CN109467063A - The fluidized-bed reactor and its apparatus system and method for production silicon nitride - Google Patents
The fluidized-bed reactor and its apparatus system and method for production silicon nitride Download PDFInfo
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- CN109467063A CN109467063A CN201710804871.2A CN201710804871A CN109467063A CN 109467063 A CN109467063 A CN 109467063A CN 201710804871 A CN201710804871 A CN 201710804871A CN 109467063 A CN109467063 A CN 109467063A
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 91
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000010438 heat treatment Methods 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005192 partition Methods 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000006698 induction Effects 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000013316 zoning Methods 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002826 coolant Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005243 fluidization Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000005439 thermosphere Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- 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
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a kind of fluidized-bed reactors for producing silicon nitride, including material reaction area and the heating device being looped around around material reaction area, the heating device includes more than two heating zones, temperature gradually rises from the bottom to top for the heating zone, material reaction area is divided at least two humidity provinces from the bottom to top under the action of the heating zone, the humidity province contains at least one low-temperature space and a high-temperature region, silicon powder and nitrogen carry out pre-reaction in the low-temperature space, in the high-temperature region, silicon powder, nitrogen, silicon nitride further react.The invention also discloses a kind of apparatus system for producing silicon nitride comprising the fluidized-bed reactor and the method using apparatus system production silicon nitride.The advantages that present invention is independently controlled the reaction temperature of the different zones of reactor by setting partition heating respectively, can guarantee that the independent of differential responses occurs, have conversion rate of products high, and purity is high, production cost is low, can be used for serialization industrial production.
Description
Technical field
The invention belongs to inorganic non-metallic powder preparation fields, and in particular to a kind of fluidized-bed reaction for producing silicon nitride
Device further relates to a kind of apparatus system of production silicon nitride comprising the fluidized-bed reactor, and raw using the apparatus system
The method for producing silicon nitride.
Background technique
Silicon nitride (Si3N4) it is the important source material for preparing silicon nitride ceramics, it has high temperature resistant, hardness high, wear-resistant, strong
The excellent physical and chemical performances such as degree is high, thermal expansion coefficient is small, thermal shock performance is good, antioxygenic property is good, be widely used in it is metallurgical,
The industries such as chemical industry, electronics and military project.
There are four types of basic skills, i.e. direct nitridation method, carbothermic method, chemical gas-phase method and heat for the preparation of silicon nitride at present
Decomposition method, wherein with direct nitridation method using relatively broad.Direct nitridation method is in certain pressure and 1000 DEG C or more high temperature
Under, nitrogen is passed through in the reaction unit for placing silicon powder and carries out redox reaction and generates silicon nitride.Since silicon nitride is easy
Bond it is blocking, it is subsequent also need to be ground, be crushed etc. processes processing after product could be used as to use.Therefore, though direct nitridation method
Right preparation process is simple, but production efficiency is low, is also easy to introduce impurity in subsequent handling, is unfavorable for being mass produced, and produce
Higher cost.
Fluidization technology is led since it is with heat-transfer effect between strong gas-solid in burning, particle drying, gas-solid reaction etc.
It gradually applies in domain.Under fluidization, a large amount of collision occurs for gas and solid particle, and heat transfer, mass transfer are violent, beneficially improve
Gas, affixed touching and reaction rate, and reaction temperature is uniform, so that continuous production silicon nitride is easily achieved.
Japanese Shin-Etsu company reports in US5817285 prepares silicon nitride using fluidized-bed reaction, so its reaction
It needs first to preheat metallic silicon at vacuum, 1000-1400 DEG C, enters back into reactor.University of Science & Technology, Beijing Wang Li etc. exists
Disclose in CN1792774 makes silicon powder quickly through high temperature fluidized bed, under high-temperature pressure by the way of dilute phase pneumatic conveying
Combustion synthesis reaction occurs and obtains alpha-silicon nitride powders, reaction process is also required to preheat silicon powder.Zhejiang University Cheng Le ring etc.
A kind of direct silicon nitride preparing fluidized bed device and method are disclosed in CN1974379, use Al2O3、SiO2、ZrO2
Etc. tiny high-temperature resistant particle as fluidized bed material, to improve fluidization quality and nitridation reaction effect.Add in silicon powder simultaneously
Enter Chemical Felter for being sintered.However the addition of these substances, influence is caused on the purity of silicon nitride product.New spy's energy
The small dragon of source limited liability company Pan etc. discloses a kind of horizontal stream in reaction chamber setting baffling mechanism in CN205634895
Change bed, baffling mechanism extends raw material in the reaction chamber indoor residence time, but is also easy to cause alpha-silicon nitride powders in baffling
Adhesion and blocking at mechanism.
In conclusion a kind of novel reactor and preparation process for preparing high purity silicon nitride silicon powder is still required, overcome
Drawbacks described above can reduce the whole preparation cost of silicon nitride, improve reactor production capacity, realize industrial-scale production,
It can also solve the problems such as production efficiency is low, product purity is low, product quality is uneven.Inventor herein passes through test of many times
Verifying, develops this patent fluidized-bed reactor and its apparatus system, and be used for the preparation of nitriding powder, further grinds
Study carefully and forms the art of this patent scheme.
Summary of the invention
The object of the present invention is to provide a kind of fluidized-bed reactor for producing silicon nitride, the fluidized-bed reactor can be protected
It demonstrate,proves the independent of differential responses to occur, realizes the uniform and stable progress of gas-solid reaction, avoid the generation of by-product impurity, be greatly improved
The purity of silicon nitride product can obtain the product of uniform quality, and can be applicable in the large-scale fluidized bed reactor of major diameter,
The production capacity for improving separate unit reactor, can overcome the problems, such as that production efficiency is low.
The device system for the production silicon nitride that it is a further object to provide a kind of comprising the fluidized-bed reactor
System.
It is a further object to provide a kind of methods using described device system production silicon nitride.
In order to realize goal of the invention, The technical solution adopted by the invention is as follows:
A kind of fluidized-bed reactor producing silicon nitride including material reaction area and is looped around adding around material reaction area
Thermal, which is characterized in that the heating device includes more than two heating zones, and temperature is gradually from the bottom to top for the heating zone
It increases, material reaction area is divided at least two humidity provinces from the bottom to top under the action of the heating zone, and the humidity province is at least
Comprising a low-temperature space and a high-temperature region, silicon powder and nitrogen carry out pre-reaction, in the high-temperature region, silicon in the low-temperature space
Powder, nitrogen, silicon nitride further react.
With the progress pre-reaction of lower temperature, the oxygen that on the one hand can be eliminated in silicon powder contains for silicon powder and nitrogen in low-temperature space
Amount, another aspect production section silicon nitride；In high-temperature region, silicon powder, nitrogen, silicon nitride further react, and it is higher to obtain conversion ratio
Silicon nitride.
In a preferred embodiment, the temperature of the low-temperature space is between 1000~1400 DEG C, the temperature of high-temperature region
Degree is between 1400~1600 DEG C.
In a preferred embodiment, the heating device includes 2 heating zones, the temperature range of the low-temperature space
Between 1000~1400 DEG C, the temperature range of the high-temperature region is between 1400~1600 DEG C.
In further preferred embodiment, the heating device includes 3 heating zones, the temperature range of the low-temperature space
Between 1000~1200 DEG C, the temperature range of the nearly high-temperature region is between 1300~1400 DEG C, the temperature of the high-temperature region
Range is between 1400~1600 DEG C.
In a preferred embodiment, the heating device is electromagnetic induction heater, including induction heating layer,
And it is looped around the line of induction ring layer around the induction heating layer.
In a preferred embodiment, the induction heating layer is conductive material layer, one in quartz, graphite
Kind is several；The side spraying silicon nitride or silicon carbide of the induction heating layer contacting material.
In a preferred embodiment, the thickness of the induction heating layer is between 10mm~300mm.
In a preferred embodiment, the reactor further includes the heat preservation being looped around around the induction heating layer
Layer, and/or the cooling layer being looped around around the line of induction ring layer.
In a preferred embodiment, the insulating layer is selected from one of refractory brick, aluminium-silica fireproof material or several
Kind；The cooling layer uses cooling water as cooling medium.
In a preferred embodiment, the fluidized-bed reactor includes at least 6 layers, i.e. material reaction from inside to outside
Area, induction heating layer, insulating layer, line of induction ring layer, cooling layer and shell.The shell can be metal shell.
The apparatus system of production silicon nitride comprising above-mentioned fluidized-bed reactor, comprising: the stream of above-mentioned production silicon nitride
Fluidized bed reactor；For cooling down the heat exchanger of reaction end gas；For separating the filter of silicon nitride, wherein the heat exchanger
One end is connect with the discharge port of the fluidized-bed reactor, and the other end is connected with filter.
In a preferred embodiment, described device system further includes silicon powder measuring tank, the silicon powder measuring tank
Discharge port is connected with the feed inlet of the fluidized-bed reactor, and silicon powder charging is controlled by the baiting valve of silicon powder measuring tank.
In a preferred embodiment, the filter is selected from bag filter or counter-blow type filter.
Using the method for above-mentioned apparatus system production silicon nitride, using fluidized-bed reactor, in the way of partition heating
So that material reaction area is divided at least two humidity provinces from the bottom to top, and temperature gradually rises from the bottom to top, and the humidity province is extremely
It less include a low-temperature space and a high-temperature region, silicon powder and nitrogen carry out pre-reaction in the low-temperature space, in the high-temperature region,
Silicon powder, nitrogen, silicon nitride further react, by the gas and silicon powder that enter from fluidized-bed reactor bottom in fluidized-bed reactor
Middle continuous zoning nitridation, tail gas is after heat exchanger and charging heat exchange, into the isolated silicon nitride of filter.
In a preferred embodiment, the gas is nitrogen and hydrogen or nitrogen and ammonia, wherein the hydrogen
The molar ratio of gas or ammonia is between 0~30%.
In a preferred embodiment, the tail gas separates after heat exchanger and charging heat exchange into filter
Obtained alpha-silicon nitride powders, nitrogen recycling utilize.
The utility model has the advantages that
Fluidized-bed reactor according to the present invention, by the way that partition heating is arranged, to the different zones such as low-temperature space of reactor
It is independently controlled respectively with the reaction temperature of high-temperature region, further ensures the independent hair of differential responses in fluidized-bed reactor
It is raw, the uniform and stable progress of gas-solid reaction is realized, the generation of by-product impurity is avoided, greatly improves the pure of silicon nitride product
Degree, can obtain the product of uniform quality.
Fluidized-bed reactor according to the present invention, due to replacing traditional electric heating or microwave heating using induction heating,
The material that inside reactor is directly directly heated by the Induced magnetic field that alternating current generates provides enough reaction heat to bed
Amount can be applicable in the large-scale fluidized bed reactor of major diameter, improve the production capacity of separate unit reactor, production efficiency can be overcome low
Problem.
The apparatus system of production silicon nitride according to the present invention, gas-solid phase contact area is very big, can be realized stable and uniform
Heat and mass reaction, the silicon nitride of generation are discharged by continuous discharge mouth, guarantee the continuous production of reaction, and production cycle
Short, whole investment is lower, greatly reduces production cost, and the industrial-scale production of silicon nitride preparation may be implemented.
Silicon nitride production method according to the present invention, using fluidized bed as main reactor, in the way of partition heating
So that material reaction area is divided at least two humidity provinces from the bottom to top, reacted in humidity province by controlling different material,
It realizes continuous zoning nitridation, high purity silicon nitride product can be obtained, uniform in quality, impurity content is few, and conversion rate of products is high,
Production cost is low, can be used for serialization industrial production.
Detailed description of the invention
Fig. 1 is fluidized-bed reactor schematic diagram of the invention；
In figure, 1- fluidized-bed reactor, 2- metal shell layer, 3- cooling layer, 4- line of induction ring layer, 5- insulating layer, 6- sense
Answer heating layer, 7- material reaction area.
Fig. 2 is the apparatus system schematic diagram of continuous production silicon nitride of the present invention；
In figure: 8- passes in and out material heat exchanger, 9- filter, 10- silicon powder measuring tank, 11- silicon powder baiting valve.
Specific embodiment
Detailed description of the preferred embodiments with reference to the accompanying drawing.
As shown in Figure 1, the present invention produces the fluidized-bed reactor of silicon nitride, including material reaction area and to be looped around material anti-
Answer the heating device around area, the heating device includes more than two heating zones, the heating zone from the bottom to top temperature by
Edge up height, and material reaction area is divided at least two humidity provinces from the bottom to top under the action of the heating zone, and the humidity province is extremely
It less include a low-temperature space and a high-temperature region, silicon powder and nitrogen carry out pre-reaction in the low-temperature space, in the high-temperature region,
Silicon powder, nitrogen, silicon nitride further react.
Innovative point of the invention, which is that, is arranged partition heating by fluid bedreactors, to the different zones of reactor
If the reaction temperature of low-temperature space and high-temperature region is independently controlled respectively, it is further ensured that differential responses in fluidized-bed reactor
It is independent to occur, to realize the uniform and stable progress of gas-solid reaction, avoid the generation of by-product impurity.Specific to embodiment party of the invention
In case, heating device includes 2 heating zones, and the temperature range of the low-temperature space is between 1000~1400 DEG C, the high-temperature region
Temperature range between 1400~1600 DEG C.Silicon powder and nitrogen are in low-temperature space with the progress pre-reaction of lower temperature, a side
Face can eliminate the oxygen content in silicon powder, another aspect production section silicon nitride；In high-temperature region, silicon powder, nitrogen, silicon nitride are into one
Step reaction, obtains the higher silicon nitride of conversion ratio.In a further preferred embodiment, heating device includes 3 heating zones,
The temperature range of the low-temperature space between 1000~1200 DEG C, the temperature range of the nearly high-temperature region 1300~1400 DEG C it
Between, the temperature range of the high-temperature region is between 1400~1600 DEG C.
In view of the heating defect of conventional heating device fluid bedreactors, heating device of the invention is selected from electromagnetism sense
Heating device, including induction heating layer are answered, and the line of induction ring layer being looped around around the induction heating layer.The present invention utilizes
Reactor is divided into two or more humidity provinces by the technology of induction heating from the bottom to top.Induction heating can be non-contact
Adjustable thermal field is stablized in offer, keeps constant reaction temperature.In a preferred embodiment, the induction heating layer is
Conductive material layer, selected from one or more of quartz, graphite；The side spraying silicon nitride of the induction heating layer contacting material
Or silicon carbide, to reduce the content of impurity in product, the purity of silicon nitride can achieve 5 nine or more.It is preferred at one
In embodiment, the temperature and work electricity of thickness heating as needed for the characteristic of conductive material, material of the induction heating layer
The frequency of stream determines, between 10mm~300mm.In a preferred embodiment, the reactor further includes being looped around
Insulating layer around the induction heating layer, and/or the cooling layer being looped around around the line of induction ring layer.It is preferred at one
In embodiment, the insulating layer is generally refractory material, is selected from one or more of refractory brick, aluminium-silica fireproof material；Institute
Stating cooling layer uses cooling water as cooling medium, for cooling down coil.
In practical operation, fluidized-bed reactor of the present invention includes at least 6 layers, i.e. material reaction area, induction hair from inside to outside
Thermosphere, insulating layer, line of induction ring layer, cooling layer and shell.The shell can be metal shell.
Another technical solution provided by the invention, i.e. the device system of the production silicon nitride comprising above-mentioned fluidized-bed reactor
System, comprising: the fluidized-bed reactor of above-mentioned production silicon nitride；For cooling down the heat exchanger of reaction end gas；It is nitrogenized for separating
The filter of silicon, wherein one end of the heat exchanger is connect with the discharge port of the fluidized-bed reactor, the other end and filter
It is connected.Continuous zoning nitrogenizes in a fluidized bed reactor for gas and silicon powder, and tail gas is after heat exchanger and charging heat exchange, into filtering
The isolated silicon nitride of device, nitrogen circulation utilize.
Specifically, described device system further includes silicon powder measuring tank, the discharge port of the silicon powder measuring tank and the fluidisation
The feed inlet of bed reactor is connected, and silicon powder charging is controlled by the baiting valve of silicon powder measuring tank.Silicon powder feeds too fast, Yi Zao
At the bonding of silicon powder in reactor；Fed slow, then production efficiency reduction.Filter is selected from bag filter or back flushing type mistake
Filter.Bag filter will regularly replace, it is therefore desirable to be operated in parallel；Counter-blow type filter can carry out blowback online, be not required to
It is spare.The heat exchanger preferably passes in and out material heat exchanger.
Method using above-mentioned apparatus system production silicon nitride of the invention, using fluidized-bed reactor, using subregion plus
The mode of heat makes material reaction area be divided at least two humidity provinces from the bottom to top, and temperature gradually rises from the bottom to top, described
Humidity province contains at least one low-temperature space and a high-temperature region, and silicon powder and nitrogen carry out pre-reaction in the low-temperature space, in institute
High-temperature region is stated, silicon powder, nitrogen, silicon nitride further react, and the gas entered from fluidized-bed reactor bottom and silicon powder are being flowed
Continuous zoning nitrogenizes in fluidized bed reactor, and tail gas is after heat exchanger and charging heat exchange, into the isolated silicon nitride of filter.
As previously mentioned, partition heating of the invention refers to electromagnetic induction partition heating, it is primarily referred to as utilizing induction heating
Reactor is divided into two or more humidity provinces by technology from the bottom to top.Induction heating can non-contact offer stabilization can
The thermal field of tune, keeps constant reaction temperature.In addition, the gas is nitrogen and hydrogen or nitrogen and ammonia, wherein described
The molar ratio of hydrogen or ammonia is between 0~30%.Hydrogen, ammonia are used as also Primordial Qi, and the oxygen element in silicon powder is restored,
Enhance the reactivity of silicon powder.The nitrogen is high pure nitrogen.Tail gas of the present invention through heat exchanger and charging heat exchange after, into
Enter the isolated alpha-silicon nitride powders of filter, nitrogen can recycle.
Comparative example 1
The preparation of silicon nitride is carried out using nitridation silicon manufacturing apparatus as shown in Figure 2, only the fluidized-bed reactor is not
Subregion is carried out to heating, i.e. heating device is identical to the heat effect of integrated fluidized bed reaction zone, and heating and temperature control is 1400
℃.By 300 μm of average grain diameter of silicon powder by baiting valve with the nitrogen of the speed of 0.5kg/h and the inlet amount of 10Nm3/h together
It is passed through the fluidized-bed reactor of DN80, controls fluidizing velocity, guarantees residence time of the reaction mass inside fluidized-bed reactor
For 60s, silicon powder and nitrogen material sufficiently react, and tail gas is after disengaging material heat exchanger and charging heat exchange, into filter
Isolated silicon nitride, nitrogen circulation utilize, and collect silicon nitride product after 2 hours, and calculate conversion ratio.
Embodiment 1
The preparation of silicon nitride is carried out using nitridation silicon manufacturing apparatus as shown in Figure 2, fluidized-bed reactor setting
Heating zone is 2, including low-temperature space and high-temperature region, wherein at 1200 DEG C, high-temperature region adds the heating and temperature control of low-temperature space
Hot temperature control is at 1400 DEG C.By 300 μm of average grain diameter of silicon powder by baiting valve with the speed and 10Nm of 0.5kg/h3/ h's
The nitrogen of inlet amount is passed through the fluidized-bed reactor of DN80 together, controls fluidizing velocity, guarantees reaction mass in fluidized-bed reaction
The residence time of device low-temperature space and high-temperature region is respectively 50s and 60s, and silicon powder and nitrogen material sufficiently react, tail gas pass through into
After material heat exchanger and charging exchange heat out, into the isolated silicon nitride of filter, nitrogen circulation is utilized, and collects nitrogen after 2 hours
SiClx powder, and calculate conversion ratio.
Embodiment 2
The preparation of silicon nitride is carried out using nitridation silicon manufacturing apparatus as shown in Figure 2, fluidized-bed reactor setting
Heating zone is 2, including low-temperature space and high-temperature region, wherein at 1100 DEG C, high-temperature region adds the heating and temperature control of low-temperature space
Hot temperature control is at 1500 DEG C.By 200 μm of average grain diameter of silicon powder by baiting valve with the speed and 5Nm of 0.4kg/h3/ h into
The nitrogen of doses is passed through the fluidized-bed reactor of DN80 together, controls fluidizing velocity, guarantees reaction mass in fluidized-bed reactor
The residence time of low-temperature space and high-temperature region is respectively 70s and 80s, and silicon powder and nitrogen material sufficiently react, and tail gas is through passing in and out
After material heat exchanger and charging heat exchange, into the isolated silicon nitride of filter, nitrogen circulation is utilized, and nitridation is collected after 5 hours
Silicon powder, and calculate conversion ratio.
Embodiment 3
The preparation of silicon nitride is carried out using nitridation silicon manufacturing apparatus as shown in Figure 2, fluidized-bed reactor setting
Heating zone is 3, including low-temperature space, nearly high-temperature region and high-temperature region, wherein the heating and temperature control of low-temperature space at 1100 DEG C,
The heating and temperature control of nearly high-temperature region is at 1300 DEG C, and the heating and temperature control of high-temperature region is at 1500 DEG C.By 150 μm of average grain diameter
Silicon powder is by baiting valve with the speed and 3Nm of 0.6kg/h3The nitrogen of the inlet amount of/h is passed through the fluidized-bed reaction of DN80 together
Device controls fluidizing velocity, guarantee residence time of the reaction mass in fluidized-bed reactor low-temperature space and high-temperature region be respectively 50s,
70s and 50s, silicon powder and nitrogen material sufficiently react, and tail gas is after disengaging material heat exchanger and charging heat exchange, into filtering
The isolated silicon nitride of device, nitrogen circulation utilize, and collect silicon nitride powder after 3 hours, and calculate conversion ratio.
Conversion ratio is listed as follows:
| Experiment | Conversion ratio (%) |
| Comparative example | 77.5 |
| Embodiment 1 | 94.7 |
| Embodiment 2 | 95.4 |
| Embodiment 3 | 94.2 |
From the list of the above conversion rate of products it can clearly be seen that compared with comparative example 1, embodiment 1, embodiment 2 and reality
The conversion ratio for applying the silicon nitride product of example 3 dramatically increases, moreover, silicon nitride product purity and quality prepared by 4 examples
From the point of view of uniformity, the product parameters of 3 embodiments are above the product parameters of comparative example.
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, but the present invention is not limited to described embodiment.For those of ordinary skill in the art, in original of the invention
Reason and technical idea in the range of, to these embodiments carry out it is a variety of variation, modification, replacement and deformation be still considered as it is of the invention
Protection scope.
Claims (12)
1. a kind of fluidized-bed reactor for producing silicon nitride, including material reaction area and the heating being looped around around material reaction area
Device, which is characterized in that the heating device includes more than two heating zones, and temperature gradually rises from the bottom to top for the heating zone
Height, material reaction area are divided at least two humidity provinces from the bottom to top under the action of the heating zone, and the humidity province is at least wrapped
Containing a low-temperature space and a high-temperature region, silicon powder and nitrogen carry out pre-reaction, in the high-temperature region, silicon in the low-temperature space
Powder, nitrogen, silicon nitride further react.
2. the fluidized-bed reactor of production silicon nitride according to claim 1, which is characterized in that the temperature of the low-temperature space
Between 1000~1400 DEG C, the temperature of high-temperature region is between 1400~1600 DEG C.
3. the fluidized-bed reactor of production silicon nitride according to claim 1, which is characterized in that the heating device is electricity
Metal-magnetic needle, including induction heating layer, and the line of induction ring layer being looped around around the induction heating layer.
4. the fluidized-bed reactor of production silicon nitride according to claim 3, which is characterized in that the induction heating layer is
Conductive material layer, selected from one or more of quartz, graphite；The side spraying silicon nitride of the induction heating layer contacting material
Or silicon carbide.
5. the fluidized-bed reactor of production silicon nitride according to claim 3, which is characterized in that the induction heating layer
Thickness is between 10mm~300mm.
6. the fluidized-bed reactor of production silicon nitride according to claim 3, which is characterized in that the reactor further includes
The insulating layer being looped around around the induction heating layer, and/or the cooling layer being looped around around the line of induction ring layer.
7. the fluidized-bed reactor of production silicon nitride according to claim 6, which is characterized in that the insulating layer is selected from resistance to
One or more of firebrick, aluminium-silica fireproof material；The cooling layer uses cooling water as cooling medium.
8. the apparatus system of the production silicon nitride comprising fluidized-bed reactor described in claim 1~7 any one, feature
It is, comprising:
The fluidized-bed reactor of silicon nitride is produced described in claim 1~7 any one；
For cooling down the heat exchanger of reaction end gas；
For separating the filter of silicon nitride；
One end of the heat exchanger is connect with the discharge port of the fluidized-bed reactor, and the other end is connected with filter.
9. the apparatus system of production silicon nitride according to claim 8, which is characterized in that described including silicon powder measuring tank
The discharge port of silicon powder measuring tank is connected with the feed inlet of the fluidized-bed reactor, and is controlled by the baiting valve of silicon powder measuring tank
Silicon powder charging processed.
10. the apparatus system of production silicon nitride according to claim 8, which is characterized in that the filter is selected from cloth
Bag dust collector or counter-blow type filter.
11. utilizing the method for apparatus system production silicon nitride according to any one of claims 8, which is characterized in that use fluidized-bed reaction
Device makes material reaction area be divided at least two humidity provinces from the bottom to top in the way of partition heating, and temperature from the bottom to top
Gradually rise, the humidity province contains at least one low-temperature space and a high-temperature region, in the low-temperature space silicon powder and nitrogen into
Row pre-reaction, in the high-temperature region, silicon powder, nitrogen, silicon nitride further react, the gas that will enter from fluidized-bed reactor bottom
Continuous zoning nitrogenizes in a fluidized bed reactor for body and silicon powder, and tail gas separates after heat exchanger and charging heat exchange into filter
Obtain silicon nitride.
12. device according to claim 11 system production silicon nitride method, which is characterized in that the gas be nitrogen with
Hydrogen or nitrogen and ammonia, wherein the molar ratio of the hydrogen or ammonia is between 0~30%.
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| CN110294465A (en) * | 2019-05-16 | 2019-10-01 | 宁夏秦氏新材料有限公司 | The preparation method of decanter type self- propagating silicon nitride |
| CN113546584A (en) * | 2021-07-14 | 2021-10-26 | 中天超容科技有限公司 | Mesoporous carbon pressurized fluidization production system and production method |
| CN114890394A (en) * | 2022-05-23 | 2022-08-12 | 邱建泉 | Continuous production equipment and process for direct nitridation of elemental silicon powder |
| CN115151399A (en) * | 2020-02-28 | 2022-10-04 | 住友重机械工业株式会社 | Preheating device and injection device |
| CN115432676A (en) * | 2021-06-04 | 2022-12-06 | 中国科学院过程工程研究所 | System and method for preparing high-quality silicon nitride powder by using multistage fluidized bed |
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