CN1064024C - Method and apparatus for production of high purity ultrafine silicon nitride - Google Patents
Method and apparatus for production of high purity ultrafine silicon nitride Download PDFInfo
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- CN1064024C CN1064024C CN97121645A CN97121645A CN1064024C CN 1064024 C CN1064024 C CN 1064024C CN 97121645 A CN97121645 A CN 97121645A CN 97121645 A CN97121645 A CN 97121645A CN 1064024 C CN1064024 C CN 1064024C
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- reactor
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- silicon nitride
- silane
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 26
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000077 silane Inorganic materials 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 239000012530 fluid Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 239000000945 filler Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000005243 fluidization Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QJGQUHMNIGDVPM-BJUDXGSMSA-N Nitrogen-13 Chemical compound [13N] QJGQUHMNIGDVPM-BJUDXGSMSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
The present invention relates to a method and equipment for preparing superfine silicon nitride of high purity. The present invention is characterized in that the gas phase chemical reaction of silane and ammonia gas is carried out in a vertical flow state reactor 3 with double temperature zones, the bottom of a fluid bed of the reactor is provided with a distribution plate 31 made of stainless steel, carrier filler 32 is the silicon crystal with the particle size of 0.1 to 0.5mm, the outer part of a bed layer is provided with a primary heater 33, the upper part space of the reactor is used as a reaction zone 34, and the outer part of the reaction zone is provided with an auxiliary heater 35. Compared with the prior art, the method and the equipment have the advantages of less equipment investment, low energy consumption, high yield, fine and uniform silicon nitride particles, smooth surface, pore-free inner structure and no aggregation phenomenon and are suitable for industrialization.
Description
The present invention relates to the binary compound of a kind of nitrogen and silicon, particularly a kind of method and apparatus of making high purity ultrafine silicon nitride.
The method of manufacturing high purity ultrafine silicon nitride commonly used is a gas-phase reaction method, is raw material with silane and ammonia, and by gas-phase chemical reaction synthesizing silicon nitride powder, its chemical equation is:
Chinese patent CN91101747, publication number is 1058194A, a kind of synthetic method for preparing the superfine silicon nitride powder of laser that adopts is provided, utilize the laser direct heating reactant gases of high degree of focus, the gas absorption laser energy, reach temperature of reaction and finish reaction in moment, the beta-silicon nitride powder of obtain high purity, ultra-fine, epigranular, not reuniting, but because conversion zone is narrow, productivity is extremely low, per hour can only obtain several grams of high purity ultrafine silicon nitride powder, still not have industrial utility value so far.
The object of the present invention is to provide a kind of method and apparatus of making high purity ultrafine silicon nitride, adopt vertical pair of warm area fluid bed reactor to realize the purpose of suitability for industrialized production high purity ultrafine silicon nitride powder, it is even to obtain product granularity, forms homogeneous, the powder densification, the yield height.
Below be described in detail particular content of the present invention.
A kind of method of making high purity ultrafine silicon nitride is a unstripped gas with silane and ammonia, and by gas-phase chemical reaction synthesizing superfine beta-silicon nitride powder, chemical equation is:
A kind of equipment of implementing aforesaid method, contain silane source of the gas 11, ammonia source 12, source nitrogen 13 and under meter L1 thereof, L2, L3 pressure warning unit P, silane and ammonia are mixed into the mixing tank 2 of unstripped gas, gas-phase chemical reaction device 3, strainer 4, exhaust processor and emptying 5, oil-sealed rotary pump 6 and connecting tube, with silane source of the gas 11, ammonia source 12, source nitrogen 13 is connected in series under meter L1 respectively, L2, L3, under meter L1, L2, L3 also connects after excess pressure meter P, mixing tank 2 is connected with gas-phase chemical reaction device 3 inlet mouths, the reactor air outlet is connected in series strainer successively, exhaust processor and emptying 5, oil-sealed rotary pump 6, it is characterized in that: gas-phase chemical reaction device 3 adopts vertical pair of warm area fluid bed reactor, its fluidised form bed bottom is provided with the distribution plate made from stainless steel 31, the carrier filler 32 of fluidised form bed is that granularity is 0.1～0.5mm silicon crystal, places on the distribution plate 31, and outside, bed district is provided with primary heater 33, the upper space of reactor 3 is a reaction zone 34, and its outside is provided with secondary heater 35; Described reactor 3 its diameters are 50～300mm, the altitude range of reactor 3 its fluidised form layers is 40～300mm, optimum height is 100～200mm, the height of reactor 3 its reaction zones is 200～1000mm, optimum height is 500～800mm, distribution plate 31 water flowings coolings is provided with one and is attached thereto the product that connects and packs the chamber below strainer 4.
With prior art relatively, outstanding advantage of the present invention is: less investment, and energy consumption is low, the yield height, the product powder granularity is thin, is evenly distributed compact structure, purity height.Because having the good silicon particle of thermal conductivity, fluidised form bed place under the air-flow effect, makes the cyclic motion that do not stop, make whole bed temperature state such as be in, the reactant gases that enters bed is heated evenly, form evenly, gas has enough reaction times and reaction compartment in reaction zone simultaneously, for strengthening reaction gas flow and improving the silane transformation efficiency and created favourable condition, reach 6600 ml/min as total flux, the silane transformation efficiency is higher than 90%, can improve product production significantly, these effects are as realizing with prior art.
Table 1 is set forth in the productive rate data of product under the different technology conditions, and wherein sequence number A7 is that the fluidised form bed is not filled out the data of putting the silicon grain.
The powder output and the productive rate that make under table 1 different condition
| The experiment sequence number | Temperature of reaction ℃ | Total gas flow rate ml/ branch | Silane flow rate ml/ branch | Powder output g/ hour | Powder productive rate % |
| A1 | 650 | 2550 | 230 | 26．8 | 93．5％ |
| A2 | 750 | 2550 | 230 | 27．0 | 93．9％ |
| A3 | 750 | 3500 | 320 | 28．6 | 93．0％ |
| A4 | 850 | 2550 | 230 | 27．0 | 94．0％ |
| A5 | 850 | 4500 | 410 | 46．6 | 93．1％ |
| A6 | 850 | 6600 | 600 | 69．3 | 92．0％ |
| A7 | 750 | 2550 | 230 | 20．1 | 70．0％ |
Table 2 is set forth in the particle size distribution data of product under the different technology conditions, and wherein sequence number B8 is that the fluidised form bed is not filled out the data of putting the silicon grain.
Beta-silicon nitride powder granularity under table 2 different condition
| The experiment sequence number | Temperature of reaction (℃) | Gas flow (ml/ branch) | NH 3／SiH 4Ratio | Particle mean size (nm) | Particle distribution range (nm) |
| B1 | 650 | 2550 | 10 | 157 | 103～240 |
| B2 | 750 | 2550 | 5 | 133 | 88～172 |
| B3 | 750 | 2550 | 10 | 140 | 90～180 |
| B4 | 750 | 2550 | 15 | 103 | 68～172 |
| B5 | 850 | 2550 | 10 | 140 | 100～220 |
| B6 | 850 | 4500 | 10 | 130 | 100～187 |
| B7 | 850 | 6600 | 10 | 100 | 73～150 |
| B8 | 750 | 2550 | 10 | 160 | 90～400 |
Fig. 1 is for making the structural representation of high purity ultrafine silicon nitride equipment.
Fig. 2 is for obtaining the transmission electron microscope TEM Photomicrograph of beta-silicon nitride powder.
Embodiment 1
Vertical pair of its internal diameter of warm area fluid bed reactor of stainless steel is 40mm, bed height is 60mm, the reaction zone height is 300mm, every square centimeter of cloth hole is 25 on the distribution plate, the aperture is 1mm, fill out on the distribution plate and put polycrysalline silcon, granularity is 0.5mm, distribution plate water flowing cooling, bed temperature is 600 ℃, reaction zone temperature is 850 ℃, respectively by primary heater and secondary heater heating, reactor is used nitrogen wash in advance, feed silane and ammonia afterwards, pressure is 1300Pa, and total flux is 6600 milliliters of per minutes, and wherein the silane per minute is 600 milliliters, move 1 hour, obtain oyster white high purity ultrafine silicon nitride powder 70 grams, detected result: productive rate is 92%, and the composition of powder is an amorphous silicon nitride with the FTIR determination of infrared spectroscopy, the granularity of powder and crystalline phase are measured with transmission electron microscope TEM, the TEM Photomicrograph shows that powder is spherical, favorable dispersity, no agglomeration, particle surface and internal structure pore-free, particle mean size 100nm, distribution range is 73～150nm, the particle that wherein is distributed in two ends is very few.
Embodiment 2:
Bed temperature is 800 ℃, temperature of reaction is 650 ℃, feeds silane and ammonia, and pressure is 1500Pa, total flux is 2550 milliliters of per minutes, wherein silane flow rate is 230 milliliters of per minutes, moves 1 hour, obtains beta-silicon nitride powder 27 grams, productive rate is 93.5%, the silicon nitride particle mean sizes is 157nm, and size distribution is 103～240nm, and all the other are identical with embodiment 1.
Claims (8)
1, a kind of method of making high purity ultrafine silicon nitride is a unstripped gas with silane and ammonia, and by gas-phase chemical reaction synthesizing superfine beta-silicon nitride powder, chemical equation is:
It is characterized in that: this gas-phase chemical reaction carries out in vertical pair of warm area fluid bed reactor (3), silane contents is 5～20% in the unstripped gas, pass through reactor from bottom to top, its flow velocity is 10～60cm/s, reaction product is taken out of by air-flow, be collected in the strainer (4), in vertical pair of warm area fluid bed reactor (3), the temperature in fluidised form bed district is 600～800 ℃, and the temperature of reaction zone (34) is 500～850 ℃, in the gas-phase chemical reaction process, the flow velocity of unstripped gas reaches 1.5～8.0 times of minimum fluidization velocity, and vertical pair of warm area fluid bed reactor washes with high pure nitrogen before unstripped gas enters and after the reaction end.
2, method according to claim 1 is characterized in that: collected superfine silicon nitride powder packs in the high pure nitrogen atmosphere.
3, a kind of equipment of implementing claim 1 method, contain silane source of the gas (11), ammonia source (12), source nitrogen (13) and under meter (L1) thereof, (L2), (L3), pressure warning unit (P), silane and ammonia are mixed into the mixing tank (2) of unstripped gas, gas-phase chemical reaction device (3), strainer (4), exhaust processor and emptying (5), oil-sealed rotary pump (6) and connecting tube, with silane source of the gas (11), ammonia source (12), source nitrogen (13) is connected in series under meter (L1) respectively, (L2), (L3), under meter (L1), (L2), (L3) and connect after excess pressure meter (P), mixing tank (2) is connected with gas-phase chemical reaction device (3) inlet mouth, the reactor air outlet is connected in series strainer (4) successively, exhaust processor and emptying (5), oil-sealed rotary pump (6), it is characterized in that: gas-phase chemical reaction device (3) adopts vertical pair of warm area fluid bed reactor, its fluidised form bed bottom is provided with the distribution plate made from stainless steel (31), the carrier filler of fluidised form bed (32) is that granularity is 0.1～0.5mm silicon crystal, place on the distribution plate (31), outside, bed district is provided with primary heater (33), the upper space of reactor (3) is reaction zone (34), and its outside is provided with secondary heater (35).
4, equipment according to claim 3 is characterized in that: its diameter of described reactor (3) is 50～300mm.
5, equipment according to claim 3 is characterized in that: the height of its fluidised form layer of reactor (3) is 40～300mm, and the height of its reaction zone (34) is 200～1000mm.
6, equipment according to claim 3 is characterized in that: the height of its fluidised form layer of reactor (3) is 100～200mm, and the height of its reaction zone (34) is 500～800mm.
7, equipment according to claim 3 is characterized in that: distribution plate (31) water flowing cooling.
8, equipment according to claim 3 is characterized in that: be provided with one in the below of strainer (4) and be attached thereto the product that connects and pack the chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121645A CN1064024C (en) | 1997-11-20 | 1997-11-20 | Method and apparatus for production of high purity ultrafine silicon nitride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121645A CN1064024C (en) | 1997-11-20 | 1997-11-20 | Method and apparatus for production of high purity ultrafine silicon nitride |
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| Publication Number | Publication Date |
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| CN1218002A CN1218002A (en) | 1999-06-02 |
| CN1064024C true CN1064024C (en) | 2001-04-04 |
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| CN97121645A Expired - Fee Related CN1064024C (en) | 1997-11-20 | 1997-11-20 | Method and apparatus for production of high purity ultrafine silicon nitride |
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| CN104641028B (en) * | 2013-06-18 | 2016-08-31 | Lg化学株式会社 | The device preparing carbon nano-tube fibre and the method utilizing described device to prepare carbon nano-tube fibre |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040559A (en) * | 1989-08-24 | 1990-03-21 | 国家建筑材料工业局山东工业陶瓷研究设计院 | The manufacture method of alpha-silicon nitride powders and equipment |
| CN1051153A (en) * | 1990-12-20 | 1991-05-08 | 清华大学 | The method of making ultrafine powder of silicon nitride by dual-tube pressuring |
| CN1058194A (en) * | 1991-03-18 | 1992-01-29 | 中国科学院安徽光学精密机械研究所 | A kind of method and device of new laser system alpha-silicon nitride powders |
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- 1997-11-20 CN CN97121645A patent/CN1064024C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040559A (en) * | 1989-08-24 | 1990-03-21 | 国家建筑材料工业局山东工业陶瓷研究设计院 | The manufacture method of alpha-silicon nitride powders and equipment |
| CN1051153A (en) * | 1990-12-20 | 1991-05-08 | 清华大学 | The method of making ultrafine powder of silicon nitride by dual-tube pressuring |
| CN1058194A (en) * | 1991-03-18 | 1992-01-29 | 中国科学院安徽光学精密机械研究所 | A kind of method and device of new laser system alpha-silicon nitride powders |
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| CN1218002A (en) | 1999-06-02 |
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