CN114314596A - Method and system for continuously synthesizing high-order silane by utilizing microwave heating fixed bed - Google Patents
Method and system for continuously synthesizing high-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 125
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000010438 heat treatment Methods 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 46
- 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 18
- YXMVRBZGTJFMLH-UHFFFAOYSA-N butylsilane Chemical compound CCCC[SiH3] YXMVRBZGTJFMLH-UHFFFAOYSA-N 0.000 claims description 10
- 150000004756 silanes Chemical class 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 239000002245 particle 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 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
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 17
- 238000005336 cracking Methods 0.000 abstract description 14
- 150000003254 radicals Chemical class 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 230000006872 improvement Effects 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
- 238000004519 manufacturing process Methods 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
- 230000008021 deposition Effects 0.000 description 4
- -1 lithium aluminum hydride Chemical compound 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 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
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-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
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 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
- 238000010521 absorption reaction Methods 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
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method for generating high-order silane by cracking silane in a silicon powder bed layer in a microwave heating mode and a reaction system thereof; in a fixed bed reaction device, silica powder is added with a catalyst to serve as a fixed bed layer, silane is introduced into the bed layer, and the bed layer material is heated in a microwave heating mode, so that the silane is subjected to cracking and free radical recombination reaction on the surface of the silica powder to generate high-order silane. The invention realizes the process of directly synthesizing high-order silane from low-order silane, has high yield of the high-order silane, simple and continuous reaction process, no excessive chemical medium, no by-product emission and easy separation and purification of products.
Description
Technical Field
The invention relates to the field of synthesis of high-order silane, in particular to a method and a system for continuously synthesizing high-order silane by using 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 silicon-element-containing films, particularly amorphous silicon and polycrystalline silicon films. At present, the most widely used silane gas is monosilane, but the decomposition temperature of monosilane for depositing the polycrystalline silicon film is higher, the deposition rate is slower, and the application of the polycrystalline silicon film is limited to a certain extent, for example, the polycrystalline silicon film is directly deposited on a glass substrate. The high-order silane has lower decomposition temperature and higher deposition rate, and the deposited and grown film has more regular lattice arrangement, thereby being more beneficial to growing and forming the large-grain polycrystalline silicon film. For example, the temperature for growing the polycrystalline silicon film by disilane deposition can be as low as about 500 ℃ and lower than the softening temperature of common glass, so that the process of directly depositing the polycrystalline silicon film on the surface of the glass substrate can be realized; the temperature for growing the polycrystalline silicon film by deposition of the trisilane can be lower than 300 ℃, so that the process for preparing the special composite film material by directly depositing the polycrystalline silicon film on the flexible substrate or combining with other materials such as graphene and the like is hopeful to be realized. Compared with the prior art, generally, the amorphous silicon film is deposited by taking monosilane as a raw material and then the polycrystalline silicon film is formed by laser-induced crystal conversion, so that the preparation efficiency is low, and the development of related application technologies is severely restricted.
The existing process routes for industrially producing disilane mainly comprise a hexachlorodisilane hydrogenation method, a magnesium silicide method and a monosilane cracking method.
Among them, the hexachlorodisilane hydrogenation method generally uses lithium aluminum hydride or sodium aluminum hydride as a reducing agent, and reacts with hexachlorodisilane in an organic solvent to produce disilane and salt, accompanied by a byproduct of chlorine. The process has the advantages of continuous production, easy production scale enlargement, complex hexachlorodisilane purification process, high difficulty, harsh preparation conditions of reducing agents lithium aluminum hydride or sodium aluminum hydride, complex whole process flow, high energy consumption, high control difficulty, high equipment investment and operation cost.
The silicon-magnesium method generally takes magnesium silicide and ammonium chloride as raw materials to react in a liquid ammonia solvent, the reaction is generally carried out under the condition of micro-positive pressure, and the temperature is controlled within the range of-20 to-30 ℃. The process is mainly used for preparing high-purity monosilane, and meanwhile, about 3-5% of disilane and a trace amount of trisilane are by-produced. The process has the advantages of short process flow, simple equipment, easy control, high purity of the obtained silane gas product and easy later purification. In the process, the first step is to mix silicon powder and magnesium powder and then ball mill the mixture, and then heat the mixture to over 500 ℃ to carry out alloying reaction to generate magnesium silicide powder. Because the industrial-grade silicon powder on the market is about 200 meshes generally, and the magnesium powder is inflammable and explosive due to the excessively fine particle size, the particle size of the powder purchased on the market is about 40 meshes generally, and the powder particle size suitable for the alloying process is 600-1000 meshes, and because the solid-solid phase reaction is adopted, the two kinds of powder need to be fully stirred and pressed to ensure that the powder has enough contact area, so the step needs to be carried out for a long time for alloying treatment firstly. And because the reaction occurs on the surface of the solid phase, after the reaction generates magnesium silicide, the magnesium silicide occupies the reaction site to prevent the further reaction, so that the full reaction inside the powder is difficult to realize, and the conversion rate of the alloying reaction is low.
The monosilane cracking method is a method in which monosilane is used as a raw material and undergoes a cracking reaction to form a radical, and then the radical is rearranged and combined to generate higher-order silane. The method uses high-purity monosilane as a raw material, generally combines the reaction condition of glow discharge, and carries out reaction under lower pressure, so that various high-order silanes such as disilane, trisilane, tetrasilane and the like can be simultaneously generated. The method adopts monosilane as a raw material, and the monosilane is easy to purify, so that the generated high-order silane has extremely high purity and is 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 high-order silane is extremely low, and silicon powder is generated as a byproduct in the reaction process, so that the raw material monosilane is greatly wasted. If the reaction pressure needs to be increased, the reaction temperature is increased, the decomposition of the high-order silane is accelerated, the by-product silicon powder is increased, and the conversion rate of the high-order silane is obviously reduced.
In conclusion, the hexachlorodisilane hydrogenation process in the prior art is complex in process and difficult to operate, the silicon-magnesium process can only be operated intermittently, the operation time is long, the conversion rate is low, and the total productivity is low.
On the basis of researching the reaction mechanism of a silane cracking method and physical parameters of various high-order silanes, the invention provides that microwave is adopted to heat silicon powder, and silane is subjected to cracking and free radical recombination reaction on the surface of the heated silicon powder to generate the high-order silanes.
Disclosure of Invention
In order to solve the problems, the invention provides a method and a system for continuously synthesizing high-order silane by using a microwave heating fixed bed, wherein the silicon powder and a catalyst in a fixed bed layer are heated by adopting microwave in a fixed bed reaction mode, and the silane is continuously introduced into a fixed bed reaction device to be contacted with the silicon powder and the catalyst in the fixed bed layer to generate cracking and free basis weight rearrangement reaction so as to generate the high-order silane.
The invention aims to provide a method for continuously synthesizing high-order silane by utilizing a microwave heating fixed bed, which comprises the following steps:
the method comprises the following steps: filling a fixed bed layer formed by uniformly mixing silicon powder and catalyst powder into a closed fixed bed reaction device, and heating bed layer materials to 250-500 ℃ by using microwaves;
step two: introducing monosilane gas into a fixed bed reaction device, allowing the monosilane gas to flow through a bed layer material to contact with the bed layer material for reaction, and discharging the reaction product 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 tetrasilane.
The further improvement lies in that: the average particle size of the silicon powder ranges from 1 to 500 mu m.
The further improvement lies in that: the catalyst powder is one or more of metal powder of lithium, iron, cobalt, nickel, copper and palladium.
The further improvement lies in that: the average particle size of the metal powder is 1 to 500 μm.
The further improvement lies in 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 high-order silane by using the microwave heating fixed bed, which comprises a fixed bed reaction device and a microwave heating device positioned around the fixed bed reaction device; the fixed bed reaction device comprises a reaction cavity, a silane inlet is formed in the bottom end of the reaction cavity, a gas distribution disc penetrates through the bottom of the reaction cavity and is positioned above the silane inlet, and a silane outlet is formed in the top of the reaction cavity; gas nozzles are distributed on the part of the gas distribution plate 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 lies in that: the fixed bed reaction device uses a material with low microwave absorptivity, and preferably glass, silicon dioxide or aluminum oxide.
The further improvement lies in 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 and the top of the heavy fraction rectifying 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 existing silane 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 reliability of the equipment 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 silane can form dynamic balance, so that the process can realize continuous long-period stable operation.
On one hand, in the reaction process of preparing the high-order silane by cracking the silane, the reaction of forming the high-order silane by the basis weight and the reaction of thermally decomposing the high-order silane are carried out simultaneously, and the reaction temperature is increased to promote the processes of generating free radicals by cracking the silane and generating silicon powder by thermally decomposing the high-order silane simultaneously. Therefore, the invention provides that the heated silicon powder surface is provided as a heating source, the process of heating and cracking the silane into free radicals mainly occurs on the silicon powder surface, and the generated high-order silane can rapidly enter the gas phase main body to reduce the temperature after leaving the silicon powder surface, so that the proportion of the high-order silane which is heated and decomposed is reduced; meanwhile, the rearrangement process of the free radicals 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 high-order silane can be promoted to be improved. On the other hand, the invention heats the silicon powder by using the microwave, does not need low-pressure conditions required by discharge, and can improve the concentration of reactants by improving the system pressure, thereby improving the production efficiency in unit time. As the silane cracking reaction process generates byproduct silicon powder simultaneously, the byproduct silicon powder and the silicon powder in the fixed bed layer can form dynamic balance, the reaction process can continuously run for a long time without supplementing the bed layer, thereby realizing long-period continuous operation.
Drawings
FIG. 1 is a schematic diagram of a reaction system of the present invention.
Wherein: the device comprises a 1-monosilane inlet, a 2-gas distribution disc, a 3-reaction cavity, a 4-silane outlet, a 5-microwave heating device, a 6-gas nozzle, a 7-fixed bed layer, an 8-coarse fraction rectifying tower, a 9-monosilane rectifying tower, a 10-disilane rectifying tower and an 11-heavy component rectifying tower.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example one
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 fixed bed layers, 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 continuous operation is carried out for 10 hours. And (4) condensing the gas discharged from the silane outlet to-180 ℃ and collecting the gas until the reaction is finished, and vacuumizing a collection tank. After the reaction is finished, firstly weighing the collection tank, and calculating the total mass of the obtained silane; heating the collected product and collecting gas until the temperature is minus 45 ℃, and weighing the collected gas, wherein the result is the mass of the monosilane; repeating the operation until the temperature reaches 10 ℃, collecting the gas and weighing the gas, wherein the result is the mass of the disilane; the above operation was repeated again until 75 ℃, and the gas was collected and weighed, the result being the mass of trisilane.
Total mass of silane: 2221 g;
mass of monosilane: 1360 g; mass conversion of monosilane: 43.3 percent
The mass of disilane is as follows: 605 g; the disilane mass yield: 25.2 percent;
the mass of the trisilane is as follows: 192 g; the mass yield of the trisilane is as follows: 8.3 percent;
mass of the butyl silane: 64 g; mass yield of the butyl silane: 2.8 percent;
total higher-order silane mass conversion: 36.3 percent.
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 fixed bed layers, after 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 continuous operation is carried out for 10 hours. And (4) condensing the gas discharged from the silane outlet to-180 ℃ and collecting the gas until the reaction is finished, and vacuumizing a collection tank. After the reaction is finished, firstly weighing the collection tank, and calculating the total mass of the obtained silane; heating the collected product and collecting gas until the temperature is minus 45 ℃, and weighing the collected gas, wherein the result is the mass of the monosilane; repeating the operation until the temperature reaches 10 ℃, collecting the gas and weighing the gas, wherein the result is the mass of the disilane; the above operation was repeated again until 75 ℃, and the gas was collected and weighed, the result being the mass of trisilane.
Total mass of silane: 4076 g;
mass of monosilane: 2600 g; mass conversion of monosilane: 45.8 percent of
The mass of disilane is as follows: 1120 grams; the disilane mass yield: 24.1 percent;
the mass of the trisilane is as follows: 277 grams; the mass yield of the trisilane is as follows: 6 percent;
mass of the butyl silane: 79 g; mass yield of the butyl silane: 1.7 percent;
total higher-order silane mass conversion: 31.8 percent.
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 fixed bed layers, after 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 continuous operation is carried out for 10 hours. And (4) condensing the gas discharged from the silane outlet to-180 ℃ and collecting the gas until the reaction is finished, and vacuumizing a collection tank. After the reaction is finished, firstly weighing the collection tank, and calculating the total mass of the obtained silane; heating the collected product and collecting gas until the temperature is minus 45 ℃, and weighing the collected gas, wherein the result is the mass of the monosilane; repeating the operation until the temperature reaches 10 ℃, collecting the gas and weighing the gas, wherein the result is the mass of the disilane; the above operation was repeated again until 75 ℃, and the gas was collected and weighed, the result being the mass of trisilane.
Total mass of silane: 2029 g;
mass of monosilane: 1205 grams; mass conversion of monosilane: 33.1 percent
The mass of disilane is as follows: 566 grams; the disilane mass yield: 32.4 percent;
the mass of the trisilane is as follows: 177 grams; the mass yield of the trisilane is as follows: 10.3 percent;
mass of the butyl silane: 81 g; mass yield of the butyl silane: 4.7 percent;
total higher-order silane mass conversion: 47.4 percent.
In the embodiment, after the fixed bed layer formed by the silicon powder and the catalyst is heated by microwaves and the monosilane is reacted through the fixed bed layer, the total conversion rate of the high-order silane exceeds 30%, meanwhile, the long-period continuous operation is realized, and the bottleneck of the existing process is broken through.
Example four
As shown in fig. 1, the present embodiment provides a system for a method for continuously synthesizing higher-order silane by using a fixed bed heated by microwaves, comprising a fixed bed reaction device and a microwave heating device 5 located around the fixed bed reaction device; the fixed bed reaction device comprises a reaction cavity 3, a stainless steel monosilane inlet 1 is arranged at the bottom end of the reaction cavity 3, a gas distribution disc 2 penetrates through the bottom of the reaction cavity 3 and is positioned above the monosilane inlet 1, and a silane outlet 4 is arranged at the top of the reaction cavity 3; a gas nozzle 6 made of alumina is distributed on the part of the gas distribution plate 2 positioned in the reaction cavity 3; 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 absorption rate, 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; the tower bottom of the coarse component rectifying tower 8 is connected with a disilane rectifying tower 10, disilane is discharged from the tower top of the disilane rectifying tower 10, the tower bottom of the disilane rectifying tower 10 is connected with a heavy component rectifying tower 11, and trisilane and butylsilane are respectively discharged from the tower top and the tower top of the heavy component rectifying tower 11.
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 enters through a monosilane inlet 1 and then reacts to produce high-order silane, the high-order silane enters into a coarse fractionating tower 8 through a silane outlet 4, gas at the top of the coarse fractionating tower 8 enters into 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; and gas at the bottom of the coarse component rectifying tower 8 enters a disilane rectifying tower 10, disilane is discharged from the top of the disilane rectifying tower 10, inlet gas at the bottom of the disilane rectifying tower 10 enters a heavy component rectifying tower 11, and trisilane and butylsilane are respectively discharged from the top and the top of the heavy component rectifying tower 11.
Although particular embodiments of the invention have been described and illustrated in detail, it should be understood that various equivalent changes and modifications could be made to the above-described embodiments in accordance with the teachings of the present invention, and its functional operation would still fall within the scope of the present invention, without departing from the spirit covered by the present specification.
Claims (8)
1. A method for continuously synthesizing high-order silane by utilizing a microwave heating fixed bed is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: filling a fixed bed layer formed by uniformly mixing silicon powder and catalyst powder into a closed fixed bed reaction device, and heating bed layer materials to 250-500 ℃ by using microwaves;
step two: introducing monosilane gas into a fixed bed reaction device, allowing the monosilane gas to flow through a bed layer material to contact with the bed layer material for reaction, and discharging the reaction product 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 tetrasilane.
2. The method for continuous synthesis of higher order silanes using a fixed bed heated by microwaves as claimed in claim 1 wherein: the average particle size of the silicon powder ranges from 1 to 500 mu m.
3. The method for continuous synthesis of higher order silanes using a fixed bed heated by microwaves as claimed in claim 1 wherein: the catalyst powder is one or more of metal powder of lithium, iron, cobalt, nickel, copper and palladium.
4. The method for continuous synthesis of higher order silanes using a fixed bed heated by microwaves as claimed in claim 3 wherein: the average particle size of the metal powder is 1 to 500 μm.
5. The method for continuous synthesis of higher order silanes using a fixed bed heated by microwaves as claimed 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 silane by using a microwave heating fixed bed according to 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), a silane inlet (1) is formed in the bottom end of the reaction cavity (3), a gas distribution disc (2) penetrates through the bottom of the reaction cavity (3) and is positioned above the silane inlet (1), and a silane outlet (4) is formed in the top of the reaction cavity (3); 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 the continuous synthesis of higher order silanes using a microwave heated fixed bed as claimed in claim 6 wherein: the fixed bed reaction device uses a material with low microwave absorptivity, and preferably glass, silicon dioxide or aluminum oxide.
8. The system for the continuous synthesis of higher order silanes using a microwave heated fixed bed as claimed in claim 6 wherein: the silane outlet (4) is connected with a coarse fractionating rectifying tower (8), the top of the coarse fractionating 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); the tower bottom of the coarse fraction rectifying tower (8) is connected with a disilane rectifying tower (10), disilane is discharged from the tower top of the disilane rectifying tower (10), the tower bottom of the disilane rectifying tower (10) is connected with a heavy component rectifying tower (11), and trisilane and butylsilane are respectively discharged from the tower top and the tower top of the heavy component rectifying tower (11).
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