CN117205842A - Silane reactive distillation process and system thereof - Google Patents
Silane reactive distillation process and system thereof Download PDFInfo
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- CN117205842A CN117205842A CN202311199029.2A CN202311199029A CN117205842A CN 117205842 A CN117205842 A CN 117205842A CN 202311199029 A CN202311199029 A CN 202311199029A CN 117205842 A CN117205842 A CN 117205842A
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 143
- 238000000066 reactive distillation Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 109
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000000746 purification Methods 0.000 claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000005192 partition Methods 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims description 37
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 25
- 239000005052 trichlorosilane Substances 0.000 claims description 25
- 239000007791 liquid phase Substances 0.000 claims description 21
- 238000011144 upstream manufacturing Methods 0.000 claims description 15
- 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 13
- 238000012856 packing Methods 0.000 claims description 13
- 239000005049 silicon tetrachloride Substances 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 46
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 16
- 229920005591 polysilicon Polymers 0.000 abstract description 16
- 239000006227 byproduct Substances 0.000 abstract description 10
- 239000007789 gas Substances 0.000 description 35
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 1
- 229910021338 magnesium silicide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910021332 silicide 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
Classifications
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Silicon Compounds (AREA)
Abstract
The application relates to the field of silane reactive distillation, and particularly discloses a silane reactive distillation process and a system thereof. A silane reaction rectification system comprises a purification tower, a reaction rectification tower, a light component removal tower and a product tower which are sequentially communicated; the upper section of the reaction rectifying tower is filled with a first catalyst bed layer and a second catalyst bed layer, a partition plate is arranged between the first catalyst bed layer and the second catalyst bed layer, and the first catalyst bed layer and the second catalyst bed layer are filled with weak base resin catalysts so as to realize the disproportionation reaction of dichlorosilane to generate silane. The application discloses a silane reaction process suitable for a silane reaction rectification system, which uses byproduct dichlorosilane in Siemens polysilicon production as a raw material, and the high-purity electronic grade monosilane electron special gas produced by the silane reaction rectification system has high purity and 8N grade, so that the economy of Siemens polysilicon process devices is improved.
Description
Technical Field
The application relates to the field of silane electron special gas, in particular to a silane reaction rectification process and a system thereof.
Background
The main process route of producing polysilicon in the world is Siemens method, the production process mainly takes industrial silicon powder and hydrogen chloride as raw materials, synthesizes trichlorosilane at a certain temperature, then carries out rectification and purification on the trichlorosilane through a series of procedures, and carries out CVD reaction on the purified trichlorosilane in a hydrogen reduction furnace to produce polysilicon. The production process of polysilicon by Siemens method generates dichlorosilane and silicon tetrachloride byproducts, and the existing Siemens production flow mostly combines cold hydrogenation treatment to convert the Siemens into trichlorosilane again for recycling, so that whether the dichlorosilane can be effectively utilized becomes an important problem for restricting polysilicon production enterprises.
Disclosure of Invention
In order to take byproduct dichlorosilane in Siemens polysilicon production as a raw material to produce high-purity electronic grade monosilane electron special gas, thereby improving the economy of Siemens polysilicon process devices, the application provides a silane reaction rectification process and a system thereof.
The application provides a silane reaction rectification process and a system thereof, which adopt the following technical scheme:
in a first aspect, the application provides a silane reactive distillation system, which adopts the following technical scheme:
a silane reaction rectification system comprises a purification tower, a reaction rectification tower, a light component removal tower and a product tower which are sequentially communicated; the purifying tower is communicated with a raw material pump for pumping the raw material of the dichlorosilane, and the discharging end at the bottom of the purifying tower is communicated with the upper section feed inlet of the reactive rectifying tower; the top discharge end of the reaction rectifying tower is communicated with the tower kettle feed inlet of the light component removing tower, the bottom discharge end of the light component removing tower is communicated with the tower kettle feed inlet of the product tower, a silane product is extracted from the top of the product tower, and the bottom of the product tower is communicated with the upper section feed inlet of the reaction rectifying tower; the upper section of the reaction rectifying tower is filled with a first catalyst bed layer and a second catalyst bed layer, a partition plate is arranged between the first catalyst bed layer and the second catalyst bed layer, and the first catalyst bed layer and the second catalyst bed layer are filled with weak base resin catalysts so as to realize the disproportionation reaction of dichlorosilane to generate silane.
By adopting the technical scheme, dichlorosilane byproducts generated in the Siemens process polysilicon production process are pumped to a purification tower through a raw material pump, light component impurities such as hydrogen chloride and the like are removed through the purification tower, dichlorosilane is subjected to disproportionation reaction in a reaction rectifying tower to generate silane, and crude silane in the reaction rectifying tower is subjected to further impurity removal through a light removal tower and a product tower to obtain high-purity monosilane, namely electronic grade monosilane electron gas. High purity monosilane is used as a gas source for providing a silicon component for the semiconductor industry, and has wide application in semiconductor manufacturing, electronic components and terminal equipment, and can be used for manufacturing high purity polysilicon, monocrystalline silicon, microcrystalline silicon, amorphous silicon, silicon nitride, silicon oxide, heterogeneous silicon, and various metal silicides. Because of its high purity and ability to achieve fine control, it has become an important specialty gas that many other silicon sources cannot replace. The preparation method of the silane mainly comprises the following three steps: magnesium silicide process, new silane process, disproportionation process. The existing chlorosilane disproportionation method for preparing silane mainly involves five compounds and three reactions:
the three reactions are carried out simultaneously, the conversion rate of reactants is very low after the equilibrium is reached, the five compounds are simultaneously present in the products in a closed state, the conversion rate of participating in the reaction is about 1% -5%, and how to change the reaction conditions in the reaction to make the reaction continuously proceed to the right becomes a main problem for restricting the economy of the device. The silane reaction rectification system provided by the application firstly removes light component impurities from the dichlorosilane byproduct through a purification tower, and the disproportionation reaction of the dichlorosilane is performed rightward between a first catalyst bed layer and a second catalyst bed layer in the reaction rectification tower, and the dichlorosilane is reacted to generate monochlorosilane and trichlorosilane, the trichlorosilane is reacted to generate dichlorosilane and tetrachlorosilane, and the monochlorosilane is reacted to generate dichlorosilane and target product silane. The generated silane is crude silane because of being mixed with other impurities, the light component impurities in the crude silane are further removed by the light component removing tower, 8N grade silane special gas is obtained by rectifying the crude silane by the product tower, and other components are returned to the reaction rectifying tower to continuously complete the reaction. Because crude silane is continuously separated from the reactive distillation column, three reactions related to the formation of silane by the disproportionation reaction of dichlorosilane in the reactive distillation column can also be continuously carried out to the right. In addition, the reaction rectifying tower separates the reaction products while disproportionation reaction occurs, and the common reaction kettle is coupled with the rectifying tower, so that the equipment investment is greatly reduced, in addition, the reaction conversion rate is improved, the material circulation quantity is reduced, and the operation cost is reduced. The weak base resin catalyst is fully utilized, and the catalyst not only has the effect of catalyzing chemical reaction in reactive distillation, but also can serve as a filler of the first catalyst bed layer and the second catalyst bed layer. In the reactive rectifying tower, the reaction temperature is convenient to adjust, and because the heat generated by the chemical reaction is consumed by the process of separating the reaction products, the temperature in the tower is limited by vapor-liquid balance and is always the bubble point of the mixture under the system pressure, the reaction temperature can be controlled by adjusting the system pressure, and the temperature runaway is effectively avoided. In a word, by taking byproduct dichlorosilane in Siemens polysilicon production as a raw material, the high-purity electronic grade monosilane electron special gas produced by the silane reaction rectification system has high purity and 8N grade, and the economy of a Siemens method polysilicon process device is improved.
Optionally, the lower part of the reaction rectifying tower is filled with structured packing to realize separation of heavy components in the reaction, and the bottom of the reaction rectifying tower is a heavy component discharge end.
By adopting the technical scheme, the disproportionation reaction of the dichlorosilane is performed rightward between the first catalyst bed layer and the second catalyst bed layer in the reaction rectifying tower, the dichlorosilane is reacted to generate the monochlorosilane and the trichlorosilane, the trichlorosilane is reacted to generate the dichlorosilane and the tetrachlorosilane, and the monochlorosilane is reacted to generate the dichlorosilane and the target product silane. The lower part of the reaction rectifying tower is filled with structured packing to realize the separation of heavy components in the reaction, namely the separation of trichlorosilane and silicon tetrachloride in the reaction, thereby further promoting the relevant three reactions of generating silane by the disproportionation reaction of dichlorosilane to go right and improving the conversion rate of the dichlorosilane participating in the reaction.
Optionally, a condenser is arranged at the top of the purifying tower.
By adopting the technical scheme, the condenser at the top of the purification tower is favorable for separating dichlorosilane and light component impurities, the dichlorosilane can return to the bottom of the purification tower after being condensed by the condenser, and the light component impurities are sent out of the system through the top of the purification tower.
Optionally, an intermediate condenser is arranged outside the reaction rectifying tower, a feeding end of the intermediate condenser is communicated with a position, close to the bottom of the partition plate, of the upper section of the reaction rectifying tower, a non-condensable gas output end of the intermediate condenser is communicated with a space below the first catalyst bed, and a liquid phase component output end of the intermediate condenser is communicated with a space above the second catalyst bed.
By adopting the technical scheme, the gas phase component above the second catalyst bed is sent to the intermediate condenser, the noncondensable gas after passing through the intermediate condenser is sent to the space below the first catalyst bed to continuously finish the disproportionation reaction, the silane generated by the reaction is mixed with the light component impurities and sent out from the top of the reactive distillation column to be processed in the next step, the liquid phase component after passing through the intermediate condenser is sent to the space above the second catalyst bed to continuously finish the disproportionation reaction, and the heavy components such as silicon tetrachloride, trichlorosilane and the like generated by the reaction are sent out from the bottom of the reactive distillation column to the outside of the system.
Optionally, a crude silane compressor is arranged between the reaction rectifying tower and the light component removing tower, the input end of the crude silane compressor is communicated with the reaction rectifying tower, and the output end of the crude silane compressor is communicated with the feed inlet of the light component removing tower.
By adopting the technical scheme, after the crude silane sent out by the reaction rectifying tower is pressurized by the crude silane compressor, the volume of the crude silane gas is smaller, which is beneficial to removing light component impurities from the crude silane in the light component removing tower. Furthermore, the crude silane gas occupies smaller space, and further, a smaller light component removing tower can be used for removing light component impurities from the crude silane, so that the cost of the light component removing tower is reduced.
In a second aspect, the application provides a silane reactive distillation process, which adopts the following technical scheme:
a silane production process suitable for use in a silane production system as described above, comprising the steps of:
the method comprises the steps of (1) pumping a raw material of dichlorosilane from the upstream into a purification tower through a raw material pump, removing light component impurities through the purification tower, and conveying the light component impurities to an upstream device through the top of the purification tower;
delivering dichlorosilane at the bottom of a purification tower to the space above a second catalyst bed layer of a reaction rectifying tower, delivering gas phase components in the space above the second catalyst bed layer to an intermediate condenser for condensation, returning liquid phase components condensed by the intermediate condenser to the space above the second catalyst bed layer, delivering noncondensable gas to the space below the first catalyst bed layer, performing disproportionation reaction on the dichlorosilane in the reaction rectifying tower to generate silane, extracting crude silane at the top of the reaction rectifying tower, and delivering trichlorosilane and silicon tetrachloride at the bottom of the reaction rectifying tower to the outside of the system;
pressurizing crude silane extracted from the top of a reactive rectifying tower to the pressure of 1.4-2.5 Mpag by a compressor crude silane compressor, and then conveying the crude silane to a light component removing tower, and removing light component impurities in the crude silane at the top of the light component removing tower;
distributing a tower bottom liquid phase component of the light component removal tower to a product tower, extracting electronic grade monosilane electronic special gas from the tower top of the product tower, and returning a heavy component of the tower bottom of the product tower to the reactive distillation tower for recycling;
the concentration of the dichlorosilane from upstream is 90wt% to 99wt%.
By adopting the technical scheme, firstly, the dichlorosilane by-product is subjected to a purification tower to remove light component impurities, and then the dichlorosilane by-product is fed from the upper section of the reaction rectifying tower, so that the contact between reactants and a catalyst can be increased, and the reaction is facilitated. And the disproportionation reaction of the dichlorosilane is carried out rightward between a first catalyst bed layer and a second catalyst bed layer in the reaction rectifying tower, and the dichlorosilane is reacted to generate monochloro silane and trichlorosilane, the trichlorosilane is reacted to generate dichlorosilane and tetrachlorosilane, and the monochloro silane is reacted to generate dichlorosilane and target product silane. In the reaction rectifying tower, the gas phase component above the second catalyst bed is sent to an intermediate condenser, the noncondensable gas after passing through the intermediate condenser is sent to the space below the first catalyst bed to continuously finish disproportionation reaction, silane generated by reaction is mixed with light component impurities and sent out from the top of the reaction rectifying tower to be processed in the next step, the liquid phase component after passing through the intermediate condenser is sent to the space above the second catalyst bed to continuously finish disproportionation reaction, and heavy components such as silicon tetrachloride, trichlorosilane and the like generated by reaction are sent out from the bottom of the reaction rectifying tower to the outside of the system. Because the reaction products are continuously removed from the reaction zone of the reactive rectifying tower, heavy components are enriched at the bottom of the tower, light components are enriched at the top of the tower, the chemical balance of the system is destroyed, the disproportionation reaction of the dichlorosilane is carried out to the right, and the conversion rate is very high. The silane generated in the reaction rectifying tower is crude silane because of being mixed with other impurities, the light component impurities in the crude silane are further removed by the light component removing tower, 8N grade silane special gas is obtained by rectifying the crude silane in the product tower, and other components are returned to the reaction rectifying tower to continuously complete the reaction. Experiments show that the high-purity electronic grade monosilane electron special gas produced by the silane reaction rectification system has high purity and 8N grade, and improves the economy of a Siemens process polysilicon process device by taking byproduct dichlorosilane in Siemens polysilicon production as a raw material.
Optionally, the operating pressure of the purifying tower is 0.25-1.0 Mpag, and the operating temperature is 55-100 ℃.
By adopting the technical scheme, the operating pressure of the purifying tower is 0.25-1.0 Mpag, the operating temperature is 55-100 ℃, and the effect of separating hydrogen component impurities by the purifying tower is good.
Optionally, the operation pressure of the reactive distillation column is 0.25-1.0 Mpag, and the operation temperature is-55-150 ℃.
By adopting the technical scheme, the operation pressure of the reaction rectifying tower is 0.25-1.0 Mpag, and the reaction rectifying tower is suitable for disproportionation reaction when the operation temperature is-55-150 ℃.
Optionally, the operating pressure of the light component removal tower is 1.4-2.5 Mpag, and the operating temperature is-40 ℃.
By adopting the technical scheme, the operating pressure of the light component removal tower is 1.4-2.5 Mpag, and the operating temperature is-40 ℃. Is favorable for removing light component impurities.
Optionally, the operating pressure of the product tower is 1.4-2.5 Mpag, and the operating temperature is-60-100 ℃.
By adopting the technical scheme, the operating pressure of the product tower is 1.4-2.5 Mpag, the operating temperature is-60-100 ℃, and the high-purity electronic grade monosilane electron special gas is obtained by rectification.
In summary, the application has the following beneficial technical effects:
1. the silane reaction rectification process uses byproduct dichlorosilane in Siemens polysilicon production as a raw material, removes light component impurities such as hydrogen chloride and the like after passing through a purification tower, then sends the light component impurities to a reaction rectification tower, and carries out disproportionation reaction on the dichlorosilane to generate silane, trichlorosilane and silicon tetrachloride are extracted from the tower bottom of the reaction rectification tower, crude silane is extracted from the tower top of the reaction rectification tower and sent to a light removal tower, light components possibly contained in the silane are removed from the tower top of the light removal tower, a product of the tower bottom of the light removal tower is sent to a product tower, high-purity electronic grade monosilane electronic special gas is extracted from the tower top, and heavy components of the tower bottom are returned to the catalytic rectification tower for recycling, so that the economy of the Siemens polysilicon process device is improved.
2. The disproportionation reaction in the reactive rectifying tower is carried out and the reaction products are separated, so that three reactions related to the formation of silane by the disproportionation reaction of dichlorosilane in the reactive rectifying tower can be continuously carried out to the right. The reaction rectifying tower couples the common reaction kettle with the rectifying tower, so that the equipment investment is greatly reduced, in addition, the reaction conversion rate is improved, the material circulation amount is reduced, and the operation cost is reduced. The weak base resin catalyst is fully utilized, and the catalyst not only has the effect of catalyzing chemical reaction in reactive distillation, but also can serve as a filler of the first catalyst bed layer and the second catalyst bed layer. In the reactive rectifying tower, the reaction temperature is convenient to adjust, and because the heat generated by the chemical reaction is consumed by the process of separating the reaction products, and the temperature in the tower is limited by vapor-liquid equilibrium and is always the bubble point of the mixture under the system pressure, the reaction temperature can be controlled by adjusting the system pressure, so that the temperature runaway is effectively avoided;
3. the silane generated by the disproportionation reaction of the dichlorosilane is primarily separated by a reactive rectifying tower, light component impurities are removed by a purifying tower, and finally the silane is further purified by a product tower, and finally the obtained silane is 8N-grade high-purity electronic grade monosilane electron special gas.
Drawings
Fig. 1 is a schematic structural view of an embodiment of the present application.
Reference numerals illustrate:
1. a purifying tower; 11. a raw material pump; 12. a condenser; 2. a reactive rectifying tower; 21. a first catalyst bed; 22. a second catalyst bed; 23. a partition plate; 24. structured packing; 3. a light component removing tower; 4. a product tower; 5. an intermediate condenser; 6. crude silane compressor.
Detailed Description
The present application will be described in further detail below.
The embodiment of the application discloses a silane reaction rectification system.
Referring to fig. 1, including purification tower 1, reaction rectifying column 2, light ends removal tower 3 and product tower 4 that communicate in proper order and install, purification tower 1, reaction rectifying column 2, light ends removal tower 3 and product tower 4 all are tower cauldron form, install the transportation pipeline between purification tower 1, reaction rectifying column 2, light ends removal tower 3 and the product tower 4, purification tower 1, reaction rectifying column 2, light ends removal tower 3 and product tower 4 are through transportation pipeline intercommunication.
Referring to fig. 1, a purification tower 1 is communicated with a raw material pump 11 for pumping dichlorosilane raw materials, a condenser 12 is installed at the top of the purification tower 1, the condenser 12 is fixedly connected with the purification tower 1 through a flange, the top of the purification tower 1 is communicated with the outside of a system through a pipeline, and the bottom discharge end of the purification tower 1 is communicated with the upper section feed inlet of a reactive distillation tower 2 through a conveying pipeline.
Referring to fig. 1, the upper section of the reactive rectifying column 2 is filled with a first catalyst bed 21 and a second catalyst bed 22, a partition plate 23 is fixedly installed between the first catalyst bed 21 and the second catalyst bed 22, and the partition plate 23 completely separates the first catalyst bed 21 and the second catalyst bed 22. In the embodiment of the present application, the heights of the first catalyst bed 21 and the second catalyst bed 22 are 5 m. The first catalyst bed 21 and the second catalyst bed 22 are filled with a weak base-based resin catalyst to realize the disproportionation reaction of dichlorosilane to generate silane. In the embodiment of the application, the weak base resin catalyst adopts a macroporous weak base anion exchange resin with tertiary amine groups. An intermediate condenser 5 is arranged outside the reaction rectifying tower 2, the feeding end of the intermediate condenser 5 is communicated with the upper section of the reaction rectifying tower 2 near the bottom of the partition plate 23, the non-condensable gas output end of the intermediate condenser 5 is communicated with the space below the first catalyst bed 21, and the liquid phase component output end of the intermediate condenser 5 is communicated with the space above the second catalyst bed 22. The lower part of the reactive rectifying tower 2 is filled with structured packing 24 to realize the separation of heavy components in the reaction. In the present embodiment, the structured packing 24 is a CY700 structured packing and its equivalent. The bottom of the reaction rectifying tower 2 is a heavy component discharge end, and the bottom of the reaction rectifying tower 2 is communicated with the outside of the system through a pipeline.
Referring to fig. 1, a top discharge end of a reactive distillation column 2 is communicated with a column bottom feed inlet of a light component removal column 3 through a conveying pipeline, a crude silane compressor 6 is installed between the reactive distillation column 2 and the light component removal column 3, an input end of the crude silane compressor 6 is communicated with the reactive distillation column 2, and an output end of the crude silane compressor 6 is communicated with the feed inlet of the light component removal column 3. The bottom discharge end of the light component removing tower 3 is communicated with the tower kettle feed inlet of the product tower 4 through a conveying pipeline, and the top of the light component removing tower 3 is communicated with the outside of the system through a pipeline. The product tower 4 is a packed tower and comprises two sections of structured packing, wherein the height of each section of structured packing is 5m, and the packing model is CY700 structured packing and the packing equivalent to the CY700 structured packing.
And the silane product is extracted from the top of the product tower 4, and the bottom of the product tower 4 is communicated with the upper section feed inlet of the reactive rectifying tower 2 through a conveying pipeline.
Embodiments 1-3 of the present application disclose a silane production process suitable for use in a silane production system as described above.
Example 1
A silane production process suitable for use in a silane production system as described above, comprising the steps of:
a silane production process suitable for use in a silane production system as described above, comprising the steps of: the raw material of dichlorosilane from upstream was fed to the purification column 1 through the raw material pump 11, and the concentration of dichlorosilane from upstream was 90% by weight.
The operating pressure of the purification column 1 was 1.0Mpag and the operating temperature was 55 ℃. The operating temperature of the condenser 12 at the top of the purification column 1 was 50 ℃. The light component impurities are removed by the purification tower 1, the light component impurities are sent to an upstream device outside the system by the tower top of the purification tower 1, and the high-purity dichlorosilane is obtained after the light component impurities are removed by the purification tower 1, wherein the concentration of the dichlorosilane is 99.99wt%.
The dichlorosilane at the bottom of the purification column 1 was fed into the space above the second catalyst bed 22 of the reactive distillation column 2, the operating pressure of the reactive distillation column 2 was 1.0Mpag, and the operating temperature was-55 ℃.
The gas phase component in the space above the second catalyst bed 22 is sent to the intermediate condenser 5 for condensation at a condensation temperature of-65 ℃. The liquid phase component condensed by the intermediate condenser 5 returns to the space above the second catalyst bed 22, noncondensable gas is conveyed to the space below the first catalyst bed 21, dichlorosilane is subjected to disproportionation reaction in the reactive distillation column 2 to generate silane, crude silane is extracted from the top of the reactive distillation column 2, trichlorosilane and silicon tetrachloride are extracted from the bottom of the reactive distillation column 2 and conveyed to the outside of the system, the concentration of the trichlorosilane is 92wt%, and the concentration of the silicon tetrachloride is 8wt%.
Crude silane was taken out from the top of the reactive rectifying column 2, and in the crude silane, 35wt% of silane, 64.91wt% of trichlorosilane and the other 0.09wt% were taken out. The crude silane was pressurized by the compressor crude silane compressor 6 to a crude silane pressure of 1.4Mpa and fed to the light ends removal column 3, the operating pressure of the light ends removal column 3 being 2.5Mpa and the operating temperature being-40 ℃. Light component impurities in the crude silane are removed at the top of the light component removal column 3.
The liquid phase component of the tower bottom of the light component removing tower 3 is distributed to a product tower 4, and the liquid phase component of the tower bottom of the light component removing tower 3 comprises 80 weight percent of silane and 20 weight percent of monochloro-silicon. The operating pressure of the product column 4 was 1.4Mpa and the operating temperature was 100 ℃. The product tower 4 further separates the tower kettle liquid phase component of the light component removal tower 3, and the heavy component of the tower kettle of the product tower 4 is returned to the reactive distillation tower 2 for recycling, wherein the heavy component of the tower kettle comprises 12wt% of silane, 87.92wt% of trichlorosilane and 0.08wt% of other components. Electronic grade monosilane electron special gas is extracted from the top of the product tower 4, and the grade of the electronic grade monosilane electron special gas is 8N.
Example 2
A silane production process suitable for use in a silane production system as described above, comprising the steps of:
a silane production process suitable for use in a silane production system as described above, comprising the steps of: the raw material of dichlorosilane from upstream was fed to the purification column 1 through the raw material pump 11, and the concentration of dichlorosilane from upstream was 95% by weight.
The operating pressure of the purification column 1 was 0.50Mpa and the operating temperature was 75 ℃. The operating temperature of the condenser 12 at the top of the purification column 1 was 55 ℃. The light component impurities are removed by the purification tower 1, the light component impurities are sent to an upstream device outside the system by the tower top of the purification tower 1, and the high-purity dichlorosilane is obtained after the light component impurities are removed by the purification tower 1, wherein the concentration of the dichlorosilane is 99.95 weight percent.
The dichlorosilane at the bottom of the purification column 1 was fed into the space above the second catalyst bed 22 of the reactive distillation column 2, and the reactive distillation column 2 was operated at a pressure of 0.50Mpa and a temperature of 100 ℃.
The gas phase component in the space above the second catalyst bed 22 is sent to the intermediate condenser 5 for condensation at a condensation temperature of-20 ℃. The liquid phase component condensed by the intermediate condenser 5 returns to the space above the second catalyst bed 22, noncondensable gas is conveyed to the space below the first catalyst bed 21, dichlorosilane is subjected to disproportionation reaction in the reactive distillation column 2 to generate silane, crude silane is extracted from the top of the reactive distillation column 2, trichlorosilane and silicon tetrachloride are extracted from the bottom of the reactive distillation column 2 and conveyed to the outside of the system, the concentration of the trichlorosilane is 95wt%, and the concentration of the silicon tetrachloride is 5wt%.
Crude silane was taken out from the top of the reactive rectifying column 2, and of the crude silane, silane 60.91wt%, trichlorosilane 39.04wt% and the other 0.05wt% were obtained. The crude silane was pressurized by the compressor crude silane compressor 6 to a crude silane pressure of 2Mpag and then sent to the light ends removal column 3, the operating pressure of the light ends removal column 3 was 2.00Mpag and the operating temperature was 0 ℃. Light component impurities in the crude silane are removed at the top of the light component removal column 3.
The liquid phase component of the tower bottom of the light component removing tower 3 is distributed to a product tower 4, and the liquid phase component of the tower bottom of the light component removing tower 3 comprises 60 weight percent of silane and 40 weight percent of monochloro-silicon. The operating pressure of the product column 4 was 2Mpag and the operating temperature was 20 ℃. The product tower 4 further separates the tower kettle liquid phase component of the light component removal tower 3, and the heavy component of the tower kettle of the product tower 4 is returned to the reactive distillation tower 2 for recycling, wherein the heavy component of the tower kettle comprises 7.85 weight percent of silane, 92.09 weight percent of silicon monochloride and the other 0.06 weight percent. Electronic grade monosilane electron special gas is extracted from the top of the product tower 4, and the grade of the electronic grade monosilane electron special gas is 8N.
Example 3
A silane production process suitable for use in a silane production system as described above, comprising the steps of:
a silane production process suitable for use in a silane production system as described above, comprising the steps of: the raw material of dichlorosilane from upstream was fed to the purification column 1 through the raw material pump 11, and the concentration of dichlorosilane from upstream was 99wt%.
The operating pressure of the purification column 1 was 0.25Mpa and the operating temperature was 100 ℃. The operating temperature of the condenser 12 at the top of the purification column 1 was 60 ℃. The light component impurities are removed by the purification tower 1, the light component impurities are sent to an upstream device outside the system by the tower top of the purification tower 1, and the high-purity dichlorosilane is obtained after the light component impurities are removed by the purification tower 1, wherein the concentration of the dichlorosilane is 99.91 weight percent.
The dichlorosilane at the bottom of the purification column 1 was fed into the space above the second catalyst bed 22 of the reactive distillation column 2, and the reactive distillation column 2 was operated at a pressure of 0.25Mpa and a temperature of 150 ℃.
The gas phase component in the space above the second catalyst bed 22 is sent to the intermediate condenser 5 to be condensed at a condensing temperature of 30 ℃. The liquid phase component condensed by the intermediate condenser 5 returns to the space above the second catalyst bed 22, noncondensable gas is conveyed to the space below the first catalyst bed 21, dichlorosilane is subjected to disproportionation reaction in the reactive distillation column 2 to generate silane, crude silane is extracted from the top of the reactive distillation column 2, trichlorosilane and silicon tetrachloride are extracted from the bottom of the reactive distillation column 2 and conveyed to the outside of the system, the concentration of the trichlorosilane is 99wt%, and the concentration of the silicon tetrachloride is 1wt%.
Crude silane was taken out from the top of the reactive rectifying column 2, and in the crude silane, 79.52wt% of silane, 20wt% of monochloro-hydrosilicon and the other 0.08wt% were taken out. The crude silane was pressurized by the compressor crude silane compressor 6 to a crude silane pressure of 2.5Mpa and fed to the light ends column 3, the operating pressure of the light ends column 3 being 1.4Mpa and the operating temperature being 40 ℃. Light component impurities in the crude silane are removed at the top of the light component removal column 3.
The liquid phase component of the tower bottom of the light component removing tower 3 is distributed to a product tower 4, and the liquid phase component of the tower bottom of the light component removing tower 3 comprises 35 weight percent of silane and 65 weight percent of monochloro-silicon. The operating pressure of the product column 4 was 2.5Mpag and the operating temperature was-60 ℃. The product tower 4 further separates the tower kettle liquid phase component of the light component removal tower 3, and the heavy component of the tower kettle of the product tower 4 is returned to the reactive distillation tower 2 for recycling, wherein the heavy component of the tower kettle comprises 15wt% of silane, 84.99wt% of silicon monochloride and 0.01wt% of the other components. Electronic grade monosilane electron special gas is extracted from the top of the product tower 4, and the grade of the electronic grade monosilane electron special gas is 8N.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (10)
1. A silane reactive distillation system, characterized by: comprises a purifying tower (1), a reactive rectifying tower (2), a light component removing tower (3) and a product tower which are sequentially communicated; the purifying tower (1) is communicated with a raw material pump (11) for pumping dichlorosilane raw material, and the bottom discharge end of the purifying tower (1) is communicated with the upper section feed inlet of the reactive rectifying tower (2); the top discharge end of the reaction rectifying tower (2) is communicated with a tower kettle feed inlet of the light component removing tower (3), the bottom discharge end of the light component removing tower (3) is communicated with a tower kettle feed inlet of the product tower (4), electronic grade monosilane electronic special gas is extracted from the top of the product tower (4), and the bottom of the product tower (4) is communicated with an upper section feed inlet of the reaction rectifying tower (2); the reaction rectifying tower (2) upper segment is filled with first catalyst bed (21) and second catalyst bed (22), is provided with baffle (23) between first catalyst bed (21) and second catalyst bed (22), first catalyst bed (21) and second catalyst bed (22) all are filled with weak base resin catalyst to realize dichloro dihydro silicon disproportionation reaction and produce silane.
2. A silane reactive distillation system according to claim 1, wherein: the lower part of the reaction rectifying tower (2) is filled with a structured packing (24) to realize the separation of heavy components in the reaction, and the bottom of the reaction rectifying tower (2) is a heavy component discharge end.
3. A silane reactive distillation system according to claim 1, wherein: the top of the purification tower (1) is provided with a condenser (12).
4. A silane reactive distillation system according to claim 1, wherein: the reaction rectifying tower (2) is externally provided with an intermediate condenser (5), the feeding end of the intermediate condenser (5) is communicated with the position, close to the bottom of the partition plate (23), of the upper section of the reaction rectifying tower (2), the non-condensable gas output end of the intermediate condenser (5) is communicated with the space below the first catalyst bed (21), and the liquid phase component output end of the intermediate condenser (5) is communicated with the space above the second catalyst bed (22).
5. A silane reactive distillation system according to claim 1, wherein: a crude silane compressor (6) is arranged between the reaction rectifying tower (2) and the light component removing tower (3), the input end of the crude silane compressor (6) is communicated with the reaction rectifying tower (2), and the output end of the crude silane compressor (6) is communicated with the feed inlet of the light component removing tower (3).
6. A silane production process suitable for use in a silane production system as claimed in any one of claims 1 to 5, characterized in that: the method comprises the following steps:
the method comprises the steps that dichlorosilane raw materials from the upstream are sent to a purification tower (1) through a raw material pump (11), light component impurities are removed through the purification tower (1), and the light component impurities are sent to an upstream device through the top of the purification tower (1);
delivering dichlorosilane at the tower bottom of the purification tower (1) to the upper space of a second catalyst bed layer (22) of the reaction rectifying tower (2), delivering gas phase components in the upper space of the second catalyst bed layer (22) to an intermediate condenser (5) for condensation, returning liquid phase components condensed by the intermediate condenser (5) to the upper space of the second catalyst bed layer (22), delivering noncondensable gas to the lower space of a first catalyst bed layer (21), performing disproportionation reaction on dichlorosilane in the reaction rectifying tower (2) to generate silane, extracting crude silane at the tower top of the reaction rectifying tower (2), and delivering trichlorosilane and silicon tetrachloride to the outside of the system;
crude silane extracted from the top of a reactive rectifying tower (2) is pressurized to the pressure of 1.4-2.5 Mpag by a compressor crude silane compressor (6) and then is sent to a light component removing tower (3), and light component impurities in the crude silane are removed from the top of the light component removing tower (3);
distributing a tower kettle liquid phase component of the light component removal tower (3) to a product tower (4), extracting electronic grade monosilane electronic special gas from the tower top of the product tower (4), and returning heavy components of the tower kettle of the product tower (4) to the reaction rectifying tower (2) for recycling;
the concentration of the dichlorosilane from upstream is 90wt% to 99wt%.
7. The process for reactive distillation of silane according to claim 6 wherein: the operating pressure of the purifying column (1) is 0.25-1.0 Mpag, and the operating temperature is 55-100 ℃.
8. The process for reactive distillation of silane according to claim 6 wherein: the operating pressure of the reactive rectifying tower (2) is 0.25-1.0 Mpag, and the operating temperature is-55-150 ℃.
9. The process for reactive distillation of silane according to claim 6 wherein: the operating pressure of the light component removing tower (3) is 1.4-2.5 Mpag, and the operating temperature is-40 ℃.
10. The process for reactive distillation of silane according to claim 6 wherein: the operating pressure of the product tower (4) is 1.4-2.5 Mpag, and the operating temperature is-60-100 ℃.
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