ppm, oxygen content 0.6wt%.
The tail gas when heat treatment of silicon diimine is collected, and keeps the temperature of tail gas at 550 DEG C.Then tail is sprayed into tail gas
Silicon tetrachloride of the air volume than 2 times and trichlorosilane mixture, wherein the molar ratio of silicon tetrachloride and trichlorosilane is 1:1, is made
Ammonia in tail gas is reacted with chlorosilane completely generates silicon diimine.With gas chromatographic detection, only contain in the gas after reaction
HCl, ammonia level are not detected.To obtained silicon diimine using same heat treatment step in example is originally applied, nitridation is finally obtained
Silicon product, after grinding, α phase content is 92.7wt%, and metals content impurity < 35ppm, chlorinity 140ppm, oxygen content is
0.6wt%.
HCl tail gas after collecting chlorosilane elution, reacts with silicon powder generate chlorosilane in a fluidized bed reactor, controls
The temperature of reactor processed is 350 DEG C, and after reaction, silicon tetrachloride accounts for 14.4wt% in the chlorosilane of generation, and trichlorosilane accounts for
85.0wt%, dichlorosilane accounts for 0.6wt%.
HCl tail gas after collecting chlorosilane elution, reacts with silicon powder generate chlorosilane in a fluidized bed reactor, controls
The temperature of reactor processed is 450 DEG C, and after reaction, silicon tetrachloride accounts for 57.6wt% in the chlorosilane of generation, and trichlorosilane accounts for
41.4wt%, dichlorosilane account for 1.0wt%.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, however the present invention is not limited thereto.For those skilled in the art, essence of the invention is not being departed from
In the case where mind and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.
Claims (11)
1. a kind of system for producing silicon nitride characterized by comprising
First reactor reacts with the first ammonia of raw material for the first chlorosilane of raw material in carrier gas, obtains the first solid mixture
With first gas mixture, wherein first solid mixture includes that first chlorosilane is reacted with first ammonia
The the first nitrogenous silane compound and the first ammonium chloride generated, the first gas mixture includes carrier gas and the first ammonia；
Heating device is connect with the first reactor, and first solid mixture in the first reactor enters institute
Heating device is stated, the heating device obtains the second solid matter and second for heating the first solid mixture reaction
Admixture of gas, wherein the second gas mixture includes ammonia and chlorination of first ammonium chloride by heating generation
Hydrogen, second solid matter include the silicon nitride for the high α phase content that the described first nitrogenous silane compound is generated by heating；
Eluting column is connect with the heating device, and the second gas mixture enters the eluting column, and the eluting column is used for
It is passed through the second chlorosilane to elute the second gas mixture, obtains third solid mixture and third gas substance,
Wherein, the third solid mixture includes that second chlorosilane with the ammonia in the second gas mixture reacts generation
The second nitrogenous silane compound and the second ammonium chloride, the third gas substance includes hydrogen chloride.
2. the system of production silicon nitride according to claim 1, which is characterized in that in the first reactor, the load
The temperature that the first chlorosilane of raw material is reacted with the first ammonia of raw material in gas is 10~100 DEG C, and pressure is 0~1MPa.
3. the system of production silicon nitride according to claim 1, which is characterized in that in the first reactor, described the
The molar ratio of one chlorosilane and first ammonia is 1:(6~30).
4. the system of production silicon nitride according to claim 1, which is characterized in that the tower reactor of the eluting column adds with described
The entrance of thermal connects, and enters the heating device for the third solid mixture.
5. the system of production silicon nitride according to claim 1, which is characterized in that the heating device includes:
Primary heater, the first outlet of entrance, primary heater including primary heater, the second of primary heater go out
Mouthful, the entrance of the primary heater is connect with the first reactor, solid for described first in the first reactor
Body mixture enters the primary heater, under non-oxidizing atmosphere, heats first solid mixture reaction, obtains the
Four solid mixtures and the 4th admixture of gas, the 4th admixture of gas include described non-oxygen in the primary heater
The ammonia and hydrogen chloride that gas, first ammonium chloride of the property changed atmosphere thermally decompose to generate, the 4th solid mixture
Including the described first nitrogenous silane compound, the first outlet of the primary heater is connect with the eluting column, and the described 4th
Admixture of gas enters the eluting column by the first outlet of the primary heater；
Secondary heater, the first outlet of entrance, secondary heater including secondary heater, the second of secondary heater go out
Mouthful, the entrance of the secondary heater is connect with the second outlet of the primary heater, in the primary heater
4th solid mixture enters in the secondary heater, under ammonia atmosphere, heats the 4th solid mixture, obtains
To the 5th solid mixture and the 5th admixture of gas, the 5th solid mixture includes the described first nitrogenous silane compound
Thermally decompose to generate unbodied silicon nitride, the 5th admixture of gas includes the gas of ammonia atmosphere, hydrogen chloride, described
The ammonia that first nitrogenous silane compound thermally decomposes to generate, the first outlet of the secondary heater and the eluting column connect
It connects, the 5th admixture of gas enters the eluting column by the first outlet of the secondary heater；
Third heater is connect with the second outlet of the secondary heater, the 5th solid in the secondary heater
Mixture enters in the third heater, for heating the 5th solid mixture, obtaining institute under non-oxidizing atmosphere
The second solid matter and the second gas mixture are stated, the unbodied silicon nitride generates high α phase content by heating
Silicon nitride.
6. the system of production silicon nitride according to claim 5, which is characterized in that described to add in the primary heater
The temperature of heat the first solid mixture reaction is 500~600 DEG C, and heating time is 1~2 hour；
In the secondary heater, the temperature of the heating the 4th solid mixture is 650~1200 DEG C, and heating time is
2~8 hours；
In the third heater, the temperature of heating the 5th solid mixture is 1250~1700 DEG C, heating time
It is 2~8 hours.
7. the system of production silicon nitride according to claim 1, which is characterized in that further include:
Second reactor, the outlet of entrance and second reactor including second reactor, the entrance of the second reactor with
The tower top of the eluting column connects, and enters second reaction by the tower top of the eluting column for the third gas substance
Device, the second reactor react to obtain third chlorosilane for being passed through silicon powder and the third gas substance and heating, and described the
The outlet of two reactors is connect with the first reactor, and the third chlorosilane enters in the first reactor.
8. the system of production silicon nitride according to claim 7, which is characterized in that further include:
Rectifier unit, the outlet of entrance and rectifier unit including rectifier unit, the entrance of the rectifier unit and described second
The outlet of reactor connects, and the outlet of the rectifier unit is connect with the first reactor, and the rectifier unit is used for institute
It states third chlorosilane and carries out rectification and purification, purified third chlorosilane enters the first reactor.
9. it is according to claim 7 production silicon nitride system, which is characterized in that the outlet of the second reactor also with
The eluting column connection, enters in the eluting column for the third chlorosilane for eluting.
10. the system of production silicon nitride according to claim 1, which is characterized in that further include:
Filter, first outlet, the second outlet of filter of entrance, filter including filter, the filter enter
Mouth is connect with the first reactor, the first solid mixture of first gas mixture and part in the first reactor
Into the filter, the filter for gas-solid be separated by filtration the part separated first solid mixture and
The first gas mixture, the first outlet of the filter are connect with the heating device, and part first solid is mixed
It closes object and the heating device is entered by the first outlet of the filter, the second outlet of the filter is anti-with described first
Device is answered to connect, the first gas mixture enters the first reactor by the second outlet of the filter.
11. the system of production silicon nitride according to claim 10, which is characterized in that further include:
Cooler, first outlet, the second outlet of cooler of entrance, cooler including cooler, the cooler enter
Mouthful connect with the second outlet of the filter, for the first gas mixture by the second outlet of the filter into
Enter the cooler, the cooler obtains liquefied ammonia and carrier gas for refrigerated separation；
Carrier gas reservoir, the outlet of entrance and carrier gas reservoir including carrier gas reservoir, the entrance of the carrier gas reservoir and the cooling
The first outlet of device connects, and enters the carrier gas by the first outlet of the cooler for the carrier gas in the cooler
The entrance of storage tank, the outlet of the carrier gas reservoir are connect with the first reactor；
Liquid ammonia storage tank, the outlet of entrance and liquid ammonia storage tank including liquid ammonia storage tank, the entrance of the liquid ammonia storage tank and the cooling
The second outlet of device connects, and enters the liquefied ammonia by the second outlet of the cooler for the liquefied ammonia in the cooler
The entrance of storage tank, the outlet of the liquid ammonia storage tank are connect with the first reactor.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040559A (en) * | 1989-08-24 | 1990-03-21 | 国家建筑材料工业局山东工业陶瓷研究设计院 | The manufacture method of alpha-silicon nitride powders and equipment |
| CN1051153A (en) * | 1990-12-20 | 1991-05-08 | 清华大学 | The method of making ultrafine powder of silicon nitride by dual-tube pressuring |
| CN102491291A (en) * | 2011-12-14 | 2012-06-13 | 合肥摩凯新材料科技有限公司 | Method for preparing high-purity silicon nitride micro-nano powder |
| WO2015160160A1 (en) * | 2014-04-14 | 2015-10-22 | 오씨아이 주식회사 | Apparatus and method for continuously preparing silicon nitride with improved particle size uniformity |
| CN205099363U (en) * | 2015-11-11 | 2016-03-23 | 新特能源股份有限公司 | System for production silicon nitride |
-
2015
- 2015-11-11 CN CN201510768516.5A patent/CN106672922B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040559A (en) * | 1989-08-24 | 1990-03-21 | 国家建筑材料工业局山东工业陶瓷研究设计院 | The manufacture method of alpha-silicon nitride powders and equipment |
| CN1051153A (en) * | 1990-12-20 | 1991-05-08 | 清华大学 | The method of making ultrafine powder of silicon nitride by dual-tube pressuring |
| CN102491291A (en) * | 2011-12-14 | 2012-06-13 | 合肥摩凯新材料科技有限公司 | Method for preparing high-purity silicon nitride micro-nano powder |
| WO2015160160A1 (en) * | 2014-04-14 | 2015-10-22 | 오씨아이 주식회사 | Apparatus and method for continuously preparing silicon nitride with improved particle size uniformity |
| CN205099363U (en) * | 2015-11-11 | 2016-03-23 | 新特能源股份有限公司 | System for production silicon nitride |
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