CN114314596B - Method and system for continuously synthesizing higher-order silane by utilizing microwave heating fixed bed - Google Patents
Method and system for continuously synthesizing higher-order silane by utilizing microwave heating fixed bed Download PDFInfo
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000010438 heat treatment Methods 0.000 title claims abstract description 35
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 43
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 33
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 150000004756 silanes Chemical class 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 16
- 238000005336 cracking Methods 0.000 abstract description 11
- 150000003254 radicals Chemical class 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 11
- 238000005303 weighing Methods 0.000 description 9
- YXMVRBZGTJFMLH-UHFFFAOYSA-N butylsilane Chemical compound CCCC[SiH3] YXMVRBZGTJFMLH-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- -1 lithium aluminum hydride Chemical compound 0.000 description 6
- 229920005591 polysilicon Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 5
- 229910021338 magnesium silicide Inorganic materials 0.000 description 5
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 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
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 230000007017 scission Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
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Abstract
The invention discloses a method for generating high-order silane by cracking reaction of monosilane in a silicon powder bed layer in a microwave heating mode and a reaction system thereof; in a fixed bed reaction device, silicon powder is added with a catalyst to serve as a fixed bed layer, monosilane is introduced into the bed layer, and a microwave heating mode is adopted to heat bed materials, so that monosilane is cracked and subjected to free radical recombination reaction on the surface of the silicon powder, and high-order silane is generated. The invention realizes the process of directly synthesizing the high-order silane from the low-order monosilane, has high yield of the high-order silane, simple and continuous reaction process, does not involve excessive chemical media, has no byproduct emission, and is easy to separate and purify the product.
Description
Technical Field
The invention relates to the field of synthesis of higher-order silane, in particular to a method and a system for continuously synthesizing higher-order silane by utilizing a microwave heating fixed bed.
Background
Silane gas is an important raw material in the semiconductor and photovoltaic industries, and is mainly used for depositing various films containing silicon elements, especially amorphous silicon and polycrystalline silicon films. The most widely used silane gas is monosilane at present, but the decomposition temperature of monosilane for depositing the polysilicon film is higher, the deposition rate is slower, and the application of the polysilicon film is limited to a certain extent, for example, the polysilicon film is directly deposited on a glass substrate. The high-order silane has lower decomposition temperature and faster deposition rate, and the deposited and grown film has more regular lattice arrangement, which is more beneficial to the growth of large-grain polysilicon film. For example, the temperature of disilane deposition to grow a polysilicon film may be as low as about 500 ℃ below the softening temperature of ordinary glass, thus allowing for the process of directly depositing a polysilicon film on the surface of a glass substrate; the temperature of the trisilane deposited and grown polycrystalline silicon film can be as low as below 300 ℃, and the process of directly depositing the polycrystalline silicon film on the flexible substrate or preparing the special composite film material by combining the trisilane deposited and grown polycrystalline silicon film with other materials such as graphene and the like is hopeful to be realized. Compared with the prior art, the amorphous silicon film is deposited by taking monosilane as a raw material and then is subjected to laser-induced crystal form conversion to form the polycrystalline silicon film, so that the preparation efficiency is low, and the development of related application technology is severely restricted.
The existing technological routes for industrially producing disilane mainly comprise a hexachlorodisilane hydrogenation method, a magnesium silicide method and a monosilane cracking method.
In the hexachlorodisilane hydrogenation method, lithium aluminum hydride or sodium aluminum hydride is generally used as a reducing agent, and the lithium aluminum hydride or sodium aluminum hydride and hexachlorodisilane are subjected to reduction reaction in an organic solvent to generate disilane and salt, and meanwhile, byproduct chlorine is generated. The process has the advantages of continuous production, easy scale up, complex purification process of hexachlorodisilane, high difficulty, harsh preparation conditions of reducing agent lithium aluminum hydride or sodium aluminum hydride, complex whole process flow, high energy consumption, high control difficulty and high equipment investment and operation cost.
The silicon-magnesium method generally takes magnesium silicide and ammonium chloride as raw materials, and the reaction is carried out in a liquid ammonia solvent, and the reaction is generally carried out under the condition of micro positive pressure, and the temperature is controlled within the range of minus 20 ℃ to minus 30 ℃. The process is mainly used for preparing high-purity monosilane, and simultaneously, about 3 to 5 percent of disilane and a trace of trisilane are produced as byproducts. The process has the advantages of short process flow, simple equipment, easy control, high purity of the obtained silane gas product and easier post purification. In the process, the first step is to mix silicon powder and magnesium powder, ball-mill the mixture, and then heat the mixture to more than 500 ℃ to perform alloying reaction to generate magnesium silicide powder. The industrial grade silicon powder in the market is generally about 200 meshes, the magnesium powder is inflammable and explosive when the particle size is too fine, the market purchase is generally about 40 meshes, the particle size of the powder which is suitable for the alloying process is 600-1000 meshes, and the two powder are required to be fully stirred and pressed for ensuring sufficient contact area because the powder is solid-solid phase reaction, so that the step is firstly required to be subjected to alloying treatment for a long time. And because the reaction occurs on the solid phase surface, after magnesium silicide is generated by the reaction, the magnesium silicide occupies the reaction site to prevent the further reaction, so that the full reaction is difficult to realize in the powder, and the conversion rate of the alloying reaction is low.
Monosilane cleavage is a method in which monosilane is used as a raw material, and is subjected to cleavage reaction to form free radicals, which are then rearranged and combined to form high-order silane. The method uses high-purity monosilane as a raw material, generally combines with the reaction condition of glow discharge, and reacts under lower pressure to simultaneously generate a plurality of high-order silanes such as disilane, trisilane, butylsilane and the like. Because the raw material adopted by the method is monosilane, and monosilane is easy to purify, the purity of the generated high-order silane is extremely high and easy to separate. However, in order to stabilize the glow discharge, the method needs to be carried out under low pressure, so that the production efficiency of the high-order silane is extremely low, silicon powder is a byproduct in the reaction process, and raw monosilane is wasted greatly. If the reaction pressure needs to be increased, the reaction temperature is increased, so that the decomposition of the high-order silane is accelerated, the silicon powder as a byproduct is increased, and the conversion rate of the high-order silane is obviously reduced.
In summary, the hexachlorodisilane hydrogenation process in the prior art has the disadvantages of complex operation, high difficulty, intermittent operation, long operation time, low conversion rate, and low overall yield, while the monosilane cracking process needs to be performed at low pressure, has low production efficiency, difficult capacity amplification, complex structure of glow discharge equipment, and high maintenance cost.
On the basis of researching the reaction mechanism of the monosilane cracking method and physical parameters of various higher-order silanes, the invention provides a method for heating silicon powder by microwaves and enabling monosilane to crack and carry out free radical recombination reaction on the surface of the heated silicon powder to generate the higher-order silanes.
Disclosure of Invention
In order to solve the problems, the invention provides a method and a system for continuously synthesizing higher-order silane by utilizing a microwave heating fixed bed, which are characterized in that a fixed bed reaction mode is used, silicon powder and a catalyst in the fixed bed layer are heated by adopting microwaves, monosilane is continuously introduced into a fixed bed reaction device to be contacted with the silicon powder and the catalyst in the fixed bed layer, and cracking and free radical rearrangement reactions are generated to generate the higher-order silane.
The invention aims to provide a method for continuously synthesizing higher-order silane by utilizing a microwave heating fixed bed, which comprises the following steps:
step one: filling a fixed bed layer in which silicon powder and catalyst powder are uniformly mixed into a closed fixed bed reaction device, and heating the bed material to 250-500 ℃ by utilizing microwaves;
step two: introducing monosilane gas into the fixed bed reaction device, enabling the monosilane gas to flow through a bed material to contact the monosilane gas for reaction, and discharging the monosilane gas out of the fixed bed reaction device, wherein the reaction pressure is 0.05-1 MPa;
step three: and (3) rectifying the discharged gas to obtain high-order silane: disilane, trisilane and butanosilane.
The further improvement is that: the average grain diameter of the silicon powder ranges from 1 μm to 500 μm.
The further improvement is that: the catalyst powder is one or more metal powders of lithium, iron, cobalt, nickel, copper and palladium.
The further improvement is that: the average particle diameter of the metal powder ranges from 1 to 500 mu m.
The further improvement is that: the mass ratio of the catalyst to the silicon powder is 1: 2-1: 20.
the invention also provides a system for continuously synthesizing the higher-order silane by utilizing the microwave heating fixed bed, which comprises a fixed bed reaction device and microwave heating devices positioned around the fixed bed reaction device; the fixed bed reaction device comprises a reaction cavity, wherein the bottom end of the reaction cavity is provided with a monosilane inlet, the bottom of the reaction cavity is positioned above the monosilane inlet, a gas distribution plate is arranged in a penetrating manner, and the top of the reaction cavity is provided with a silane outlet; the gas nozzles are distributed on the part of the gas distribution plate, which is positioned in the reaction cavity; the reaction cavity is internally provided with a fixed bed layer formed by silicon powder and catalyst powder.
The further improvement is that: the fixed bed reactor uses a material with low microwave absorptivity, preferably glass, silica or alumina.
The further improvement is that: the silane outlet is connected with a coarse fraction rectifying tower, the top of the coarse fraction rectifying tower is connected with a monosilane rectifying tower, hydrogen is discharged from the top of the monosilane rectifying tower, and monosilane is discharged from the bottom of the monosilane rectifying tower; the bottom of the coarse fraction rectifying tower is connected with a disilane rectifying tower, disilane is discharged from the top of the disilane rectifying tower, the bottom of the disilane rectifying tower is connected with a heavy fraction rectifying tower, and trisilane and butylsilane are respectively discharged from the top of the heavy fraction rectifying tower and the top of the tower.
The invention has the beneficial effects that: according to the method for continuously and efficiently synthesizing the high-order silane, the technical difficulty of synthesizing the high-order silane by cracking the prior monosilane is overcome, the production efficiency can be obviously improved by improving the reaction pressure, the thermal decomposition of the high-order silane is effectively inhibited, and the yield of the high-order silane is improved.
According to the method for efficiently and continuously producing disilane, glow discharge equipment with a complex structure is not needed, the equipment reliability is improved, the reaction energy consumption is reduced, and the reaction conditions are mild and controllable.
According to the method for continuously and efficiently synthesizing the high-order silane, the silicon powder in the fixed bed layer and the byproduct silicon powder generated by cracking the monosilane can form dynamic balance, so that the process can realize continuous long-period stable operation.
On the one hand, in the reaction process of preparing the high-order silane by cracking monosilane, the reaction of rearranging the free radicals to form the high-order silane and the reaction of thermal decomposition of the high-order silane are carried out simultaneously, and the process of generating the free radicals by cracking monosilane and generating the silicon powder by thermal decomposition of the high-order silane can be simultaneously promoted by increasing the reaction temperature. Therefore, the invention provides the heated silicon powder surface as a heating source, so that the process of thermal cracking monosilane into free radicals mainly occurs on the silicon powder surface, and the generated high-order silane can quickly enter a gas phase main body to reduce the temperature after leaving the silicon powder surface, thereby reducing the proportion of thermal decomposition of the high-order silane; meanwhile, the free radical rearrangement process occurs on the surfaces of the silicon powder and the catalyst, so that more activated solid-phase silicon atoms are combined with the free radicals to form chemical bonds and enter a gas-phase system, and the yield of the high-order silane can be promoted. On the other hand, the invention heats the silicon powder by utilizing microwaves without low pressure conditions required by discharge, and can improve the concentration of reactants by improving the pressure of the system, thereby improving the production efficiency in unit time. Because the monosilane cracking reaction process can generate byproduct silicon powder at the same time, dynamic balance can be formed between the monosilane cracking reaction process and silicon powder consumption in the fixed bed layer, the reaction process can run continuously for a long time without supplementing the bed layer, and thus long-period continuous running is realized.
Drawings
FIG. 1 is a schematic diagram of a reaction system of the present invention.
Wherein: 1-monosilane inlet, 2-gas distribution plate, 3-reaction cavity, 4-silane outlet, 5-microwave heating device, 6-gas nozzle, 7-fixed bed layer, 8-coarse fraction rectifying tower, 9-monosilane rectifying tower, 10-disilane rectifying tower and 11-heavy fraction rectifying tower.
Detailed Description
The present invention will be further described in detail with reference to examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
Example 1
A microwave heating device with the volume of a reaction cavity of 8L and the power of 3kW is adopted, 2kg of silicon powder and 0.5kg of nickel powder are filled as a fixed bed layer, after the microwave heating is started for 10 minutes, monosilane with the pressure of 0.1MPa is introduced at the flow rate of 4g/min, and the operation is continuously carried out for 10 hours. Condensing the gas discharged from the silane outlet to-180 ℃ for collection until the reaction is finished, and vacuumizing the collection tank. Weighing a collecting tank after the reaction is finished, and calculating the total mass of the obtained silane; heating the collected product, collecting gas until the temperature reaches-45 ℃, and weighing the collected gas, wherein the result is the mass of monosilane; repeating the operation until the temperature reaches 10 ℃, collecting gas for weighing, and obtaining the disilane mass as a result; the above operation was repeated up to 75 ℃, and the gas was collected and weighed, resulting in trisilane mass.
Total mass of silane: 2221 grams;
monosilane mass: 1360 g; silyl mass conversion: 43.3%
Disilane mass: 605 g; disilane mass yield: 25.2%;
trisilane mass: 192 g; trisilane mass yield: 8.3%;
mass of the butylsilane: 64 g; mass yield of butylsilane: 2.8%;
higher order silane total mass conversion: 36.3%.
Example two
A microwave heating device with the volume of a reaction cavity of 8L and the power of 3kW is adopted, 2.5kg of silicon powder and 0.5kg of copper powder are filled as a fixed bed layer, after the microwave heating is started for 15 minutes, monosilane with the pressure of 0.3MPa is introduced at the flow rate of 8g/min, and the operation is continuously carried out for 10 hours. Condensing the gas discharged from the silane outlet to-180 ℃ for collection until the reaction is finished, and vacuumizing the collection tank. Weighing a collecting tank after the reaction is finished, and calculating the total mass of the obtained silane; heating the collected product, collecting gas until the temperature reaches-45 ℃, and weighing the collected gas, wherein the result is the mass of monosilane; repeating the operation until the temperature reaches 10 ℃, collecting gas for weighing, and obtaining the disilane mass as a result; the above operation was repeated up to 75 ℃, and the gas was collected and weighed, resulting in trisilane mass.
Total mass of silane: 4076 g;
monosilane mass: 2600 grams; silyl mass conversion: 45.8%
Disilane mass: 1120 grams; disilane mass yield: 24.1%;
trisilane mass: 277 grams; trisilane mass yield: 6%;
mass of the butylsilane: 79 g; mass yield of butylsilane: 1.7%;
higher order silane total mass conversion: 31.8%.
Example III
A microwave heating device with the volume of a reaction cavity of 8L and the power of 3kW is adopted, 3kg of silicon powder and 0.5kg of palladium powder are filled as a fixed bed layer, after the microwave heating is started for 15 minutes, monosilane with the pressure of 0.07MPa is introduced at the flow rate of 3g/min, and the operation is continuously carried out for 10 hours. Condensing the gas discharged from the silane outlet to-180 ℃ for collection until the reaction is finished, and vacuumizing the collection tank. Weighing a collecting tank after the reaction is finished, and calculating the total mass of the obtained silane; heating the collected product, collecting gas until the temperature reaches-45 ℃, and weighing the collected gas, wherein the result is the mass of monosilane; repeating the operation until the temperature reaches 10 ℃, collecting gas for weighing, and obtaining the disilane mass as a result; the above operation was repeated up to 75 ℃, and the gas was collected and weighed, resulting in trisilane mass.
Total mass of silane: 2029 grams;
monosilane mass: 1205 g; silyl mass conversion: 33.1%
Disilane mass: 566 grams; disilane mass yield: 32.4%;
trisilane mass: 177 g; trisilane mass yield: 10.3%;
mass of the butylsilane: 81 g; mass yield of butylsilane: 4.7%;
higher order silane total mass conversion: 47.4%.
In the embodiment, after the fixed bed layer formed by the silicon powder and the catalyst is heated by microwaves and monosilane is reacted through the fixed bed layer, the total conversion rate of the high-order silane is more than 30 percent, and meanwhile, the long-period continuous operation is realized, and the bottleneck of the existing process is broken through.
Example IV
As shown in fig. 1, the present embodiment provides a system for a method for continuously synthesizing higher order silane by heating a fixed bed using microwaves, comprising a fixed bed reaction unit and a microwave heating unit 5 located around the fixed bed reaction unit; the fixed bed reaction device comprises a reaction cavity 3, wherein a monosilane inlet 1 made of stainless steel is arranged at the bottom end of the reaction cavity 3, a gas distribution plate 2 is arranged above the monosilane inlet 1 in a penetrating way at the bottom of the reaction cavity 3, and a silane outlet 4 is arranged at the top of the reaction cavity 3; the part of the gas distribution plate 2 positioned in the reaction cavity 3 is distributed with gas nozzles 6 made of aluminum oxide; a fixed bed layer 7 formed by silicon powder and catalyst powder is arranged in the reaction cavity 3; the fixed bed reaction device is made of a material with low microwave absorptivity, preferably glass, silicon dioxide or aluminum oxide; the silane outlet 4 is connected with a coarse fraction rectifying tower 8, the top of the coarse fraction rectifying tower 8 is connected with a monosilane rectifying tower 9, hydrogen is discharged from the top of the monosilane rectifying tower 9, and monosilane is discharged from the bottom of the monosilane rectifying tower 9; disilane rectifying tower 10 is connected to the bottom of coarse fraction rectifying tower 8, disilane is discharged from the top of disilane rectifying tower 10, heavy fraction rectifying tower 11 is connected to the bottom of disilane rectifying tower 10, and trisilane and butanosilane are respectively discharged from the top of heavy fraction rectifying tower 11 and the top of the tower.
Silicon powder and metal powder are added into a reaction cavity 3 to form a fixed bed layer 7, the fixed bed layer is heated by a microblog heating device 5, monosilane is fed through a monosilane inlet 1, then high-order silane is produced by reaction, the high-order silane enters a coarse fraction rectifying tower 8 through a silane outlet 4, gas at the top of the coarse fraction rectifying tower 8 enters a monosilane rectifying tower 9, hydrogen is discharged from the top of the monosilane rectifying tower 9, and monosilane is discharged from the bottom of the monosilane rectifying tower 9; the gas at the bottom of the coarse fraction rectifying tower 8 enters an disilane rectifying tower 10, disilane is discharged from the top of the disilane rectifying tower 10, the gas at the bottom of the disilane rectifying tower 10 enters a heavy fraction rectifying tower 11, and trisilane and monosilane are respectively discharged from the top of the heavy fraction rectifying tower 11 and the top of the monosilane rectifying tower.
While the invention has been described and illustrated in detail in the foregoing description with reference to specific embodiments thereof, it should be noted that various equivalent changes and modifications could be made to the above described embodiments without departing from the spirit of the invention as defined by the appended claims.
Claims (8)
1. A method for continuously synthesizing higher-order silane by utilizing a microwave heating fixed bed is characterized in that: the method comprises the following steps:
step one: filling a fixed bed layer in which silicon powder and catalyst powder are uniformly mixed into a closed fixed bed reaction device, and heating the bed material to 250-500 ℃ by utilizing microwaves;
step two: introducing monosilane gas into the fixed bed reaction device, enabling the monosilane gas to flow through a bed material to contact the monosilane gas for reaction, and discharging the monosilane gas out of the fixed bed reaction device, wherein the reaction pressure is 0.05-1 MPa;
step three: and (3) rectifying the discharged gas to obtain high-order silane: disilane, trisilane and butanosilane.
2. The method for continuously synthesizing higher-order silanes by using a microwave heating fixed bed as claimed in claim 1, wherein: the average grain diameter of the silicon powder ranges from 1 μm to 500 μm.
3. The method for continuously synthesizing higher-order silanes by using a microwave heating fixed bed as claimed in claim 1, wherein: the catalyst powder is one or more metal powders of lithium, iron, cobalt, nickel, copper and palladium.
4. The method for continuously synthesizing higher-order silanes by heating a fixed bed with microwaves as set forth in claim 3, wherein: the average particle diameter of the metal powder ranges from 1 to 500 mu m.
5. The method for continuously synthesizing higher-order silanes by heating a fixed bed with microwaves as set forth in claim 3, wherein: the mass ratio of the catalyst to the silicon powder is 1: 2-1: 20.
6. a system based on the method for continuously synthesizing higher order silanes using microwave heating fixed bed as claimed in any one of claims 1 to 5, characterized in that: comprises a fixed bed reaction device and a microwave heating device (5) positioned around the fixed bed reaction device; the fixed bed reaction device comprises a reaction cavity (3), wherein a monosilane inlet (1) is formed in the bottom end of the reaction cavity (3), a gas distribution plate (2) is arranged above the monosilane inlet (1) in a penetrating way at the bottom of the reaction cavity (3), and a silane outlet (4) is formed in the top of the reaction cavity (3); the gas nozzles (6) are distributed on the part of the gas distribution plate (2) positioned in the reaction cavity (3); the reaction cavity (3) is internally provided with a fixed bed layer (7) formed by silicon powder and catalyst powder.
7. The system for continuous synthesis of higher order silanes using microwave heating fixed bed as claimed in claim 6, wherein: the fixed bed reaction device uses a material with low microwave absorptivity, and is glass, silicon dioxide or aluminum oxide.
8. The system for continuous synthesis of higher order silanes using microwave heating fixed bed as claimed in claim 6, wherein: the silane outlet (4) is connected with a coarse separation rectifying tower (8), the top of the coarse separation rectifying tower (8) is connected with a monosilane rectifying tower (9), hydrogen is discharged from the top of the monosilane rectifying tower (9), and monosilane is discharged from the bottom of the monosilane rectifying tower (9); disilane rectifying tower (10) is connected at the bottom of the coarse fraction rectifying tower (8), disilane is discharged from the top of the disilane rectifying tower (10), heavy fraction rectifying tower (11) is connected at the bottom of the disilane rectifying tower (10), and trisilane and butanosilane are respectively discharged from the top of the heavy fraction rectifying tower (11) and the top of the tower.
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