CN113603093A - Method and equipment for preparing micro silicon powder - Google Patents
Method and equipment for preparing micro silicon powder Download PDFInfo
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- CN113603093A CN113603093A CN202110800710.2A CN202110800710A CN113603093A CN 113603093 A CN113603093 A CN 113603093A CN 202110800710 A CN202110800710 A CN 202110800710A CN 113603093 A CN113603093 A CN 113603093A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011863 silicon-based powder Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 93
- 239000010703 silicon Substances 0.000 claims abstract description 61
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 61
- 239000012495 reaction gas Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000012159 carrier gas Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910021487 silica fume Inorganic materials 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005052 trichlorosilane Substances 0.000 claims description 8
- 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 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000005049 silicon tetrachloride Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical group [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- 238000002309 gasification Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 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
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- 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
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
-
- 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
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane
-
- 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
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a method and equipment for preparing micro silicon powder. The preparation method of the micro silicon powder provided by the embodiment of the invention comprises the following steps: A) heating the tubular reactor so that the temperature in the tubular reactor reaches a reaction temperature; B) mixing silicon-based reaction gas with carrier gas to obtain mixed gas, and introducing the mixed gas into the tubular reactor; C) plasmatizing the mixed gas entering the tubular reactor by using a plasma unit so as to enhance the chemical reaction activity of the mixed gas; D) thermally decomposing the silicon-based reaction gas subjected to plasma ionization in the tubular reactor so as to generate silicon particles, wherein the silicon particles are agglomerated and generate micro silicon powder; and E) separating and collecting the micro silicon powder. The invention has the advantages of low production cost, low energy consumption, sustainable production and convenient large-scale production.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method and equipment for preparing micro silicon powder.
Background
The nanometer silica fume is an important raw material and an application material, can be used as a lithium ion battery cathode material in new energy industry and a raw material of advanced functional materials such as silicon carbide, silicon nitride, organic silicon, electronic packaging filler and the like, and the application fields require the silica fume to have higher purity, controllable micro-morphology and particle size distribution and proper production cost.
In the related technology, the most common method for preparing the nano-silica fume is a grinding method, but the operation time is long (in order to ensure the uniformity of the particle size, the material needs to be back-mixed and repeatedly ground), the loss amount is large, the pollution is large (the grinding medium is worn and enters the material, extra metal impurities are introduced to easily catalyze the decomposition of electrolyte), the material is easy to oxidize, usually, in order to ensure the small enough particle size, a liquid grinding medium needs to be added, so the post-treatment procedures such as solid-liquid separation and drying are needed, and the material loss in different degrees exists in each link from grinding to post-treatment; in order to ensure the grinding effect, the solid content is generally not high, so the single-batch processing capacity is not high.
The preparation of the nanometer silica fume by evaporation and condensation requires extra energy and operation cost for pretreatment of the silica fume, and the single-silicon gasification energy consumption is very high (high energy consumption, low yield, low concentration in the gasification process, high agglomeration and easy formation of large particles, low production efficiency), is difficult to amplify, and is not suitable for large-scale production.
Chemical vapor deposition is commonly used to prepare bulk or thin film materials with effective purity control, but is a batch process and rarely used to prepare microsilica. In the field of silicon materials, a chemical vapor phase method is one of the main processes for producing polycrystalline silicon, a powder material manufacturer does not master a core technology, and each link of safety, environmental protection, raw material gas preparation, storage, use, post-treatment, circulation and the like has a high technical barrier and cannot effectively control the production cost.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a method and equipment for preparing micro silicon powder.
The preparation method of the micro silicon powder provided by the embodiment of the invention comprises the following steps:
A) heating the tubular reactor so that the temperature in the tubular reactor reaches a reaction temperature;
B) mixing silicon-based reaction gas with carrier gas to obtain mixed gas, and introducing the mixed gas into the tubular reactor;
C) plasmatizing the mixed gas entering the tubular reactor by using a plasma unit so as to enhance the chemical reaction activity of the mixed gas;
D) thermally decomposing the silicon-based reaction gas subjected to plasma ionization in the tubular reactor so as to generate silicon particles, wherein the silicon particles are agglomerated and generate micro silicon powder; and
E) and separating and collecting the micro silicon powder.
Therefore, the method for preparing the micro silicon powder has the advantages of low production cost, low energy consumption, sustainable production and convenience for large-scale production.
In some embodiments, the step a) comprises:
a-1) closing the gas inlet of the tubular reactor;
a-2) vacuumizing the tubular reactor;
a-3) stopping vacuumizing, opening a gas inlet of the tubular reactor, and filling inert gas into the tubular reactor; and
a-4) heating the tubular reactor so that the temperature in the tubular reactor reaches the reaction temperature;
optionally, the inert gas is nitrogen;
optionally, step A-1), step A-2) and step A-3) are repeated at least 3 times.
In some embodiments, the step a) comprises: replacing the inert gas with a carrier gas, so that the carrier gas is filled in the tubular reactor, wherein the carrier gas is one of nitrogen, argon and hydrogen;
optionally, the carrier gas is hydrogen.
In some embodiments, said step B) comprises:
b-1) gasifying a liquid silicon-based raw material so as to obtain the silicon-based reaction gas; and
b-2) mixing the silicon-based reaction gas with the carrier gas to obtain the mixed gas, and introducing the mixed gas into the tubular reactor;
optionally, the silicon-based reaction gas is one of silane, dichlorosilane, trichlorosilane, and silicon tetrachloride.
In some embodiments, said step B) comprises:
the step B-2) is to mix the silicon-based reaction gas, the carrier gas and the auxiliary gas to obtain the mixed gas, and introduce the mixed gas into the tubular reactor;
optionally, the auxiliary gas is one of phosphine, arsine and borane.
In some embodiments, the reaction temperature is between 300 ℃ and 1300 ℃.
The invention also provides a micro silicon powder preparation device, which comprises:
a gas mixer having a first gas inlet, a second gas inlet, and a first gas outlet;
the tubular reactor is provided with a third air inlet and a first discharge hole, and the third air inlet is connected with the first air outlet;
the heating device comprises a heating element and a temperature sensor, and the heating element is sleeved at the lower end part of the tubular reactor;
the plasma device comprises a radio frequency power supply and a radio frequency coil, and the radio frequency coil is sleeved at the upper end part of the tubular reactor;
the collector is provided with a first feeding hole, a second discharging hole and a second gas outlet, and the first feeding hole is connected with the first discharging hole; and
and the exhaust device comprises a vacuum generator and a filter, the inlet of the filter is connected with the second air outlet, and the outlet of the filter is connected with the inlet of the vacuum generator.
The equipment for preparing the micro silicon powder according to the embodiment of the invention also comprises:
the liquid evaporation device comprises a first liquid inlet and a third air outlet, and the third air outlet is connected with the first air inlet; and
a mass flow meter cooperating with the gas mixer;
optionally, the liquid evaporation apparatus comprises a flash evaporator and a bubbler.
In some embodiments, the material of the tubular reactor is quartz or corundum;
the first discharge hole of the tubular reactor is of a conical reducing structure.
In some embodiments, the heating element is a silicon molybdenum rod.
Drawings
Fig. 1 is a schematic structural view of a micro silicon powder preparation apparatus according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The preparation method of the micro silicon powder provided by the embodiment of the invention comprises the following steps:
A) the tubular reactor 20 is heated so that the temperature inside the tubular reactor 20 reaches the reaction temperature.
B) The silicon-based reaction gas and the carrier gas are mixed to obtain a mixed gas, and the mixed gas is introduced into the tubular reactor 20.
C) The mixed gas entering the pipe reactor 20 is plasmatized by the plasma unit so as to enhance the chemical reactivity of the mixed gas.
D) The plasmatized silicon-based reaction gas is thermally decomposed in the tubular reactor 20 to produce silicon particles, which are agglomerated and produce microsilica.
E) Separating and collecting the micro silicon powder.
In the related technology, in the method for preparing the nano-silica fume, the grinding method needs to repeatedly grind materials, so the operation time is long, the loss is large, and the pollution is large. The preparation of the nanometer silica fume by evaporation and condensation requires extra energy and operation cost for silica fume preprocessing, and the single-substance silicon gasification energy consumption is very high, so that the method is not suitable for large-scale production. Chemical vapor deposition is commonly used to prepare bulk or thin film materials with effective purity control, but is a batch process and does not effectively control production costs.
According to the method for preparing the micro silicon powder, silicon-based reaction gas is used as a raw material, mixed gas obtained by mixing the silicon-based reaction gas and carrier gas is introduced into the tubular reactor 20, and the carrier gas can provide atmosphere required by reaction for preparing the micro silicon powder.
The mixed gas entering the pipe reactor 20 is plasmatized by the plasma unit so as to enhance the chemical reactivity of the mixed gas. Namely, the silicon-based reaction gas and the carrier gas entering the tubular reactor 20 are plasmatized by the plasma unit, so that the silicon-based reaction gas and the carrier gas are ionized under the action of the radio-frequency electric field and glow discharge is generated. Besides positive particles and negative particles, a large amount of active radicals are generated due to the collision of low-speed electrons and gas atoms, so that the chemical activity of the silicon-based reaction gas is enhanced (the chemical reaction rate of the silicon-based reaction gas is increased), namely, the conversion rate of the raw material gas (silicon-based reaction gas) is accelerated and the overall conversion efficiency of the gas is increased.
The silicon-based reaction gas after the plasma reaction (for enhancing the chemical reaction activity) reaches the reaction temperature and then is easily thermally decomposed in the tubular reactor 20, that is, the silicon-based reaction gas after the plasma reaction (for enhancing the chemical reaction activity) reaches the reaction temperature and then can generate silicon particles, and the silicon particles are agglomerated in the tubular reactor 20 and generate micro silicon powder. And separating and collecting the micro silicon powder to finish the preparation of the micro silicon powder. The silicon-based reaction gas is easy to obtain, the production cost is low, no other solid impurities are mixed in the preparation process of the silica fume, continuous production can be realized without interruption, and the obtained silica fume has high purity, does not need grinding post-treatment and is convenient for large-scale production.
Therefore, the method for preparing the micro silicon powder has the advantages of low production cost, low energy consumption, sustainable production and convenience for large-scale production.
As shown in fig. 1, the present invention also proposes a micro silicon powder preparation apparatus 100, and the micro silicon powder preparation apparatus 100 according to an embodiment of the present invention includes a gas mixer 10, a tubular reactor 20, a heating device 30, a plasma device 40, a collector 50, and an exhaust device.
The gas mixer 10 has a first gas inlet 11, a second gas inlet 12 and a first gas outlet 13. The tubular reactor 20 has a third inlet 21 and a first outlet 22, the third inlet 21 being connected to the first outlet 13. The heating device 30 comprises a heating element and a temperature sensor, wherein the heating element is sleeved at the lower end of the tubular reactor 20.
The plasma device 40 comprises a radio frequency power supply 41 and a radio frequency coil 42, wherein the radio frequency coil 42 is sleeved on the upper end part of the tubular reactor 20. The collector 50 has a first inlet 51, a second outlet 52 and a second outlet 53, the first inlet 51 being connected to the first outlet 22. The exhaust means comprises a vacuum generator and a filter, the inlet of which is connected to the second outlet 53 and the outlet of which is connected to the inlet of the vacuum generator.
According to the micro silicon powder preparation equipment 100 provided by the embodiment of the invention, the heating device 30 and the plasma device 40 are arranged, the radio frequency coil 42 is sleeved at the upper end part of the tubular reactor 20, and the heating element is sleeved at the lower end part of the tubular reactor 20, so that the silicon-based reaction gas and the carrier gas are ionized under the action of a radio frequency electric field and glow discharge is generated. Besides positive particles and negative particles, a large number of active groups are generated due to the collision of low-speed electrons and gas atoms, so that the chemical activity of the silicon-based reaction gas is enhanced (the chemical reaction rate of the silicon-based reaction gas is increased), namely the preparation efficiency of the micro silicon powder is increased.
The heating device 30 heats the gas in the tubular reactor 20 to a reaction temperature, and the silicon-based reaction gas after plasma ionization (chemical reaction activity enhancement) reaches the reaction temperature and is then easily thermally decomposed in the tubular reactor 20, i.e., the silicon-based reaction gas after plasma ionization (chemical reaction activity enhancement) reaches the reaction temperature and then generates silicon particles, and the silicon particles agglomerate in the tubular reactor 20 and generate silica fume.
The collector 50 and the exhaust device are used for separating and collecting the micro silicon powder, and the preparation of the micro silicon powder is completed. The silicon-based reaction gas is easy to obtain, the production cost is low, no other solid impurities are mixed in the preparation process of the silica fume, intermittent sustainable production is not needed in the middle, and the obtained silica fume has high purity, does not need grinding and is convenient for large-scale production.
Therefore, the apparatus 100 for preparing the micro silicon powder according to the embodiment of the present invention has the advantages of low production cost, low energy consumption, sustainable production and convenience for mass production.
The method for preparing the microsilica according to the embodiment of the present invention is specifically described below.
In some embodiments, step a) comprises:
a-1) closing the air inlet of the tubular reactor 20, preventing air from re-entering the tubular reactor 20.
A-2) evacuating the tubular reactor 20 and drawing out air from the tubular reactor 20.
And A-3) stopping vacuumizing, opening a gas inlet of the tubular reactor, and filling gas in the tubular reactor 20 by using inert gas to further reduce gas impurities in the tubular reactor 20, thereby reducing the pollution of the impurities.
A-4) heating the tubular reactor 20 so that the temperature inside the tubular reactor 20 reaches the reaction temperature, so that the silicon-based reaction gas can be thermally decomposed after entering the tubular reactor 20.
Optionally, the inert gas is nitrogen.
Optionally, the step A-1), the step A-2) and the step A-3) are repeatedly carried out for at least 3 times, so that impurities in the tubular reactor 20 are further reduced, and the pollution caused by the impurities in the process of preparing the micro silicon powder is reduced.
In some embodiments, step a) comprises: the inert gas is replaced with a carrier gas (which is not required if both the carrier gas and the inert gas are nitrogen) so that the carrier gas is filled in the tubular reactor 20, the carrier gas being one of nitrogen, argon and hydrogen. The carrier gas can provide the atmosphere required by the reaction for preparing the micro silicon powder and simultaneously has the function of conveying the silicon powder product.
Alternatively, the carrier gas is hydrogen, and hydrogen generated after plasma ionization can react with some particles (other than silicon particles) in the silicon-based reaction gas more easily to facilitate silicon particle generation.
In some embodiments, step B) comprises:
b-1) gasifying liquid silicon-based raw material gas so as to obtain silicon-based reaction gas. The raw material cost can be reduced by gasifying cheap liquid silicon-based raw materials so as to obtain silicon-based reaction gas required by the reaction, thereby facilitating the obtaining of gas raw materials.
B-2) mixing the silicon-based reaction gas with a carrier gas to obtain a mixed gas, and introducing the mixed gas into the tubular reactor 20. The mixed gas contains a silicon-based reaction gas and a carrier gas so that the inlet into the tubular reactor 20 has an atmosphere suitable for the reaction to occur.
Optionally, the silicon-based reaction gas is one of silane, dichlorosilane, trichlorosilane, and silicon tetrachloride. For example, when the silicon-based reaction gas is trichlorosilane, trichlorosilane is thermally decomposed to generate microsilica, hydrogen chloride, silicon tetrachloride and the like. The micro silicon powder is collected, and the chlorine hydride, the silicon tetrachloride and the remaining part of the trichlorosilane which is not completely reacted are discharged.
In some embodiments, step B) comprises:
and the step B-2) is to mix the silicon-based reaction gas, the carrier gas and the auxiliary gas so as to obtain mixed gas, and the mixed gas is introduced into the tubular reactor 20. The auxiliary gas can provide a gas environment for facilitating agglomeration of the nano-silica powder, and the auxiliary gas can modify the nano-silica powder, for example, the auxiliary gas can provide 3-valent or 5-valent heteroatoms to form p-type or n-type doping, thereby increasing the conductivity of the nano-silica powder.
Optionally, the assist gas is one of phosphine, arsine and borane.
In some embodiments, the reaction temperature is between 300 ℃ and 1300 ℃. The silicon-based reaction gas comprises silane, dichlorosilane, trichlorosilane and silicon tetrachloride, the decomposition temperatures of the silane, dichlorosilane, trichlorosilane and silicon tetrachloride are sequentially increased, and the appropriate reaction temperature can be selected according to different silicon-based reaction gases.
As shown in fig. 1, a micro silicon powder preparation apparatus 100 according to an embodiment of the present invention includes a liquid evaporation device, a mass flow meter, a gas mixer 10, a tubular reactor 20, a heating device 30, a plasma device 40, a collector 50, and an exhaust device.
The liquid evaporation device is used for vaporizing the liquid precursor into the gaseous raw material, i.e. the liquid silicon-based raw material is vaporized into the silicon-based reaction gas, and optionally, the liquid evaporation device comprises a flash evaporator and a bubbler.
The gas mixer 10 has a first gas inlet 11, a second gas inlet 12 and a first gas outlet 13.
In some embodiments, the liquid evaporation device comprises a first liquid inlet and a third air outlet, the third air outlet being connected to the first air inlet 11. The mass flow meter is matched with the gas mixer 10 for metering and controlling the silicon-based reaction gas entering the gas mixer 10, for example, an inlet of the mass flow meter is connected with the third gas outlet, and an outlet of the mass flow meter is connected with the first gas inlet 11. The silicon-based reaction gas after the gasification of the liquid silicon-based raw material is discharged from the third gas outlet, passes through the mass flow meter, and then enters the first gas inlet 11, so as to enter the gas mixer 10. The carrier gas and the auxiliary gas may enter the gas mixer 10 from the second gas inlet 12.
The tubular reactor 20 has a third inlet 21 and a first outlet 22, the third inlet 21 being connected to the first outlet 13. The tubular reactor 20 is of a vertical structure with the material direction going downwards.
In some embodiments, the tubular reactor 20 is made of quartz or corundum. The first discharge hole 22 of the tubular reactor 20 is of a tapered diameter-variable structure, the first discharge hole 22 is located at the bottom of the tubular reactor 20, and the tapered diameter-variable structure facilitates sliding of the micro silicon powder, so that the micro silicon powder is collected conveniently.
The plasma device 40 comprises a radio frequency power supply 41 and a radio frequency coil 42, wherein the radio frequency coil 42 is sleeved on the upper end part of the tubular reactor 20. The mixed gas can be ionized immediately after entering the tubular reactor 20, so that the silicon-based reaction gas and the carrier gas are ionized under the action of the radio-frequency electric field and glow discharge is generated. Besides positive particles and negative particles, a large amount of other active groups can be generated due to the collision of low-speed electrons and gas atoms, so that the chemical activity of the silicon-based reaction gas is enhanced (the chemical reaction rate and efficiency of the silicon-based reaction gas are increased), namely, the preparation of the micro silicon powder is accelerated.
The heating device 30 comprises a heating element and a temperature sensor, wherein the heating element is sleeved at the lower end of the tubular reactor 20. The heating element is a silicon-molybdenum rod which has unique high-temperature oxidation resistance, and the heating element adopts independent multi-section intelligent program control arrangement with multiple temperature zones. The shell of the heating unit is steel openable, and alumina fiber heat-insulating material is filled between the shell of the heating unit and the tubular reactor 20, so that heat insulation and energy conservation are facilitated. The heating device 30 heats the gas in the tubular reactor 20 to a reaction temperature, and the silicon-based reaction gas after plasma ionization (chemical reaction activity enhancement) reaches the reaction temperature and is then easily thermally decomposed in the tubular reactor 20, i.e., the silicon-based reaction gas after plasma ionization (chemical reaction activity enhancement) reaches the reaction temperature and then generates silicon particles, and the silicon particles agglomerate in the tubular reactor 20 and generate silica fume.
The collector 50 has a first inlet 51, a second outlet 52 and a second outlet 53, the first inlet 51 being connected to the first outlet 22. The exhaust means comprises a vacuum generator and a filter, the inlet of which is connected to the second outlet 53 and the outlet of which is connected to the inlet of the vacuum generator.
The collector 50 and the exhaust device are used for separating and collecting the micro silicon powder, and the preparation of the micro silicon powder is completed. The silicon-based reaction gas is easy to obtain, the production cost is low, no other solid impurities are mixed in the preparation process of the silica fume, intermittent sustainable production is not needed in the middle, and the obtained silica fume has high purity, does not need grinding and is convenient for large-scale production. In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; may be mechanically coupled, may be electrically coupled or may be in communication with each other; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The method for preparing the micro silicon powder is characterized by comprising the following steps of:
A) heating the tubular reactor so that the temperature in the tubular reactor reaches a reaction temperature;
B) mixing silicon-based reaction gas with carrier gas to obtain mixed gas, and introducing the mixed gas into the tubular reactor;
C) plasmatizing the mixed gas entering the tubular reactor by using a plasma unit so as to enhance the chemical reaction activity of the mixed gas;
D) thermally decomposing the silicon-based reaction gas subjected to plasma ionization in the tubular reactor so as to generate silicon particles, wherein the silicon particles are agglomerated and generate micro silicon powder; and
E) and separating and collecting the micro silicon powder.
2. The method for preparing microsilica according to claim 1, wherein step a) comprises:
a-1) closing the gas inlet of the tubular reactor;
a-2) vacuumizing the tubular reactor; a-3) stopping vacuumizing, opening a gas inlet of the tubular reactor, and filling inert gas into the tubular reactor; and
a-4) heating the tubular reactor so that the temperature in the tubular reactor reaches the reaction temperature;
optionally, the inert gas is nitrogen;
optionally, step A-1), step A-2) and step A-3) are repeated at least 3 times.
3. The method for preparing microsilica according to claim 2, wherein step a) comprises: replacing the inert gas with a carrier gas, so that the carrier gas is filled in the tubular reactor, wherein the carrier gas is one of nitrogen, argon and hydrogen;
optionally, the carrier gas is hydrogen.
4. The method for preparing the micro silicon powder according to claim 2, wherein the step B) comprises:
b-1) gasifying a liquid silicon-based raw material so as to obtain the silicon-based reaction gas; and
b-2) mixing the silicon-based reaction gas with the carrier gas to obtain the mixed gas, and introducing the mixed gas into the tubular reactor;
optionally, the silicon-based reaction gas is one of silane, dichlorosilane, trichlorosilane, and silicon tetrachloride.
5. The method for preparing microsilica according to claim 4, wherein step B) comprises:
the step B-2) is to mix the silicon-based reaction gas, the carrier gas and the auxiliary gas to obtain the mixed gas, and introduce the mixed gas into the tubular reactor;
optionally, the auxiliary gas is one of phosphine, arsine and borane.
6. The method for preparing microsilica according to claim 1, wherein the reaction temperature is between 300 ℃ and 1300 ℃.
7. A silica fume preparation equipment is characterized by comprising:
a gas mixer having a first gas inlet, a second gas inlet, and a first gas outlet;
the tubular reactor is provided with a third air inlet and a first discharge hole, and the third air inlet is connected with the first air outlet;
the heating device comprises a heating element and a temperature sensor, and the heating element is sleeved at the lower end part of the tubular reactor;
the plasma device comprises a radio frequency power supply and a radio frequency coil, and the radio frequency coil is sleeved at the upper end part of the tubular reactor;
the collector is provided with a first feeding hole, a second discharging hole and a second gas outlet, and the first feeding hole is connected with the first discharging hole; and
and the exhaust device comprises a vacuum generator and a filter, the inlet of the filter is connected with the second air outlet, and the outlet of the filter is connected with the inlet of the vacuum generator.
8. The apparatus for preparing microsilica according to claim 7, further comprising:
the liquid evaporation device comprises a first liquid inlet and a third air outlet, and the third air outlet is connected with the first air inlet; and
a mass flow meter cooperating with the gas mixer;
optionally, the liquid evaporation apparatus comprises a flash evaporator and a bubbler.
9. The apparatus for preparing microsilica according to claim 7, wherein,
the tubular reactor is made of quartz or corundum;
the first discharge hole of the tubular reactor is of a conical reducing structure.
10. The apparatus of claim 7, wherein the heating element is a silicon-molybdenum rod.
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