CN112028926B - Separation device and separation method for removing silicon tetrachloride in organosilicon monomer azeotrope - Google Patents
Separation device and separation method for removing silicon tetrachloride in organosilicon monomer azeotrope Download PDFInfo
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- CN112028926B CN112028926B CN201910477294.XA CN201910477294A CN112028926B CN 112028926 B CN112028926 B CN 112028926B CN 201910477294 A CN201910477294 A CN 201910477294A CN 112028926 B CN112028926 B CN 112028926B
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- 238000000926 separation method Methods 0.000 title claims abstract description 196
- 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 title claims abstract description 72
- 239000000178 monomer Substances 0.000 title claims abstract description 72
- 239000005049 silicon tetrachloride Substances 0.000 title claims abstract description 72
- IJOOHPMOJXWVHK-UHFFFAOYSA-N trimethylsilyl-trifluoromethansulfonate Natural products C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 80
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 49
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 9
- 239000010703 silicon Substances 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 63
- 238000009835 boiling Methods 0.000 description 22
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 19
- 239000005051 trimethylchlorosilane Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 150000001412 amines Chemical group 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- 229920005591 polysilicon Polymers 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- -1 methyl hydrogen Chemical compound 0.000 description 3
- 239000005055 methyl trichlorosilane Substances 0.000 description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 150000001367 organochlorosilanes Chemical class 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a separation device and a separation method for removing silicon tetrachloride in an organosilicon monomer azeotrope, wherein the separation device comprises the following components: a first separation column for separating the organosilicon monomer azeotrope; the fixed bed reactor is connected with the top of the first separation tower, and the material at the top of the first separation tower flows into the fixed bed reactor to react with the dichlorosilane product under the catalysis of the catalyst to generate the trichlorosilane through the anti-disproportionation reaction; and the second separation tower is connected with the fixed bed reactor and is used for separating materials flowing out of the fixed bed reactor, a trimethyl monochlorosilane product is obtained at the tower bottom of the second separation tower, and a dichlorosilane product is obtained at the tower top of the second separation tower. The method can greatly reduce the load of a rectifying device in the prior art, remove the silicon tetrachloride azeotrope in the organic silicon monomer azeotrope, and convert the silicon tetrachloride into trichlorosilane.
Description
Technical Field
The invention belongs to the technical field of separation of organochlorosilane monomers, and particularly relates to a separation device and a separation method for removing silicon tetrachloride in an organosilicon monomer azeotrope.
Background
The organosilicon compound generally refers to a compound containing Si-C bonds, and the polymer has a plurality of excellent properties due to the properties of inorganic materials and organic materials, so that the organosilicon compound is widely applied to various industries such as electronics and electrics, construction, chemical industry, textile, light industry, medical treatment and the like, and is called as industrial monosodium glutamate. And organosilicon monomers are important in the organosilicon industry as starting materials for the production of organosilicon polymers. Methyl chlorosilane mainly refers to methyl hydrogen-containing dichlorosilane, methyl trichlorosilane, dimethyl dichlorosilane and trimethyl monochlorosilane, and is used as an important organic silicon monomer, and the purity of the separated product plays an important role in the processing of subsequent products.
Regardless of the method used to produce the organochlorosilanes, multicomponent mixed products are obtained, with direct products being particularly complex. In particular, when synthesizing methyl chlorosilane, the components are more, the boiling point difference is small, and the separation and purification are quite difficult. However, in order to prepare polysiloxane products, monomers with different functional groups of higher purity are required to be used as raw materials, so that separation and purification of methylchlorosilanes are important in the organosilicon industry and the investment ratio thereof.
At present, the crude product of methyl chlorosilane monomer is synthesized by a direct method in industry, and according to data, the raw product is reported to have 41 components, and low-boiling-point substances and chloromethane are removed through preliminary separation and then enter a separation process. In fact, the method is not necessary to separate each product component one by one in the downstream industry, and the main purpose of separating and mixing methylchlorosilane is to extract as many products with high purity such as dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, dimethylhydrogen-containing chlorosilane, silicon tetrachloride and high-boiling substances as possible, and the requirements on the purity of the methylchlorosilane with various different functionalities mainly depend on the actual requirements of polysiloxane production. In the industry of producing methyl chlorosilane monomer by a direct method, because of the restriction of factors such as a catalyst, process conditions and the like, silicon tetrachloride and trimethyl monochlorosilane which are byproducts in a crude product of the monomer are relatively close in boiling point (the boiling point of the trimethyl monochlorosilane is 57.9 ℃,101KPa and the boiling point of the silicon tetrachloride is 57.6 ℃, and 101 KPa) except for methyl chlorosilane which is a target product, and an azeotrope is easy to form. In addition to the small difference in boiling points between components, the difficulty in separating and purifying methyl chlorosilane mainly has the problem of azeotropy between trimethyl monochlorosilane and methyl hydrosilane and silicon tetrachloride (the boiling point of trimethyl monochlorosilane is 57.9 ℃ and 101KPa; the boiling point of silicon tetrachloride is 57.6 ℃ and 101 KPa), so that the purity of the separated product cannot meet the expected requirement, and meanwhile, in the hydrolysis process, silicon tetrachloride reacts with water to produce solid matters of silicon dioxide, and adverse factors such as equipment and pipeline blockage can be caused for a long time.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the separation device and the separation method for removing the silicon tetrachloride in the organic silicon monomer azeotrope, which can greatly reduce the load of a rectifying device in the prior art, remove the silicon tetrachloride azeotrope in the organic silicon monomer azeotrope and convert the silicon tetrachloride into trichlorosilane.
The technical scheme adopted for solving the technical problem of the invention is to provide a separation device for removing silicon tetrachloride in an organosilicon monomer azeotrope, wherein the direct method for synthesizing methyl chlorosilane monomer to obtain a methyl chlorosilane monomer crude product, the methyl chlorosilane monomer crude product is subjected to primary rectification to remove high-boiling substances and low-boiling substances to obtain the organosilicon monomer azeotrope, and the organosilicon monomer azeotrope comprises: trimethyl monochlorosilane, silicon tetrachloride, the separator includes:
the first separation tower is used for separating the organosilicon monomer azeotrope, a dimethyl dichlorosilane product is obtained at the tower bottom of the first separation tower, a tower top material of the first separation tower is obtained at the tower top of the first separation tower, and the tower top material of the first separation tower comprises silicon tetrachloride;
the fixed bed reactor is connected with the top of the first separation tower, the inlet of the fixed bed reactor is also used for introducing dichlorosilane, a catalyst for catalyzing the anti-disproportionation reaction of the dichlorosilane and the silicon tetrachloride to generate the trichlorosilane is arranged in the fixed bed reactor, and the material at the top of the first separation tower flows into the fixed bed reactor and contains the dichlorosilane product introduced into the fixed bed reactor, and the anti-disproportionation reaction is carried out to generate the trichlorosilane under the catalysis of the catalyst;
and the second separation tower is connected with the fixed bed reactor and is used for separating materials flowing out of the fixed bed reactor, a trimethyl monochlorosilane product is obtained at the tower bottom of the second separation tower, and a dichlorosilane product is obtained at the tower top of the second separation tower.
Preferably, the separation device for removing silicon tetrachloride in the organosilicon monomer azeotrope further comprises:
the inlet of the feed mixer is also used for introducing a product containing dichlorosilane, and the feed mixer is used for mixing the tower top material of the first separation tower with the product containing dichlorosilane.
Preferably, the top of the second separation column is connected with the inlet of the fixed bed reactor, and the dichlorosilane product separated from the top of the second separation column flows into the fixed bed reactor.
Preferably, the second separation column is provided with a side-track column plate which is used for side-track extraction of trichlorosilane products with purity of more than 99mas percent.
The invention also provides a separation method using the separation device for removing silicon tetrachloride in the organosilicon monomer azeotrope, which comprises the following steps:
separating the organosilicon monomer azeotrope through a first separation tower, obtaining a dimethyl dichlorosilane product at the tower bottom of the first separation tower, and obtaining a tower top material of the first separation tower at the tower top of the first separation tower, wherein the tower top material of the first separation tower comprises silicon tetrachloride;
introducing the tower top material of the first separation tower into a fixed bed reactor, introducing a product containing dichlorosilane into the fixed bed reactor, and performing a reverse disproportionation reaction under the catalysis of a catalyst to generate trichlorosilane;
separating the materials flowing out of the fixed bed reactor through a second separation tower, obtaining a trimethyl monochlorosilane product at the tower bottom of the second separation tower, and obtaining a dichlorosilane product at the tower top of the second separation tower.
Preferably, the pressure in the first separation column is 200 to 300Kpa, and the temperature is the saturation temperature of the organosilicon monomer azeotrope. The number of the trays of the first separation column is 100 to 110.
Preferably, the pressure in the fixed bed reactor is 200 to 350Kpa and the temperature is 80 to 100 ℃.
Preferably, the pressure in the second separation column is 350 to 450Kpa and the temperature is 55 to 60 ℃.
Preferably, the molar ratio of the dichlorosilane-containing product to the silicon tetrachloride in the overhead material of the first separation column which is fed into the fixed bed reactor is (1.1 to 1.25): 1.
preferably, the separation method further comprises the steps of: and introducing the dichlorosilane product separated from the top of the second separation tower into a fixed bed reactor.
Preferably, the separation method further comprises the steps of: trichlorosilane products are extracted from the side line of the side line tower plate on the second separation tower, and the tower plate number of the side line tower plate is 45-50.
Preferably, the catalyst is a basic quaternary amine-based macroporous cross-linked resin dry-based catalyst and/or an anionic resin. The diameter of the catalyst is 0.5-1.5 mm, the bulk density is 0.30-0.50 g/ml, and the wear resistance is more than 95%.
In summary, the separation device and the method for removing the silicon tetrachloride in the organic silicon monomer azeotrope use dichlorosilane to remove the azeotropic silicon tetrachloride in the organic silicon monomer, and propose a new process route and device equipment, so that the load of a rectifying device in the prior art can be greatly reduced, the silicon tetrachloride in the organic silicon monomer azeotrope is removed, the silicon tetrachloride is converted into trichlorosilane, the difference of boiling points between the trichlorosilane and the trimethylchlorosilane is large, the trichlorosilane and the trimethylchlorosilane can be separated by a simple rectifying mode, the purity of the separated trimethylchlorosilane product is improved to more than 98%, the consumption of cooling water and steam of a rectifying tower in the prior art is effectively reduced, the load and energy consumption are reduced, the purity of the trimethylchlorosilane is improved, the difficult problems of pipeline and equipment blockage caused by solid silicon dioxide generated in the hydrolysis process of the monomer silicon tetrachloride in the subsequent process are avoided, and the shutdown overhaul cost and the risk of the production process caused by equipment blockage are reduced.
Drawings
FIG. 1 is a schematic structural view of a separation device for removing silicon tetrachloride in an organosilicon monomer azeotrope in example 2 of the present invention.
In the figure: 1-a first separation column; a 2-fixed bed reactor; 3-a second separation column; 4-a feed mixer; 5-a first condenser; 6-a second condenser; 7-a third condenser; 8-a fourth condenser; 9-side tray.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of better understanding of the technical solution of the present invention to those skilled in the art.
Embodiments of the present patent are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary only for explaining the present patent and are not to be construed as limiting the present patent.
Example 1
The embodiment provides a separation device for removing silicon tetrachloride in an organosilicon monomer azeotrope, wherein methyl chlorosilane monomers are synthesized directly to obtain methyl chlorosilane monomer crude products, the methyl chlorosilane monomer crude products are subjected to primary rectification to remove high-boiling substances and low-boiling substances to obtain the organosilicon monomer azeotrope, and the organosilicon monomer azeotrope comprises: trimethyl monochlorosilane, silicon tetrachloride, the separator includes:
the first separation tower is used for separating the organosilicon monomer azeotrope, a dimethyl dichlorosilane product is obtained at the tower bottom of the first separation tower, a tower top material of the first separation tower is obtained at the tower top of the first separation tower, and the tower top material of the first separation tower comprises silicon tetrachloride;
the fixed bed reactor is connected with the top of the first separation tower, the inlet of the fixed bed reactor is also used for introducing dichlorosilane, a catalyst for catalyzing the anti-disproportionation reaction of the dichlorosilane and the silicon tetrachloride to generate the trichlorosilane is arranged in the fixed bed reactor, and the material at the top of the first separation tower flows into the fixed bed reactor and contains the dichlorosilane product introduced into the fixed bed reactor, and the anti-disproportionation reaction is carried out to generate the trichlorosilane under the catalysis of the catalyst;
and the second separation tower is connected with the fixed bed reactor and is used for separating materials flowing out of the fixed bed reactor, a trimethyl monochlorosilane product is obtained at the tower bottom of the second separation tower, and a dichlorosilane product is obtained at the tower top of the second separation tower.
The embodiment also provides a separation method using the separation device for removing silicon tetrachloride in the organosilicon monomer azeotrope, which comprises the following steps:
separating the organosilicon monomer azeotrope through a first separation tower, obtaining a dimethyl dichlorosilane product at the tower bottom of the first separation tower, and obtaining a tower top material of the first separation tower at the tower top of the first separation tower, wherein the tower top material of the first separation tower comprises silicon tetrachloride;
introducing the tower top material of the first separation tower into a fixed bed reactor, introducing a product containing dichlorosilane into the fixed bed reactor, and performing a reverse disproportionation reaction under the catalysis of a catalyst to generate trichlorosilane;
separating the materials flowing out of the fixed bed reactor through a second separation tower, obtaining a trimethyl monochlorosilane product at the tower bottom of the second separation tower, and obtaining a dichlorosilane product at the tower top of the second separation tower.
According to the separation device and the separation method for removing the silicon tetrachloride in the organosilicon monomer azeotrope, the dichlorosilane is used for removing the azeotropic silicon tetrachloride in the organosilicon monomer, a new process route and device equipment are provided, the load of a rectifying device in the prior art can be greatly reduced, the silicon tetrachloride azeotrope with the content of 20-30 mas% in the organosilicon monomer azeotrope is removed, the silicon tetrachloride is converted into the trichlorosilane, the difference between the boiling points of the trichlorosilane and the trimethylchlorosilane is large, the trichlorosilane and the trimethylchlorosilane can be separated in a simple rectifying manner, the purity of a separated trimethylchlorosilane product is improved to more than 98%, the consumption of cooling water and steam of a rectifying tower in the prior art is effectively reduced, the load and the energy consumption are reduced, the purity of the trimethylchlorosilane is improved, the difficult problems of pipeline and equipment blockage caused by solid silicon dioxide generated in the monomer hydrolysis process in the subsequent process are avoided, and the overhaul cost caused by equipment blockage and the risk of the production process are reduced.
Example 2
As shown in fig. 1, this embodiment provides a separation device for removing silicon tetrachloride in an organosilicon monomer azeotrope, the direct method synthesizes methyl chlorosilane monomer to obtain a methyl chlorosilane monomer crude product, the methyl chlorosilane monomer crude product is subjected to primary rectification separation, high-boiling substances and low-boiling substances are removed, and the organosilicon monomer azeotrope is obtained, and mainly includes: trimethyl monochlorosilane, silicon tetrachloride, separator includes:
the first separation tower 1 is used for separating the organosilicon monomer azeotrope, a dimethyl dichlorosilane product with the content of more than 99mas percent is obtained at the tower bottom of the first separation tower 1, a tower top material of the first separation tower 1 is obtained at the tower top of the first separation tower 1, and the tower top material of the first separation tower 1 comprises silicon tetrachloride;
the fixed bed reactor 2 is connected with the top of the first separation tower 1, the inlet of the fixed bed reactor 2 is also used for introducing dichlorosilane, a catalyst for catalyzing the anti-disproportionation reaction of the dichlorosilane and the silicon tetrachloride to generate the trichlorosilane is arranged in the fixed bed reactor 2, and the material at the top of the first separation tower 1 flows into the fixed bed reactor 2 and the product containing the dichlorosilane introduced into the fixed bed reactor 2, and the anti-disproportionation reaction is carried out under the catalytic action of the catalyst to generate the trichlorosilane; specifically, the fixed bed reactor 2 in this example had a capacity of 8 cubic meters per bed, a diameter of 1.5 meters and a height of 6 meters, and was internally filled with an alkaline quaternary amine-based macroporous crosslinked resin (available from Tianjin university, a catalyst used in this example, and manufactured by a large number of domestic enterprises).
The second separation tower 3 is connected with the fixed bed reactor 2, the second separation tower 3 is used for separating materials flowing out of the fixed bed reactor 2, a trimethyl monochlorosilane product with purity higher than 98mas percent is obtained at the tower bottom of the second separation tower 3, and a dichlorosilane product with purity not lower than 99mas percent is obtained at the tower top of the second separation tower 3.
Specifically, the fixed bed reactor 2 in the present embodiment is also provided with a temperature detector for monitoring temperature, a pressure detector for monitoring pressure. The solid bed reactor is divided into two sets, wherein one set is used, and the other set is standby, so that the maintenance and the switching are convenient.
It should be noted that, the separation device for removing silicon tetrachloride in the organosilicon monomer azeotrope in this embodiment further includes:
the feed mixer 4 is arranged between the first separation tower 1 and the fixed bed reactor 2, the inlet of the feed mixer 4 is connected with the top of the first separation tower 1, the outlet of the feed mixer 4 is connected with the fixed bed reactor 2, the inlet of the feed mixer 4 is also used for introducing the product containing dichlorosilane, and the feed mixer 4 is used for mixing the top material of the first separation tower 1 with the product containing dichlorosilane. Specifically, the outsourced byproduct dichlorosilane product of the polysilicon production process is stored in a tank area, is conveyed to a feed mixer 4 through a pump to be fully mixed with the tower top material of the first separation tower 1, and is fed into the fixed bed reactor 2 through the inlet at the bottom of the fixed bed reactor 2. If the method is an enterprise with the production capacity of polysilicon and organic silicon, the byproduct dichlorosilane of polysilicon can be directly utilized.
It should be noted that, the separation device for removing silicon tetrachloride in the organosilicon monomer azeotrope in this embodiment further includes:
the first condenser 5 is connected with the top of the first separation tower 1, after the material at the top of the first separation tower 1 is condensed by the first condenser 5, one part of the material is used as reflux liquid of the first separation tower 1 to maintain the balance of the tower, and the other part of the material is introduced into the feed mixer 4 to be mixed;
the second condenser 6 is connected with the tower bottom of the first separation tower 1, and the second condenser 6 is used for condensing tower bottom liquid of the first separation tower 1;
the third condenser 7 is connected with the top of the second separation tower 3, after the material at the top of the second separation tower 3 is condensed by the third condenser 7, one part of the material is used as reflux liquid of the second separation tower 3 to maintain the balance of the tower, and the other part of the material is introduced into the feed mixer 4 to be mixed;
and the fourth condenser 8 is connected with the tower kettle of the second separation tower 3, and the fourth condenser 8 is used for condensing tower kettle liquid of the second separation tower 3.
In this embodiment, the top of the second separation column 3 is connected to the inlet of the fixed bed reactor 2, and the dichlorosilane product separated from the top of the second separation column 3 flows into the fixed bed reactor 2.
In this embodiment, a side-line tray 9 is disposed on the second separation column 3, and the side-line tray 9 is used for side-line extracting trichlorosilane product with purity of more than 99 mas%.
The embodiment also provides a separation method using the separation device for removing silicon tetrachloride in the organosilicon monomer azeotrope, which comprises the following steps:
(1) The organosilicon monomer azeotrope is separated by a first separation column 1. The organosilicon monomer azeotrope mainly comprises trimethyl monochlorosilane and silicon tetrachloride and also comprises a small amount of dimethyl dichlorosilane, wherein the ratio of the trimethyl monochlorosilane is 60-75 mas, the ratio of the silicon tetrachloride is 20-30 mas, the pressure in the first separation tower 1 is 300Kpa, and the temperature is the saturation temperature of the organosilicon monomer azeotrope. The top temperature of the first separation column 1 is the saturation temperature of the corresponding mixture. The number of trays of the first separation column 1 was 105. And obtaining a dimethyl dichlorosilane product with the content of more than 99mas% at the tower bottom of the first separation tower 1, and obtaining a tower top material of the first separation tower 1 at the tower top of the first separation tower 1, wherein the tower top material of the first separation tower 1 comprises silicon tetrachloride, and the content of trichlorosilane is 60-75 mas%.
(2) The tower top material of the first separation tower 1 is introduced into a feed mixer 4, and the outsourced byproduct dichlorosilane product in the polysilicon production process is stored in a tank area and is conveyed to the feed mixer 4 through a pump to be fully mixed with the tower top material of the first separation tower 1. The dichlorosilane product separated off at the top of the second separation column 3 is also passed into a feed mixer 4. The temperature in the feed mixer 4 was 50℃and the pressure was 5bar. The mixed material in the feed mixer 4 is then introduced into the fixed bed reactor 2. In this example, the molar ratio of the dichlorosilane-containing product introduced into the fixed bed reactor 2 to the silicon tetrachloride in the overhead mass of the first separation column 1 was 1.1:1, under the catalysis of a catalyst, performing an inverse disproportionation reaction to generate trichlorosilane; the pressure in the fixed bed reactor 2 in this example was 350Kpa and the temperature was 80 c, liquid feed. The reaction conversion rate of the silicon tetrachloride and the dichlorosilane is more than 97 percent. Preferably, the catalyst is a basic quaternary amine-based macroporous cross-linked resin (free amine-based anion exchange resin) dry-based catalyst and/or an anionic resin. Specifically, the catalyst in this embodiment is a dry-based catalyst of a basic quaternary amine-based macroporous crosslinked resin (free amine-based anion exchange resin). The diameter of the catalyst is 0.5-1.5 mm, the bulk density is 0.30-0.50 g/ml, and the wear resistance is more than 95%. After conversion in the fixed bed reactor 2, the material flowing out of the fixed bed reactor 2 comprises: trichlorosilane, dichlorosilane and trimethylchlorosilane, wherein the ratio of the trichlorosilane is 20-30 mas, the ratio of the dichlorosilane is 10-15 mas, and the balance is trimethylchlorosilane.
(3) The material flowing out of the fixed bed reactor 2 was separated by the second separation column 3, and the pressure in the second separation column 3 in this example was 400Kpa and the temperature was 57 ℃. In the fixed bed reactor 2, silicon tetrachloride and dichlorosilane react to generate trichlorosilane, the boiling point of the trichlorosilane at the standard atmospheric pressure is 31.8 ℃, the boiling point of the dichlorosilane is 8.2 ℃, the boiling point difference between the trichlorosilane and the trimethylchlorosilane is about 25 ℃, and the trichlorosilane can be separated through a simple second separation tower 3. And (3) obtaining a trimethyl monochlorosilane product with purity higher than 98mas% at the tower bottom of the second separation tower 3, obtaining a dichlorosilane product with purity not lower than 99mas% at the tower top of the second separation tower 3, and continuously introducing the dichlorosilane product separated from the tower top of the second separation tower 3 into the fixed bed reactor 2 to continuously participate in the reaction. Trichlorosilane products with purity of more than 99mas% are laterally extracted through a lateral line plate 9 on the second separation tower 3, and the number of the lateral line plate 9 is 50 th piece. Trichlorosilane products are used as raw materials for preparing silane coupling agents, and can also be used for producing chloropropyl trichlorosilane, vinyl trichlorosilane and phenyl trichlorosilane products
According to the separation device and the separation method for removing the silicon tetrachloride in the organosilicon monomer azeotrope, the dichlorosilane is used for removing the azeotropic silicon tetrachloride in the organosilicon monomer, a new process route and device equipment are provided, the load of a rectifying device in the prior art can be greatly reduced, the silicon tetrachloride azeotrope with the content of 20-30 mas% in the organosilicon monomer azeotrope is removed, the silicon tetrachloride is converted into the trichlorosilane, the difference between the boiling points of the trichlorosilane and the trimethylchlorosilane is large, the trichlorosilane and the trimethylchlorosilane can be separated in a simple rectifying manner, the purity of a separated trimethylchlorosilane product is improved to more than 98%, the consumption of cooling water and steam of a rectifying tower in the prior art is effectively reduced, the load and the energy consumption are reduced, the purity of the trimethylchlorosilane is improved, the difficult problems of pipeline and equipment blockage caused by solid silicon dioxide generated in the monomer hydrolysis process in the subsequent process are avoided, and the overhaul cost caused by equipment blockage and the risk of the production process are reduced. The method in the embodiment can simultaneously solve the problem of difficult treatment of the byproduct dichlorosilane of the polysilicon in the production of the polysilicon and the organosilicon, and simultaneously solve the problem of difficult treatment of the azeotropic silicon tetrachloride in the production of the organosilicon. The device in the embodiment relates to a process flow without adding movable equipment, and has low equipment failure rate, small investment and long service life.
Example 3
Boiling point of trimethylchlorosilane: 57.9 ℃,101KPa; the boiling point of the silicon tetrachloride is 57.6 ℃ and 101KPa; in the prior art, the mixture of the two substances cannot be effectively separated through common rectification. Feeding the methyl chlorosilane monomer crude product synthesized by a direct method into a first-stage high-removal tower to remove high-boiling-point multicomponent compounds mainly comprising silicon bonds, silicon-oxygen bonds and the like; condensing the tower top product, sending the condensed product to a secondary low-pressure removing tower, rectifying to remove low-boiling-point multi-component compounds consisting of chloromethane, silicon tetrachloride, trimethyl monochlorosilane and monomethyl hydrogen dichlorosilane, and continuously sending the multi-component compounds to a subsequent light separation tower for separation; the product obtained from the tower bottom is continuously sent to a three-stage separation tower, the high-purity dimethyl dichlorosilane product (with the weight ratio of more than 99.5 percent) is obtained from the tower bottom, and the light component obtained from the tower top is sent to the downstream white carbon black for treatment; and continuously conveying the product obtained from the top of the secondary stripping tower to a light component separation tower, obtaining a product with the methyl trichlorosilane as a main component at the top of the light component separation tower, and obtaining an organosilicon monomer azeotrope at the bottom of the light component separation tower, wherein the organosilicon monomer azeotrope uses trimethyl chlorosilane and silicon tetrachloride as main components (the silicon tetrachloride component content is 20-30% (mass fraction)).
This example also provides a separation method using the separation device for removing silicon tetrachloride in the organosilicon monomer azeotrope in example 2, which is different from the method in example 2 in that:
in the step (1), the pressure in the first separation tower is 250Kpa, and the temperature is the saturation temperature of the organosilicon monomer azeotrope. The number of trays in the first separation column was 100.
In step (2), the temperature in the feed mixer was 30℃and the pressure was 7bar.
The molar ratio of the dichlorosilane-containing product to the silicon tetrachloride in the overhead material of the first separation column, which was fed into the fixed bed reactor, was 1.15:1. the catalyst is an anionic resin.
The pressure in the fixed bed reactor was 200Kpa and the temperature was 90 ℃.
In step (3), the pressure in the second separation column was 350Kpa and the temperature was 55 ℃. The number of the side-stream trays was 45 th.
Example 4
This example also provides a separation method using the separation device for removing silicon tetrachloride in the organosilicon monomer azeotrope in example 2, which is different from the method in example 2 in that:
in the step (1), the pressure in the first separation tower is 200Kpa, and the temperature is the saturation temperature of the organosilicon monomer azeotrope. The number of trays of the first separation column was 110.
In step (2), the temperature in the feed mixer was 60℃and the pressure was 6bar.
The molar ratio of the dichlorosilane-containing product to the silicon tetrachloride in the overhead mass of the first separation column fed to the fixed bed reactor was 1.25:1.
the pressure in the fixed bed reactor was 300Kpa and the temperature was 100 ℃.
In the step (3), the pressure in the second separation column was 450Kpa and the temperature was 60 ℃. The number of the side-stream trays was 47.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Claims (8)
1. A separation method using a separation device for removing silicon tetrachloride in an organosilicon monomer azeotrope, comprising the steps of:
separating the organosilicon monomer azeotrope through a first separation tower, obtaining a dimethyldichlorosilane product at the tower bottom of the first separation tower, and obtaining a tower top material of the first separation tower at the tower top of the first separation tower, wherein the tower top material of the first separation tower comprises silicon tetrachloride, the organosilicon monomer azeotrope mainly comprises trimethyl monochlorosilane and silicon tetrachloride, and also comprises a small amount of dimethyldichlorosilane, wherein the trimethyl monochlorosilane accounts for 60-75 mas, and the silicon tetrachloride accounts for 20-30 mas;
introducing the tower top material of the first separation tower into a fixed bed reactor, introducing a product containing dichlorosilane into the fixed bed reactor, and performing a reverse disproportionation reaction under the catalysis of a catalyst to generate trichlorosilane;
separating the materials flowing out of the fixed bed reactor through a second separation tower, obtaining a trimethyl monochlorosilane product at the tower bottom of the second separation tower, and obtaining a dichlorosilane product at the tower top of the second separation tower;
the trichlorosilane product is extracted from the side line of the side line tower plate on the second separation tower,
the separation device includes:
the first separation tower is used for separating the organosilicon monomer azeotrope, a dimethyl dichlorosilane product is obtained at the tower bottom of the first separation tower, a tower top material of the first separation tower is obtained at the tower top of the first separation tower, and the tower top material of the first separation tower comprises silicon tetrachloride;
the fixed bed reactor is connected with the top of the first separation tower, the inlet of the fixed bed reactor is also used for introducing dichlorosilane, a catalyst for catalyzing the anti-disproportionation reaction of the dichlorosilane and the silicon tetrachloride to generate the trichlorosilane is arranged in the fixed bed reactor, and the material at the top of the first separation tower flows into the fixed bed reactor and contains the dichlorosilane product introduced into the fixed bed reactor, and the anti-disproportionation reaction is carried out to generate the trichlorosilane under the catalysis of the catalyst;
the second separation tower is connected with the fixed bed reactor and is used for separating materials flowing out of the fixed bed reactor, a trimethyl monochlorosilane product is obtained at the tower bottom of the second separation tower, a dichlorosilane product is obtained at the tower top of the second separation tower, a side-line tower plate is arranged on the second separation tower and is used for side-line extraction of the trichlorosilane product, wherein the pressure in the second separation tower is 350-450 Kpa, and the temperature is 55-60 ℃.
2. The separation process of claim 1 wherein the pressure in the first separation column is from 200 to 300Kpa and the temperature is the saturation temperature of the organosilicon monomer azeotrope.
3. The separation process according to claim 1, wherein the pressure in the fixed bed reactor is 200 to 350Kpa and the temperature is 80 to 100 ℃.
4. The process according to claim 1, wherein the molar ratio of silicon tetrachloride in the dichlorosilane-containing product fed to the fixed bed reactor to the overhead mass of the first separation column is from (1.1 to 1.25): 1.
5. the separation method according to claim 1, further comprising the steps of: and introducing the dichlorosilane product separated from the top of the second separation tower into a fixed bed reactor.
6. The separation method according to any one of claims 1 to 5, wherein the number of the side-stream trays is 45 to 50.
7. The separation method according to claim 1, wherein the separation device further comprises:
the inlet of the feed mixer is also used for introducing a product containing dichlorosilane, and the feed mixer is used for mixing the tower top material of the first separation tower with the product containing dichlorosilane.
8. The separation method according to claim 1, wherein the top of the second separation column is connected to the inlet of the fixed bed reactor, and the dichlorosilane product separated from the top of the second separation column flows into the fixed bed reactor.
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