CN109422251A - Silicon powder for fluidized reaction and preparation method thereof, silicon nitride and its production method - Google Patents
Silicon powder for fluidized reaction and preparation method thereof, silicon nitride and its production method Download PDFInfo
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- CN109422251A CN109422251A CN201710724683.9A CN201710724683A CN109422251A CN 109422251 A CN109422251 A CN 109422251A CN 201710724683 A CN201710724683 A CN 201710724683A CN 109422251 A CN109422251 A CN 109422251A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000011863 silicon-based powder Substances 0.000 title claims abstract description 145
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 83
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 60
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 117
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 62
- 239000007789 gas Substances 0.000 claims abstract description 44
- 238000005243 fluidization Methods 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 23
- 239000000428 dust Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 239000008247 solid mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000005501 phase interface Effects 0.000 abstract description 6
- 239000007790 solid phase Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 3
- 235000013339 cereals Nutrition 0.000 description 21
- 239000012071 phase Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000011361 granulated particle Substances 0.000 description 3
- -1 silicon powder nitride Chemical class 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XURIQWBLYMJSLS-UHFFFAOYSA-N 1,4,7,10-tetrazacyclododecan-2-one Chemical compound O=C1CNCCNCCNCCN1 XURIQWBLYMJSLS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000016784 immunoglobulin production Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005550 wet granulation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
- C01B21/0682—Preparation by direct nitridation of silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/20—Powder free flowing behaviour
Abstract
The silicon powder and preparation method thereof that the invention discloses a kind of for fluidized reaction, silicon nitride and its production method, the inside of silicon powder in the present invention has hole, substantially increase the specific surface area and porosity of silicon powder, when silicon powder and nitrogen carry out fluidized reaction, nitrogen is entered in the channel of the hole formation of the inside of silicon powder to come into full contact with and be contacted with silicon powder, not only substantially increase gas, solid phase interface product, and improve velocity of liquid assets of the nitrogen in the channel of the hole formation of the inside of silicon powder, to improve the speed of fluidized reaction, so that not only silicon nitride can be generated on the surface of silicon powder, and silicon nitride can be also generated in the inside of silicon powder, and substantially increase the conversion ratio of silicon powder.Fluidized reaction is carried out using the internal silicon powder with hole, the silicon powder that bulky grain can be used forms fluidisation state, and silicon powder will not be prevented to react with the further of nitrogen, and from greatly reducing the resistance of nitridation reaction.
Description
Technical field
The invention belongs to silicon nitride production technical fields, and in particular to a kind of for the silicon powder of fluidized reaction and its preparation side
Method, silicon nitride and its production method.
Background technique
Silicon nitride has that high mechanical strength, self-lubricating, thermal stability be good, good chemical stability, in high temperature, height
In particular job environment such as speed, strong corrosive medium and high abrasion, have a wide range of applications.Silicon nitride molecular formula is Si3N4, it is one
Kind has α-Si with the compound of Covalent bonding together3N4、β-Si3N4、γ-Si3N4Three kinds of phases, α phase silicon nitride kinetically compared with
It is easy to generate, is undergone phase transition under high temperature and generate thermodynamically stable phase beta phase silicon nitride, γ phase silicon nitride is only under high pressure and high temperature
It could synthesize.α phase silicon nitride is more active, is easy to sinter product into, therefore industrial application is with α-Si3N4Based on.
There are four types of current industrialized silicon nitride powder Antibody Production Techniques: (1) silicon powder direct nitridation method, i.e., silicon powder is straight
Connect nitridation；(2) reduction nitridation method is occurred redox reaction in nitrogen by silica and carbon dust and generates silicon nitride；(3) low
Warm halosilanes method generates Si-N-H intermediate product by the halosilanes such as silicon tetrachloride or trichlorosilane and ammonia, then again at low temperature
Si-N-H intermediate product is pyrolyzed as silicon nitride, wherein Si-N-H compound is Si6N13H15、Si6N12H12、Si6N11H9Etc. some
The common name of column compound；(4) high temperature halosilanes or silane thermal decomposition process, at high temperature directly and ammonia by the halosilanes such as silicon tetrachloride or silane
Gas, which reacts, generates silicon nitride.In the above-mentioned methods, direct nitridation method has simple process, is suitable for a systems such as large-scale production
Column advantage is current main nitridation silicon preparation method.
Since there are many phases for silicon nitride, reaction temperature is different, will generate out of phase beta-silicon nitride powder, therefore temperature
Control directly affect the quality of beta-silicon nitride powder.But silicon powder nitride is exothermic process, the heat generated in reaction process is not
Can remove in time will cause hot-spot phenomenon, and the α phase silicon nitride generated is caused to undergo phase transition, and generate it also occur that silicon powder melts
The phenomenon that flowing silicon.
In view of fluidized bed has heat transfer between fluid and particle, mass transfer rate high, gas, solid phase interface product are big, reaction speed
The advantages that rate is fast, the problem of can solve non-uniform temperature during silicon powder nitride, domestic and international Some Enterprises and colleges and universities attempt to make
Beta-silicon nitride powder is prepared with fluidized bed process.
However, during preparing silicon nitride using fluidized bed process, if it may be implemented to fluidize using bulky grain silicon powder, but
It is that silicon powder reacts with nitrogen and silicon powder can be prevented to react with the further of nitrogen in the Surface Creation silicon nitride layer of silicon powder；Using
Small particle silicon powder can reduce the resistance of nitridation reaction, but solid particle is too thin, then be difficult to fluidize, the prior art does not consider that
This problem, therefore the relevant technologies are difficult to realize industrial applications.
Summary of the invention
It is a kind of for flowing the technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide
Change silicon powder of reaction and preparation method thereof, silicon nitride and its production method, the inside of the silicon powder in the present invention has hole, significantly
The specific surface area and porosity of silicon powder is improved, when silicon powder and nitrogen carry out fluidized reaction, nitrogen enters the inside of silicon powder
It comes into full contact in the channel of hole formation and is contacted with silicon powder, not only substantially increase gas, solid phase interface product.
It solves technical solution used by present invention problem and is to provide a kind of silicon powder for fluidized reaction, the silicon
The inside of powder has hole.
Preferably, the porosity of the silicon powder is 15~40%.
Preferably, the partial size of the silicon powder is 20~120 mesh.The partial size of silicon powder is big, and fluidized reaction occurs convenient for silicon powder
When formed fluidisation state, reach fluidized reaction requirement, and silicon powder is come into full contact with nitrogen.
Preferably, the silicon powder in the case where fluidizing state for fluidized reaction generation to occur with the nitrogen being passed into fluidized bed
Silicon nitride.
The present invention also provides a kind of preparation methods of above-mentioned silicon powder for fluidized reaction, comprising the following steps:
(1) silica fine powder, binder, water are mixed, is machined as bulky grain silicon powder by being granulated, bulky grain silicon powder is thin by silicon
Powder is bonded by binder；
(2) bulky grain silicon powder is heated, so that binder decomposition escapes in gaseous form, obtains the internal silicon with hole
Powder.Binder can generate many tiny holes after thermally decomposing in silicon powder particle, convenient for the infiltration of nitrogen when fluidized reaction,
Increase the contact area of nitrogen and silicon powder.After binder decomposes evolution in gaseous form in bulky grain silicon powder, inside silicon powder
Tiny channel is generated, while moisture removes.
Preferably, the mass ratio of water and silica fine powder is (1:9)~(3:7).
Preferably, the mass ratio of binder described in the step (1) and the silica fine powder is (5~10): 100.
Preferably, the heating temperature in the step (2) is 250~400 DEG C, and heating time is 1~4 hour.
Preferably, the partial size of the silica fine powder≤500 mesh.
It is further preferred that the partial size of the silica fine powder is 500~1000 mesh.
Preferably, the binder includes one or more of methylcellulose, plant fiber, starch.
The present invention also provides a kind of methods for producing silicon nitride, comprising the following steps:
The silicon powder of fluidized reaction is used for by above-mentioned preparation method preparation；
The silicon powder of preparation is added in fluidized bed, silicon powder is flowed with the nitrogen being passed into fluidized bed in the case where fluidizing state
Change reaction and generates silicon nitride.
Fluid and solid particle heat transfer, mass transfer rate are fast in fluidized-bed reaction bed, the reaction temperature of each point in fluidized bed
Control range can achieve ± 1 DEG C, the accurate control of reaction temperature may be implemented.But it is raw using fixed bed in the prior art
Silicon nitride is produced, then due to that can not exchange heat, the reaction temperature difference of each point is big in fixed bed.
Preferably, the method for the production silicon nitride is further comprising the steps of:
Cyclone separator is connect with fluidized bed, and the material in fluidized bed enters cyclone separator and carries out gas solid separation, separation
Solid particle afterwards falls back in fluidized bed, and the gas-solid mixture after separation is flowed into the bag hose connecting with cyclone separator
It is interior, after bag hose dust removal by filtration, obtain tail gas.
Preferably, be additionally provided with heat exchanger between cyclone separator and bag hose, heat exchanger respectively with cyclone separator,
Bag hose connection enters heat exchanger and temperature control medium by the gas-solid mixture that cyclone separator obtain after gas solid separation
Heat exchange flows into dust removal by filtration in bag hose by the gas-solid mixture to be cooled down after heat exchange in heat exchanger, in heat exchanger again
The interior gaseous state temperature control medium by being heated up after heat exchange.
Preferably, the temperature control medium is nitrogen, and the temperature control medium outlet of heat exchanger is also connect with the entrance of fluidized bed,
It is passed into fluidized bed in heat exchanger by the gaseous nitrogen atmosphere of the heating obtained after heat exchange.
Preferably, the temperature control medium is nitrogen, and the temperature control medium outlet of heat exchanger is also connect with bag hose, bag hose
It connect with the entrance of fluidized bed, is obtained bag hose dust removal by filtration by the gaseous nitrogen atmosphere of the heating obtained after heat exchange in heat exchanger
To solid particle be blown into fluidized bed.
Preferably, the preparation method of silicon powder of the preparation for fluidized reaction heats bulky grain by heat drier
Silicon powder, heat drier are set between pelletizer and fluidized bed, and heat drier is connect with pelletizer, fluidized bed respectively, institute
Stating temperature control medium is nitrogen, and the temperature control medium outlet of heat exchanger is also connect with heat drier, after passing through heat exchange in heat exchanger
The gaseous nitrogen atmosphere of obtained heating is passed into heat drier.
Preferably, cyclone separator includes the cyclone separating chamber for cyclonic separation, and cyclone separating chamber is set to fluidisation
In bed, the feed inlet of cyclone separator is located at the settling section of fluidized bed, and the slag-drip opening of cyclone separator is located at the reaction of fluidized bed
Section, the gas vent of cyclone separator are located at outside fluidized bed.
Preferably, the temperature of the reaction in the fluidized bed is 1200~1300 DEG C.
The present invention also provides a kind of silicon nitrides, to be produced by above-mentioned method.
The inside of silicon powder in the present invention has hole, substantially increases the specific surface area and porosity of silicon powder, silicon powder with
When nitrogen carries out fluidized reaction, nitrogen is entered in the channel of the hole formation of the inside of silicon powder to come into full contact with and be contacted with silicon powder,
Gas, solid phase interface product are not only substantially increased, and improves nitrogen in the channel of the hole formation of the inside of silicon powder
Velocity of liquid assets, so that the speed of fluidized reaction is improved, so that silicon nitride not only can be generated on the surface of silicon powder, and in silicon
The inside of powder can also generate silicon nitride, and substantially increase the conversion ratio of silicon powder.It is flowed using the internal silicon powder with hole
Change reaction, the silicon powder that bulky grain can be used forms fluidisation state, and silicon powder will not be prevented to react with the further of nitrogen, and significantly
Reduce the resistance of nitridation reaction.
Detailed description of the invention
Fig. 1 is in the embodiment of the present invention 4 for producing the device of silicon nitride.
In figure: 1- pelletizer；2- elevator；3- heat drier；4- fluidized bed；5- cyclone separator；6- cyclonic separation
The feed inlet of device；The slag-drip opening of 7- cyclone separator；The gas vent of 8- cyclone separator；9- heat exchanger；The pipe of 10- heat exchanger
Journey；The shell side of 11- heat exchanger；12- shell-side outlet；13- bag hose；14- gas distribution grid；15- solid discharge mouth；16- whirlwind
Separation chamber；17- valve.
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
The present embodiment provides a kind of preparation methods of above-mentioned silicon powder for fluidized reaction, comprising the following steps:
(1) silica fine powder, binder, water are mixed, the mass ratio of water and silica fine powder is 1:9, is machined as greatly by being granulated
Particle spherical silicon powder particle, bulky grain silicon powder are bonded by silica fine powder by binder, the mass ratio of binder and silica fine powder
For 5:100,500 mesh of partial size of silica fine powder, binder is methylcellulose；
(2) heat bulky grain silicon powder, heating temperature be 400 DEG C, heating time be 2.5 hours so that binder decompose with
The form of gas escapes, and obtains the internal silicon powder with hole, and the porosity of silicon powder is 25%, and the partial size of silicon powder is 20 mesh.It should
There is the silicon powder of hole to generate silicon nitride for fluidized reaction to occur in the case where fluidizing state with the nitrogen being passed into fluidized bed for inside.
Embodiment 2
The present embodiment provides a kind of preparation methods of above-mentioned silicon powder for fluidized reaction, comprising the following steps:
(1) silica fine powder, binder, water are mixed, the mass ratio of water and silica fine powder is 1:5, is machined as greatly by being granulated
Particle spherical silicon powder particle, bulky grain silicon powder are bonded by silica fine powder by binder, the mass ratio of binder and silica fine powder
For 10:100,800 mesh of partial size of silica fine powder, binder is plant fiber；Specifically, pelletizer is made by wet process in the present embodiment
Grain processing obtains bulky grain silicon powder.The partial size of silicon powder is big, forms fluidisation state when fluidized reaction occurs convenient for silicon powder, it is anti-to reach fluidisation
It should require, silicon powder particle comes into full contact with nitrogen.Specifically, pelletizer includes but is not limited to high-speed stirring tooth pelletizer, horizontal height
Fast mixed granulation machine.
(2) bulky grain silicon powder being heated by heat drier, heating temperature is 320 DEG C, and heating time is 1 hour, so that
Binder decomposition escapes in gaseous form, obtains the internal silicon powder with hole, and the porosity of silicon powder is 15%, the grain of silicon powder
Diameter is 120 mesh.Electric heating is provided with outside heat drier, heat drier bottom is provided with pipeline for being passed through high temperature nitrogen
For being heated, after binder decomposes evolution in gaseous form in bulky grain silicon powder, tiny lead to is generated inside silicon powder
Road, while moisture removes.Inside has the silicon powder of hole for flowing with the nitrogen being passed into fluidized bed in the case where fluidizing state
Change reaction and generates silicon nitride.Binder can generate many tiny holes after thermally decomposing in silicon powder particle, anti-convenient for fluidisation
The infiltration of seasonable nitrogen, increases the contact area of nitrogen and silicon powder.
Embodiment 3
The present embodiment provides a kind of preparation methods of above-mentioned silicon powder for fluidized reaction, comprising the following steps:
(1) silica fine powder, binder, water are mixed, the mass ratio of water and silica fine powder is 3:7, is machined as greatly by being granulated
Particle spherical silicon powder particle, bulky grain silicon powder are bonded by silica fine powder by binder, the mass ratio of binder and silica fine powder
For 7:100,1200 mesh of partial size of silica fine powder, binder includes plant fiber and starch (mass ratio 2:1)；Specifically, this implementation
Pelletizer is processed to obtain bulky grain silicon powder by wet granulation in example.
(2) bulky grain silicon powder is heated, heating temperature is 250 DEG C, and heating time is 4 hours, so that binder is decomposed with gas
The form of body escapes, and obtains the internal silicon powder with hole, and the porosity of silicon powder is 40%, and the partial size of silicon powder is 80 mesh.This is interior
There is the silicon powder of hole to generate silicon nitride for fluidized reaction to occur in the case where fluidizing state with the nitrogen being passed into fluidized bed in portion.
Embodiment 4
As shown in Figure 1, the present embodiment provides a kind of for producing the device of silicon nitride, comprising:
Pelletizer 1, for mixed silica fine powder and binder to be processed as bulky grain silicon powder；
Elevator 2 is connect with pelletizer 1, and elevator 2 is used to that obtained bulky grain silicon powder will to be granulated by pelletizer 1 and mentions
It is raised in heat drier 3；Elevator 2 in the present embodiment is bucket elevator.
Heat drier 3 is connect with elevator 2, and heat drier 3 is used for heat drying bulky grain silicon powder, so that bonding
Agent decomposition escapes in gaseous form, obtains the internal silicon powder with hole；
Fluidized bed 4 is connect with heat drier 3, and fluidized bed 4 is used under the fluidisation state of silicon powder and nitrogen in it flow
Change reaction；
Cyclone separator 5 is connect with fluidized bed 4, and the material in fluidized bed 4 enters cyclone separator 5 and carries out gas solid separation,
Solid particle after separation falls back in fluidized bed 4, and the gas after separation is flowed into heat exchanger 9；Cyclone separator 5 includes using
In the cyclone separating chamber 16 of cyclonic separation, cyclone separating chamber 16 is set in fluidized bed 4, and the feed inlet 6 of cyclone separator is located at
The settling section of fluidized bed 4, the slag-drip opening 7 of cyclone separator are located at the conversion zone of fluidized bed 4, the gas vent 8 of cyclone separator
Outside fluidized bed 4.
Heat exchanger 9 is connect with cyclone separator 5, and heat exchanger 9 carries out gas solid separation for exchanging heat, by cyclone separator 5
The gas-solid mixture obtained afterwards enters heat exchanger 9 and temperature control medium and exchanges heat, by being cooled down after heat exchange in heat exchanger 9
Gas is flowed into again in bag hose 13, the gaseous state temperature control medium in heat exchanger 9 by being heated up after heat exchange；Specifically, this reality
Applying the temperature control medium in example is nitrogen；Specifically, in the present embodiment heat exchanger 9 be gas-to-gas heat exchanger, vertical installation, and for pipe
Formula heat exchanger.The tube side 10 that heat exchanger is walked by the gas-solid mixture that cyclone separator 5 obtain after gas solid separation, from heat exchange
The top end socket of the tube side 10 of device enters, and leaves from the bottom bulkhead of the tube side 10 of heat exchanger.Nitrogen walks the shell side 11 of heat exchanger,
Enter from the bottom of the shell side 11 of heat exchanger, is left from the top of the tube side 10 of heat exchanger.
Bag hose 13 is connect with heat exchanger 9, is flowed again in heat exchanger 9 by the gas-solid mixture to be cooled down after heat exchange
Enter dust removal by filtration in bag hose 13.
The temperature control medium outlet of heat exchanger 9 is also connect with the entrance of fluidized bed 4, by obtaining after heat exchange in heat exchanger 9
The gaseous nitrogen atmosphere of heating be passed into fluidized bed 4；Specifically, the temperature control medium outlet of the heat exchanger 9 in the present embodiment is specific
For the shell-side outlet 12 of heat exchanger.
The temperature control medium outlet of heat exchanger 9 is also connect with bag hose 13, and bag hose 13 is connect with the entrance of fluidized bed 4,
The solid particle that 13 dust removal by filtration of bag hose obtains is blown by the gaseous nitrogen atmosphere of the heating obtained after heat exchange in heat exchanger 9
In fluidized bed 4；
The temperature control medium outlet of heat exchanger 9 also connect with heat drier 3, by obtaining after exchanging heat in the heat exchanger 9
The gaseous nitrogen atmosphere of heating is passed into heat drier 3.
The present embodiment provides a kind of methods for producing silicon nitride, comprising the following steps:
The silicon powder of fluidized reaction is used for by any preparation method preparation of Examples 1 to 3.
The silicon powder of preparation is added in fluidized bed 4,4 lower part of fluidized bed is provided with gas distribution grid 14, silicon powder be passed through
Nitrogen in fluidized bed 4 after gas distribution grid 14 is divided equally forms 4 layers of fluidized bed in the conversion zone of fluidized bed 4, is fluidizing
Fluidized reaction occurs under state and generates silicon nitride, the temperature of the reaction in fluidized bed 4 is 1200~1300 DEG C, and nitrogen is High Purity Nitrogen
Gas, nitrogen content >=99.99mas% in high pure nitrogen.Tail gas after reaction carries solid particle and is upwardly into the heavy of fluidized bed 4
Section drops, and the flow velocity of gas is reduced, and the partial particulate carried in gas settles down in the settling section of fluidized bed 4 into fluidized bed 4
Conversion zone the reaction was continued, enter cyclone separator 5 by the reaction end gas of settling section.Silicon powder for being reacted in fluidized bed 4
Partial size be 20~120 mesh, porosity be 15~40%.Fixed bed process, which is reacted by silicon powder with nitrogen, in the prior art generates nitrogen
SiClx, the partial size of silicon powder in the prior art are generally less than 600 mesh, abundant convenient for gas-solid contact in fixed bed reaction.This implementation
In example, the inside of the silicon powder reacted for fluidized bed 4 has hole, and porosity is big, can also be with so even if the partial size of silicon powder is big
It in fluidized reaction, is come into full contact with nitrogen, and the partial size of silicon powder is 20~120 mesh, and silicon powder can be made in the atmosphere of nitrogen
It is lower to form fluidisation state well.
Cyclone separator 5 is connect with fluidized bed 4, and the material in fluidized bed 4 enters cyclone separator 5 and carries out gas solid separation,
Solid particle after separation falls back in fluidized bed 4 that the reaction was continued, and the gas after separation is flowed into be connect with cyclone separator 5
In heat exchanger 9.Solid particle of the partial size carried in gas in cyclone separator 5 greater than 10 μm is separated by whirlwind point
Scum pipe from device 5 returns to the conversion zone of fluidized bed 4.The gas-solid obtained after gas solid separation dedusting is carried out by cyclone separator 5
Mixture enters heat exchanger 9 and temperature control medium exchanges heat.
It is flowed into bag hose 13 again in heat exchanger 9 by the gas to be cooled down after heat exchange, by changing in heat exchanger 9
The gaseous state temperature control medium to be heated up after heat.Temperature control medium is nitrogen.By the gas-solid mixture after 5 dedusting of cyclone separator from
The top of fluidized bed 4 comes out the tube side 10 for entering heat exchanger from top, is changed with the cold nitrogen for the shell side 11 for entering heat exchanger
Heat, gas-solid mixture are cooled to 300 DEG C hereinafter, cold nitrogen is heated to 180 DEG C or more.
After 13 dust removal by filtration of bag hose, tail gas is obtained, containing minimal amount of in the tail gas obtained by above-mentioned processing
Dust, main component are unreacted nitrogen, tail gas emptying.
Tail gas after 13 dedusting of bag hose contains nitrogen, and is mixed in micro dust therein (dust includes nitrogen
SiClx, metallic silicon), dust content is less than 100mg/m3。
The temperature control medium outlet of heat exchanger 9 is also connect with the entrance of fluidized bed 4, by obtaining after heat exchange in heat exchanger 9
The gaseous nitrogen atmosphere of heating be passed into fluidized bed 4, the nitrogen after heating, which enters in fluidized bed 4, to be formed fluidisation state and continues anti-
It answers.13 filter core of bag hose uses metal agglomeration filter core, and it is 100~500 DEG C using temperature that separation accuracy, which is 200 mesh,.Due to fluidisation
The temperature of reaction in bed 4 is 1200~1300 DEG C, and the temperature for the gas being discharged in fluidized bed 4 is excessively high, is carried out by heat exchanger 9
Heat exchange cooling, enters back into bag hose 13, bag hose 13 can be effectively protected, avoid the aging at high temperature of bag hose 13.
The temperature control medium outlet of heat exchanger 9 is also connect with bag hose 13, and bag hose 13 is connect with the entrance of fluidized bed 4,
The solid particle that 13 dust removal by filtration of bag hose obtains is blown by the gaseous nitrogen atmosphere of the heating obtained after heat exchange in heat exchanger 9
In fluidized bed 4, the reaction was continued.The temperature control medium of heat exchanger 9 exports and is provided with valve 17 on the pipeline between bag hose 13, by
The nitrogen of the temperature control medium outlet outflow of heat exchanger 9 carries out purging deslagging to bag hose 13 as purging nitrogen.Pass through regulating valve
The opening and closing of door 17, control purging nitrogen periodically carry out purging deslagging to bag hose 13.Solid particle in bag hose 13 is by blowing
It sweeps and re-enters into fluidized bed 4, can solid particle be recycled, the waste of the material avoided.By heat exchanger 9
Temperature control medium outlet outflow nitrogen be heat up gas nitrogen, the solid particle being obtained by filtration in bag hose 13 is blown
It sweeps, the temperature of solid particle can be promoted, so that there is certain temperature when these solid particles are entered in reactor
Degree, so as to save the energy that solid particle is heated.
The temperature control medium outlet of heat exchanger 9 also connect with heat drier 3, by obtaining after exchanging heat in the heat exchanger 9
The gaseous nitrogen atmosphere of heating is passed into heat drier 3, can save the energy of the offer of heat drier 3.
The cylinder body outer wall of fluidized bed 4 is provided with insulating layer and heating device, every on the corresponding cylinder of the conversion zone of fluidized bed 4
Rice is arranged the accurate control that temperature measurer realizes bed temperature, during fluidized reaction, the temperature control of the conversion zone of fluidized bed 4
Range processed is 1200~1300 DEG C, heating device and temperature measurer composed cascade interlocked control circuit.When the temperature of conversion zone is higher than
At 1300 DEG C, heater stop heating, when the temperature of conversion zone is lower than 1200 DEG C, heating device starting heating.
In fluidized bed 4, after silicon powder reacts a period of time with nitrogen, most of silicon powder generates silicon nitride, fluidized bed 4 by nitridation
Conversion zone deslagging pipeline at take a small amount of nitridation silicon sample to be detected, when silicon nitride content is more than 95% or more, stopping
Beta-silicon nitride powder in fluidized bed 4 is discharged by solid discharge mouth 15 after device is cooling for reaction.
When fluidized bed 4 diameter be 100mm, be highly 1100mm, silica fine powder additional amount be 200g when, the flow of nitrogen is
2-10m3Under conditions of/hour, there is preferable fluid effect.
The present embodiment also provides a kind of silicon nitride, to be produced by above-mentioned method.
The inside of silicon powder in the present embodiment has hole, substantially increases the specific surface area and porosity of silicon powder, silicon powder
When carrying out fluidized reaction with nitrogen, nitrogen is entered in the channel of the hole formation of the inside of silicon powder to come into full contact with and be connect with silicon powder
Touching not only substantially increases gas, solid phase interface product, but also improves nitrogen in the channel of the hole formation of the inside of silicon powder
Velocity of liquid assets, so that the speed of fluidized reaction is improved, so that silicon nitride not only can be generated on the surface of silicon powder, but also in silicon powder
Inside can also generate silicon nitride, and substantially increase the conversion ratio of silicon powder.
Silicon powder comes into full contact with nitrogen in the present embodiment, and gas, solid phase interface product are big, and reaction rate is fast, after reacting 2 hours
The conversion ratio of silicon powder can reach 95% or more, and reaction time is short.And silicon nitride is prepared using fixed bed in currently available technology
Reaction technology in reach the reaction time that 95% or more conversion ratio needs be 40 more than hour.
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 (17)
1. a kind of silicon powder for fluidized reaction, which is characterized in that the inside of the silicon powder has hole.
2. the silicon powder according to claim 1 for fluidized reaction, which is characterized in that the porosity of the silicon powder be 15~
40%.
3. the silicon powder according to claim 1 or 2 for fluidized reaction, which is characterized in that the partial size of the silicon powder is 20
~120 mesh.
4. the preparation method described in a kind of claims 1 to 3 any one for the silicon powder of fluidized reaction, which is characterized in that packet
Include following steps:
(1) silica fine powder, binder, water are mixed, is machined as bulky grain silicon powder by being granulated, bulky grain silicon powder is led to by silica fine powder
Binder is crossed to bond；
(2) bulky grain silicon powder is heated, so that binder decomposition escapes in gaseous form, obtains the internal silicon powder with hole.
5. the preparation method of the silicon powder according to claim 4 for fluidized reaction, which is characterized in that the step (1)
Described in the mass ratio of binder and the silica fine powder be (5~10): 100.
6. the preparation method of the silicon powder according to claim 4 for fluidized reaction, which is characterized in that the step (2)
In heating temperature be 250~400 DEG C, heating time be 1~4 hour.
7. the preparation method according to claim 4~6 any one for the silicon powder of fluidized reaction, which is characterized in that
The partial size of the silica fine powder≤500 mesh.
8. the preparation method according to claim 4~6 any one for the silicon powder of fluidized reaction, which is characterized in that
The binder includes one or more of methylcellulose, plant fiber, starch.
9. a kind of method for producing silicon nitride, which comprises the following steps:
The silicon powder of fluidized reaction is used for by the preparation of preparation method described in claim 4~8 any one；
The silicon powder of preparation is added in fluidized bed, fluidisation occurs in the case where fluidizing state for silicon powder and the nitrogen being passed into fluidized bed instead
Silicon nitride should be generated.
10. the method for production silicon nitride according to claim 9, which is characterized in that further comprising the steps of:
Cyclone separator is connect with fluidized bed, and the material in fluidized bed enters cyclone separator and carries out gas solid separation, after separation
Solid particle falls back in fluidized bed, and the gas-solid mixture after separation is flowed into the bag hose connecting with cyclone separator, leads to
After crossing bag hose dust removal by filtration, tail gas is obtained.
11. the method for production silicon nitride according to claim 10, which is characterized in that between cyclone separator and bag hose
It is additionally provided with heat exchanger, heat exchanger is connect with cyclone separator, bag hose respectively, after carrying out gas solid separation by cyclone separator
Obtained gas-solid mixture enters heat exchanger and temperature control medium exchanges heat, the gas-solid in heat exchanger by being cooled down after heat exchange
Mixture flows into dust removal by filtration in bag hose again, the gaseous state temperature control medium in heat exchanger by being heated up after heat exchange.
12. the method for production silicon nitride according to claim 11, which is characterized in that the temperature control medium is nitrogen, is changed
The temperature control medium outlet of hot device is also connect with the entrance of fluidized bed, by the gaseous nitrogen of the heating obtained after heat exchange in heat exchanger
Gas is passed into fluidized bed.
13. the method for production silicon nitride according to claim 11, which is characterized in that the temperature control medium is nitrogen, is changed
The temperature control medium outlet of hot device is also connect with bag hose, and the entrance connection of bag hose and fluidized bed passes through heat exchange in heat exchanger
The solid particle that bag hose dust removal by filtration obtains is blown into fluidized bed by the gaseous nitrogen atmosphere of the heating obtained afterwards.
14. the method for production silicon nitride according to claim 11, which is characterized in that the preparation is for fluidized reaction
The preparation method of silicon powder heats bulky grain silicon powder by heat drier, heat drier be set to pelletizer and fluidized bed it
Between, heat drier is connect with pelletizer, fluidized bed respectively, and the temperature control medium is nitrogen, and the temperature control medium of heat exchanger exports
It is also connect with heat drier, heat drier is passed by the gaseous nitrogen atmosphere of the heating obtained after heat exchange in heat exchanger
It is interior.
15. the method for silicon nitride is produced described in 0~14 any one according to claim 1, which is characterized in that cyclone separator
Including the cyclone separating chamber for cyclonic separation, cyclone separating chamber is set in fluidized bed, and the feed inlet of cyclone separator is located at
The settling section of fluidized bed, the slag-drip opening of cyclone separator are located at the conversion zone of fluidized bed, and the gas vent of cyclone separator is located at
Outside fluidized bed.
16. the method for silicon nitride is produced described in 0~14 any one according to claim 1, which is characterized in that the fluidized bed
The temperature of interior reaction is 1200~1300 DEG C.
17. a kind of silicon nitride, which is characterized in that it is the production of the method as described in claim 9~16 any one.
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