CN116272684A - System and method for preparing trimethylchlorosilane - Google Patents
System and method for preparing trimethylchlorosilane Download PDFInfo
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- CN116272684A CN116272684A CN202211390367.XA CN202211390367A CN116272684A CN 116272684 A CN116272684 A CN 116272684A CN 202211390367 A CN202211390367 A CN 202211390367A CN 116272684 A CN116272684 A CN 116272684A
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000005051 trimethylchlorosilane Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 47
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000000203 mixture Substances 0.000 claims abstract description 85
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 82
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 61
- 239000000047 product Substances 0.000 claims abstract description 53
- 239000007789 gas Substances 0.000 claims abstract description 40
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 33
- 238000003860 storage Methods 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 16
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 60
- 239000007791 liquid phase Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 239000000543 intermediate Substances 0.000 description 23
- 238000011049 filling Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 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 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/123—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-halogen linkages
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to a system for preparing trimethylchlorosilane, which comprises the following components in turn: the device comprises a feeding unit, a preheating unit, a reaction unit and a light component removing unit; the feeding unit comprises a hydrogen chloride purifying device and a tetramethylsilane mixture storage tank; a preheating unit: the preheating unit comprises a preheater; the raw material tetramethylsilane mixture and hydrogen chloride gas enter a reaction unit after being preheated by a preheating unit; and (3) a reaction unit: comprises a fixed bed reactor, wherein the preheated raw materials react in a reaction unit to obtain a product; light unit: the method comprises a light component removing tower, wherein a reaction product enters the light component removing tower, and is rectified and separated to obtain a light component removing mixture containing a target product trimethylchlorosilane. On the basis of not consuming other organic silicon monomers, TMS is comprehensively utilized by utilizing hydrogen chloride gas generated by the hydrolysis of methyl chlorosilane, the TMS is converted into trimethylchlorosilane, and the content of trimethylchlorosilane in the product reaches more than 93 percent.
Description
Technical Field
The invention belongs to the technical field of methyl chlorosilane preparation, and relates to a novel process and a method for preparing trimethyl chlorosilane in the field of organic silicon.
Background
Methyl chlorosilane is an important monomer for producing organic silicon materials, and the dosage in the organic silicon industry accounts for more than 90% of the total organic silicon monomers. At present, methylchlorosilanes are prepared by adopting a direct method synthesis process in large industrial production, namely by directly reacting chloromethane with metallic silicon under the action of heating and copper catalyst. Because of the large number of reaction products obtained by the direct method, the required dimethyl dichlorosilane, trimethyl chlorosilane, monomethyl trichlorosilane, low-boiling point fraction (hereinafter referred to as a tetramethyl silane mixture) and high-boiling point fraction are obtained by rectification and separation, wherein the trimethyl chlorosilane accounts for about 1% -3% of the total product, and the trimethyl chlorosilane can be used for producing organosilicon polymers and intermediates in organosilicon synthesis reaction, can also be used as raw materials of macromolecular compound sealing agents, drying agents, dehydrators, high-temperature adhesives and resins, and is an organosilicon monomer with very wide application.
In addition, the tetramethylsilane mixture accounts for about 0.5% -1.5% of the total product, wherein the content of Tetramethylsilane (TMS) is about 30% -50%, and high-purity TMS (the content is more than or equal to 99% wt) can be used as nuclear magnetic resonance reference reagent, foaming agent and fuel auxiliary agent. However, TMS has very similar boiling points to other components in the low-boiling fraction, and purification by a rectification method requires very high theoretical plate number and operation pressure, has high energy consumption and numerous required safety measures, and is very unfavorable for industrial production. For this purpose, it is common practice for most companies to convert tetramethylsilane mixtures, monomethyltrichlorosilane and trimethylchlorosilanes or high boilers or azeotropes into dimethyldichlorosilane by disproportionation. For example, in CN113831362a, tetramethylsilane mixture, methyltrichlorosilane, trimethylchlorosilane, and the like are disproportionated to obtain dimethyldichlorosilane by reactive distillation, and the content of dimethyldichlorosilane in the finished product is about 80% -90%, but this process consumes important organosilicon monomers, such as methyltrichlorosilane and trimethylchlorosilane.
The invention provides a novel process and a method for preparing trimethylchlorosilane from tetramethylsilane mixture, and aims to comprehensively utilize TMS (methyl chlorosilane) after purifying hydrogen chloride gas generated by hydrolyzing methylchlorosilane on the basis of not consuming other organic silicon monomers, so that the trimethylchlorosilane content in the product reaches more than 93 percent.
Disclosure of Invention
The invention provides a system for preparing trimethylchlorosilane, which comprises the following components in sequence: a feeding unit, a preheating unit, a reaction unit and a light component removing unit.
1. And the feeding unit comprises a hydrogen chloride purifying device and a tetramethylsilane mixture storage tank.
The raw material hydrogen chloride gas is from a purification device 1, and the tetramethylsilane mixture is stored in a TMS storage tank 2;
specifically, the hydrogen chloride gas of the purification device is hydrogen chloride produced after the hydrolysis of methyl chlorosilane and water, the hydrogen chloride is sent to the purification device after being dehydrated and deoiled, and the purification device further carries out the dehydration and deoiling treatment on the hydrogen chloride gas.
The tetramethylsilane mixture refers to a low boiling fraction or tetramethylsilane mixture produced during the synthesis of the silicone monomer by the "direct process".
Generally, the tetramethylsilane mixture (i.e., low boiling fraction) is a mixture having a boiling point of less than 40℃and the main component is (CH) 3 ) 4 Si、CH 3 HSiCl 2 、(CH 3 ) 2 SiHCl and a small amount of silicon tetrachloride.
The tetramethylsilane mixture accounts for about 0.5% -1.5% of the total product, wherein the content of Tetramethylsilane (TMS) is about 30% -50%, but the boiling point of TMS is very close to that of other components in the low boiling point fraction, and the rectification energy consumption and cost for purification are very high.
The TMS is comprehensively utilized by utilizing the hydrogen chloride gas generated by the hydrolysis of the methylchlorosilane, and is converted into the target product trimethylchlorosilane, wherein the content of trimethylchlorosilane in the product can be more than 80 percent (even more than 93 percent), the loss of other organosilicon monomers can be reduced, and the utilization rate of the low-boiling fraction is improved.
Preferably, the feed mixture of hydrogen chloride and tetramethylsilane is subjected to at least 3 passes of high purity nitrogen before being fed.
2. A preheating unit: the raw material tetramethylsilane mixture and hydrogen chloride gas enter a reaction unit after being preheated by a preheating unit according to a certain proportion and flow.
The invention controls the ratio of the tetramethylsilane mixture (calculated by tetramethylsilane) to the hydrogen chloride gas, specifically, the ratio of the mass of hydrogen chloride to the mass of tetramethylsilane is 0.2-1.25, preferably 0.4-1.0.
The preheating unit comprises a preheater; the temperature of the preheater is 30-50 ℃.
The reaction unit is preheated and mixed by the preheater, the mixture of raw material hydrogen chloride gas and methyl chlorosilane enters the reaction unit, the reaction efficiency is improved, the reaction unit products are subjected to heat exchange by the preheater, and enter the intermediate buffer storage tank through the recooler, so that the heat of the reaction raw materials and the products can be fully utilized, the energy consumption is greatly reduced, and the method is suitable for industrialized popularization.
Further, it was found that the purity and proportion of trimethylchlorosilane in the product can be further improved by controlling the appropriate preheating temperature of the raw materials, respectively.
Preferably, the preheating unit comprises a multistage preheater, namely preheater I and preheater II.
The preheater I controls the preheating temperature of raw material hydrogen chloride, and the temperature range of the preheater I is 40-50 ℃.
The preheating temperature of the raw material tetramethylsilane mixture is controlled by a preheater II, and the temperature of the preheater II is in the range of 32-45 ℃.
More preferably, the temperature of preheater I is higher than the temperature of preheater II. For example, the temperature of preheater I is 5-10deg.C higher than the temperature of preheater II.
The tetramethylsilane mixture is derived from tetramethylsilane mixture generated in the process of synthesizing an organosilicon monomer by a direct method, is a multicomponent mixture containing TMS, and can be quickly contacted with TMS of the tetramethylsilane mixture or dispersed around the TMS due to higher molecular hydrogen chloride temperature in the process of contacting with HCl preheated at higher temperature after preheating, so that the probability of contacting hydrogen chloride with other components in the mixture and generating side reaction is reduced, the reaction efficiency of raw material hydrogen chloride is improved, and the selectivity of chemical reaction is improved.
3. And (3) a reaction unit: comprises a fixed bed reactor, and the preheated raw materials react in a reaction unit as follows to obtain a product.
(CH 3 ) 4 Si+HCl→(CH 3 ) 3 SiCl+CH 4
1) The fixed bed reactor is selected from a continuous fixed bed reactor or a batch fixed bed reactor.
The fixed bed reactor is selected from a vertical pipe type fixed bed reactor, a kettle type reactor or a rectifying tower type reactor, and is preferably a vertical pipe type fixed bed reactor.
In particular, the fixed bed reactor may be a DN50 riser or kettle type fixed bed reactor based on a continuous process, or a kettle type reactor under batch process conditions or a rectifying tower reactor integrating catalyst on trays or packing, preferably a riser type fixed bed reactor.
Preferably, the reactor is a multitubular fixed bed reactor.
The upper section, the middle section and the lower section of the fixed bed reactor are respectively filled with inert porcelain balls, a catalyst and the inert porcelain balls. The filling amount of the inert porcelain balls of each layer is about 1.2-1.8 times of the filling height of the catalyst, and the filling amount of the catalyst is determined by the residence time and a tetramethylsilane mixture feeding pump.
2) Catalyst
The catalyst used in the invention is Lewis acid type solid or powder catalyst, the catalyst is spherical or cylindrical or bar-shaped or powder-shaped, and the catalyst comprises and is not limited to gamma-Al 2 O 3 、AlCl 3 Molecular sieves, zeolites, or gamma-Al 2 O 3 Loaded with active component AlCl 3 。
More preferably, the catalyst is gamma-Al 2 O 3 Load AlCl 3 +MgCl 2 Mg is used as a catalyst auxiliary agent, wherein the molar ratio of Al to Mg is 1: (0.05-0.5), mg is used as an auxiliary agent to form a difunctional metal active center with Al, so as to excite more catalytic sites.
The gamma-Al can be obtained by adopting a conventional dipping method 2 O 3 Load AlCl 3 +MgCl 2 The catalyst and the preparation method are simple.
The supported catalyst and the active component are combined to form a multi-stage catalyst structure, so that the mechanical strength of the catalyst is optimized, and the efficiency and selectivity of the catalytic reaction are improved.
3) Residence time
The residence time is measured by tetramethylsilane TMS, and the residence time is 0.5 to 90 minutes, preferably 50 to 70 minutes.
4) Reaction temperature
The reaction temperature of the invention is 55-280 ℃, preferably 90-140 ℃.
5) Reaction pressure of fixed bed
The reaction pressure of the invention is 0.01 MPa.g-0.8 MPa.g, preferably 10 KPa.g-50 KPa.g.
In the reaction unit, the preheated tetramethylsilane mixture and hydrogen chloride gas are reacted in a fixed bed reactor under the conditions of catalyst, certain temperature and residence time to obtain a reaction product.
The reaction principle is as follows:
(CH 3 ) 4 Si+HCl→(CH 3 ) 3 SiCl+CH 4
the reaction unit also comprises a recooler and an intermediate buffer tank, and a reaction product obtained by the fixed bed reactor enters the intermediate buffer tank through the recooler after exchanging heat with raw materials through a preheater of the preheating unit; further, the reaction product enters the light unit through an intermediate buffer tank.
When the multi-stage preheater is adopted to preheat the raw materials to different temperatures respectively, the reaction product exchanges heat with the raw materials through a preheater II (preheating tetramethylsilane mixture) of the preheating unit and then enters an intermediate buffer storage tank through a recooler.
4. Light unit
The light component removing unit comprises a light component removing tower, and the reaction product enters the light component removing tower to be rectified and separated to obtain a light component removing mixture containing the target product trimethylchlorosilane.
The light component removal tower operation conditions are as follows: the tower operating pressure is 0.1 MPa.g-0.4 MPa.g, preferably 0.2MPa.g; the temperature of the tower top is 40-60 ℃; column reflux ratio: 15 to 25, most preferably 20.
After rectifying and separating by a light component removal tower, the liquid phase product containing trimethylchlorosilane at the tower bottom is sent to a reaction product collection tank; the gas phase material at the top of the tower passes through a cooler and then is subjected to a certain reflux ratio to obtain a liquid phase light component material which is not completely reacted and contains TMS, and the liquid phase material at the top of the tower is sent to a TMS storage tank to form TMS circulation, so that the use amount of additional raw materials is reduced, and the utilization rate of the raw materials is improved; the non-condensable gas containing methane at the top of the tower is sent to incineration, so that the comprehensive collection of the product is realized.
In a second aspect, the present invention provides a process for the preparation of trimethylchlorosilane: the method comprises the following steps:
(1) Feeding: raw material 1 hydrogen chloride gas comes from a purification device, and raw material 2 tetramethylsilane mixture comes from tetramethylsilane mixture generated in the process of synthesizing organosilicon monomers by a direct method;
preferably, the feed mixture of hydrogen chloride and tetramethylsilane is subjected to at least 3 passes of high purity nitrogen before being fed.
(2) Preheating and mixing: the tetramethylsilane mixture and hydrogen chloride gas enter a fixed bed reactor after being preheated by a preheater according to a certain proportion and flow;
wherein the ratio of the mass of hydrogen chloride to the mass of tetramethylsilane is 0.2 to 1.25, preferably 0.4 to 1.0.
The temperature of the preheater is 30-50 ℃.
Preferably, a multistage preheater is used to preheat the feed hydrogen chloride and tetramethylsilane mixture separately.
Wherein, the preheater I controls the preheating temperature of the raw material hydrogen chloride, and the temperature range of the preheater I is 40-50 ℃.
The preheating temperature of the raw material tetramethylsilane mixture is controlled by a preheater II, and the temperature of the preheater II is in the range of 32-45 ℃.
More preferably, the temperature of preheater I is higher than the temperature of preheater II. For example, the temperature of preheater I is 5-10deg.C higher than the temperature of preheater II.
The tetramethylsilane mixture is derived from tetramethylsilane mixture generated in the process of synthesizing an organosilicon monomer by a direct method, is a multicomponent mixture containing TMS, and can be contacted or dispersed around TMS rapidly due to higher temperature of micromolecular hydrogen chloride in the process of contacting with HCl preheated at higher temperature after preheating, so that the probability of contacting hydrogen chloride with other components in the mixture and generating side reaction is reduced, the reaction efficiency of raw material hydrogen chloride is improved, and the selectivity of chemical reaction is improved.
(3) The reaction: the preheated tetramethylsilane mixture and hydrogen chloride gas raw material react in a fixed bed reactor in the presence of a catalyst to obtain a reaction product; the product enters a preheater to exchange heat with the raw materials, and then passes through a recooler and is input into an intermediate buffer storage tank.
The reaction principle is as follows:
(CH 3 ) 4 Si+HCl→(CH 3 ) 3 SiCl+CH 4
the catalyst used in the invention is Lewis acid type solid or powder catalyst, the catalyst is spherical or cylindrical or bar-shaped or powder-shaped, and the catalyst comprises and is not limited to gamma-Al 2 O 3 、AlCl 3 Molecular sieves, zeolites, or gamma-Al 2 O 3 Supported catalysts, preferably zeolite or gamma-Al 2 O 3 Loaded with active component AlCl 3 。
More preferably, the catalyst is gamma-Al 2 O 3 Loaded with double active components AlCl 3 +MgCl 2 Wherein the mole ratio of Al to Mg is 1: (0.1-0.5), mg is used as an auxiliary agent to form a difunctional metal active center with Al,more catalytic sites are excited. The loading of the single or double active components is 10-40wt%.
The gamma-Al can be obtained by adopting a conventional dipping method 2 O 3 Load AlCl 3 +MgCl 2 The catalyst and the preparation method are simple.
The supported catalyst and the active components are combined to form a multi-stage catalyst structure, so that the mechanical strength of the catalyst is optimized, the efficiency and selectivity of the catalytic reaction are improved, and the purity of the product is higher.
The residence time in the reactor is measured by tetramethylsilane TMS, and the residence time is 0.5 to 90min, preferably 50 to 70min.
The reaction temperature of the invention is 55-280 ℃, preferably 90-140 ℃.
The reaction pressure of the fixed bed is 0.01 MPa.g-0.8 MPa.g, preferably 10 KPa.g-50 KPa.g.
(4) Light separation: the product enters a light component removing tower through an intermediate buffer storage tank, and after rectification and separation, a liquid phase product containing trimethylchlorosilane of a tower bottom product is sent to a reaction product collecting tank for collection; cooling the gas-phase material at the top of the tower to obtain a liquid-phase material containing TMS completely unreacted at a certain reflux ratio, and leading the liquid-phase material obtained at the top of the tower to a TMS storage tank to form TMS circulation, thereby improving the utilization rate of raw materials; the non-condensable gas containing methane at the top of the tower is sent to incineration.
The light component removal tower operation conditions are as follows: the tower operating pressure is 0.1 MPa.g-0.4 MPa.g; the temperature of the tower top is 40-60 ℃; column reflux ratio: 15-25.
For implementing the method of the invention, the device of the process comprises a purification device 1 for HCl gas, a TMS storage tank 2 for storing the tetramethylsilane mixture, a preheater 3 for heat exchange of raw materials and reaction products, a fixed bed reactor 4, a recooler 5, a reaction product intermediate buffer storage tank 6, a light component removal tower 7, a light component removal tower condensation cooler 8 and a reaction product collection tank 9.
The invention has the beneficial effects that:
1) The TMS is comprehensively utilized by utilizing hydrogen chloride gas generated by the hydrolysis of methyl chlorosilane, the TMS is converted into the target product trimethylchlorosilane, the content of trimethylchlorosilane in the product reaches more than 80%, the loss of other organosilicon monomers, namely, the trimethylchlorosilane and the trimethylchlorosilane is reduced, and the utilization rate of low-boiling-point fractions is improved.
2) According to the invention, the preheater is arranged in the preheating unit, so that the mixture of raw material hydrogen chloride gas and methyl chlorosilane can be preheated and mixed and then enter the reaction unit, the reaction efficiency is improved, meanwhile, the product of the reaction unit is subjected to heat exchange by the preheater, and enters the intermediate buffer storage tank through the recooler, so that the heat of the reaction raw material and the product can be fully utilized, the energy consumption is reduced, and the method is suitable for industrialized popularization.
3) The invention controls the proper preheating temperature of the raw materials respectively, and can further improve the purity and the proportion of the trimethylchlorosilane in the product. In the process of contacting the tetramethylsilane mixture with HCl preheated at a higher temperature, the temperature of hydrogen chloride is higher, the tetramethylsilane mixture can be quickly contacted with TMS of the tetramethylsilane mixture or dispersed around TMS, the probability of contacting hydrogen chloride with other components and generating side reactions is reduced, the reaction efficiency of raw material hydrogen chloride is improved, and the selectivity of chemical reaction is improved.
4) The invention selects proper Lewis acid catalyst, forms a double-structure catalyst by alumina-supported aluminum chloride and magnesium chloride, not only improves the active site and the number of active sites of the catalyst and improves the catalytic reaction efficiency and the purity of the product trimethylchlorosilane, but also can further improve the mechanical strength and the service life of the catalyst by using carrier alumina.
Drawings
FIG. 1 is a block diagram and process scheme of a system for preparing trimethylchlorosilane of example 1.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
The initial state of the system device is 10KPa.g nitrogen sealing state, the temperature of the device is normal temperature, and the device is replaced by high-purity nitrogen for at least 3 times before feeding materials.
Example 1
The embodiment provides a preparation system of trimethylchlorosilane, which comprises the following components in turn: a feeding unit, a preheating unit, a reaction unit and a light component removing unit. The feeding unit comprises a hydrogen chloride purifying device and a tetramethylsilane mixture storage tank. The raw material hydrogen chloride gas is from a purification device 1, and the tetramethylsilane mixture is stored in a TMS storage tank 2. The raw material mixture of hydrogen chloride and tetramethylsilane is replaced by high-purity nitrogen at least 3 times before the raw material mixture is fed.
The preheating unit comprises a preheater 3, and raw materials of tetramethylsilane mixture and hydrogen chloride gas enter the reaction unit after being preheated by the preheating unit according to a certain proportion and flow.
The reaction unit comprises a fixed bed reactor 4, a recooler 5 and a reaction product intermediate buffer storage tank 6. The upper, middle and lower sections of the fixed bed reactor 4 are filled with inert porcelain balls, catalyst and inert porcelain balls, respectively. The filling amount of the inert porcelain balls of each layer is 1.5 times of the filling height of the catalyst, and the filling amount of the catalyst is determined by the residence time and a tetramethylsilane mixture feeding pump.
The reaction product obtained by the fixed bed reactor 4 exchanges heat with the raw material through the preheater 3 of the preheating unit and then enters the intermediate buffer storage tank 6 through the recooler 5; further, the reaction product enters the light unit through an intermediate buffer tank 6.
The light component removing unit comprises a light component removing tower 7, and the reaction product enters the light component removing tower to carry out rectification and a light component removing mixture containing the target product trimethylchlorosilane. After rectifying and separating by a light component removal tower, the liquid phase product containing trimethylchlorosilane at the tower bottom is sent to a reaction product collection tank 9; the gas phase material at the top of the tower passes through a condensing cooler 8 of the light component removal tower and then extracts liquid phase material containing TMS which is not completely reacted at a certain reflux ratio, and the liquid phase material at the top of the tower goes to a TMS storage tank 2; the non-condensable gas containing methane at the top of the tower is sent to incineration.
The embodiment also provides a preparation method of trimethylchlorosilane, which is completed by using the system of the embodiment, and comprises the following steps:
(1) Feeding: the raw material hydrogen chloride gas is from a purification device 1, and the raw material tetramethylsilane mixture is from a TMS storage tank 2 of the tetramethylsilane mixture generated in the process of synthesizing the organosilicon monomer by a direct method;
(2) Preheating and mixing: the ratio of the mass of hydrogen chloride to the mass of tetramethylsilane is 0.954, and the mixture is preheated to 40 ℃ by a preheater 3 and then enters a fixed bed reactor;
(3) The reaction: the preheated tetramethylsilane mixture and hydrogen chloride gas raw material are reacted in the presence of a catalyst in a fixed bed reactor 4 to obtain a reaction product; the product enters the preheater 3 to exchange heat with the raw material, passes through the recooler 5 and is input into the intermediate buffer storage tank 6.
The reaction principle is as follows:
(CH 3 ) 4 Si+HCl→(CH 3 ) 3 SiCl+CH 4
in a fixed bed reactor, the residence time is 60min, the reaction temperature is 140 ℃, the fixed bed reaction pressure is 40KPa.g, and the catalyst is gamma-Al 2 O 3 Load AlCl 3 The active component loading was 20%.
(4) Light separation: the product enters a light component removing tower 7 through an intermediate buffer storage tank, the operating pressure of the light component removing tower is 0.2MPa.g, and the tower top temperature of the light component removing tower is 45 ℃. After rectification separation, the liquid phase product of the tower kettle product containing trimethylchlorosilane is sent to a reaction product collection tank 9 for collection; the gas phase material at the top of the tower is cooled and then is extracted to the liquid phase material containing TMS which is not completely reacted at the reflux ratio of R=20, the liquid phase material extracted at the top of the tower is sent to a TMS storage tank 2, and the non-condensable gas containing methane at the top of the tower is sent to incineration.
After the light component removal tower 7 is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of trimethylchlorosilane in the liquid phase product of the tower kettle is 93.5 percent.
Example 2
This example provides a system for preparing trimethylsilane in the same manner as in example 1. Meanwhile, this example also provides a preparation method of trimethylchlorosilane, which differs from example 1 only in that: catalytic reactionThe catalyst was gamma-Al based on the same catalyst loading, with the catalyst being different 2 O 3 Load AlCl 3 And MgCl 2 The catalyst is prepared by adopting a conventional impregnation method, and the molar ratio of Al to Mg is 1:0.1; the dual active component loading was 20%. The other steps were the same as in example 1.
After the light component removal tower 7 is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of trimethylchlorosilane in the liquid phase product of the tower kettle can be obtained to be 94.0%.
Example 3
The production system was the same as in example 1 except that the ratio of the mass of hydrogen chloride to the mass of tetramethylsilane was adjusted to 0.4 in the production of trimethylchlorosilane. After the light component removal tower kettle is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of trimethylchlorosilane in the liquid phase product of the tower kettle can be obtained by 82.2 percent.
Example 4
The preparation system was the same as in example 1, except that in the preparation of trimethylchlorosilane, the ratio of the mass of hydrogen chloride to the mass of tetramethylsilane was 1.244, the reaction residence time was 90min, and the reaction temperature was 180 ℃. After the light component removal tower kettle is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of trimethylchlorosilane in the liquid phase product of the tower kettle can be 73.8 percent.
Example 5
The preparation system was the same as in example 1, except that the fixed bed reactor temperature was 240℃during the preparation of trimethylchlorosilane. After the light component removal tower kettle is extracted for 2 hours, sampling is carried out for gas chromatographic analysis, and the content of trimethylchlorosilane in the liquid phase product of the tower kettle can be obtained by 86.9 percent.
Example 6
The preparation system was the same as in example 1, except that the fixed bed reactor temperature was 80℃during the preparation of trimethylchlorosilane. After the light component removal tower kettle is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of trimethylchlorosilane in the liquid phase product of the tower kettle can be obtained by 79.2 percent.
Example 7 (preheating unit using multistage preheater)
The embodiment provides a preparation system of trimethyl rate silane, which comprises the following components in turn: a feeding unit, a preheating unit, a reaction unit and a light component removing unit. The feed unit, the light unit were identical to example 1, with the only difference being the preheating unit and the reaction unit.
The preheating unit comprises a preheater I and a preheater II, wherein the preheater I and the preheater II are respectively arranged on a feed line of a mixture of raw material hydrogen chloride and tetramethylsilane, and the preheater I controls the preheating temperature of the raw material hydrogen chloride to 40 ℃. The preheater II controls the preheating temperature of the feed tetramethylsilane mixture to 45 ℃. The raw materials are respectively preheated to different temperatures and enter a reaction unit.
The reaction unit comprises a fixed bed reactor 4, a recooler 5 and a reaction product intermediate buffer storage tank 6. The upper, middle and lower sections of the fixed bed reactor 4 are filled with inert porcelain balls, catalyst and inert porcelain balls, respectively. The filling amount of the inert porcelain balls of each layer is 1.5 times of the filling height of the catalyst, and the filling amount of the catalyst is determined by the residence time and a tetramethylsilane mixture feeding pump.
The reaction product obtained by the fixed bed reactor 4 exchanges heat with the raw material through a preheater II of a preheating unit and then enters an intermediate buffer storage tank 6 through a recooler 5; further, the reaction product enters the light unit through an intermediate buffer tank 6.
The system of the embodiment is used for preparing trimethylchlorosilane, and comprises the following steps:
(1) Feeding: the raw material hydrogen chloride gas is from a purification device 1, and the raw material tetramethylsilane mixture is from a TMS storage tank 2 of the tetramethylsilane mixture generated in the process of synthesizing the organosilicon monomer by a direct method;
(2) Preheating and mixing: hydrogen chloride is preheated to 40 ℃ by a preheater I; preheating the tetramethylsilane mixture to 45 ℃ by a preheater II, and then entering a fixed bed reactor; the ratio of the mass of hydrogen chloride to the mass of tetramethylsilane was 0.954;
(3) The reaction: the preheated tetramethylsilane mixture and hydrogen chloride gas raw material are reacted in the presence of a catalyst in a fixed bed reactor 4 to obtain a reaction product; the product enters a preheater II to exchange heat with the raw material, passes through a recooler 5 and is input into an intermediate buffer storage tank 6.
The reaction principle is as follows:
(CH 3 ) 4 Si+HCl→(CH 3 ) 3 SiCl+CH 4
in a fixed bed reactor, the residence time is 60min, the reaction temperature is 140 ℃, the fixed bed reaction pressure is 40KPa.g, and the catalyst is gamma-Al 2 O 3 Load AlCl 3 The active component loading was 20%.
(4) Light separation: the same procedure as in example 1 was followed.
After the light component removal tower 7 is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of the trimethylchlorosilane in the liquid phase product of the tower kettle can be 95.70 percent.
Example 8
The preparation system was the same as in example 7, using preheater I and preheater II to preheat the feed hydrogen chloride and tetramethylsilane mixture, respectively.
The preparation is identical to example 7, except that: hydrogen chloride is preheated to 38 ℃ by a preheater I; the tetramethylsilane mixture was preheated to 44℃by preheater II and fed into a fixed bed reactor.
After the light component removal tower 7 is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of trimethylchlorosilane in a liquid phase product of a tower kettle can be obtained to be 96.20%.
Example 9
The preparation system was the same as in example 7, using preheater I and preheater II to preheat the feed hydrogen chloride and tetramethylsilane mixture, respectively.
The preparation is identical to example 7, except that: hydrogen chloride is preheated to 38 ℃ by a preheater I; the tetramethylsilane mixture was preheated to 41℃by preheater II and fed into a fixed bed reactor.
After the light component removal tower 7 is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of trimethylchlorosilane in a liquid phase product of a tower kettle can be obtained to be 94.4%.
Example 10 (multistage Pre-heating+Multi catalyst)
The preparation system was the same as in example 7, using preheater I and preheater II to preheat the feed hydrogen chloride and tetramethylsilane mixture, respectively.
The preparation is identical to example 7, except that: the catalysts are different and gamma-Al is adopted based on the same catalyst loading 2 O 3 Load AlCl 3 And MgCl 2 The catalyst is prepared by adopting a conventional impregnation method, the molar ratio of Al to Mg is 1:0.1, and the loading amount of the double active components is 20%.
After the light component removal tower 7 is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the trimethyl chlorosilane content in the liquid phase product of the tower kettle can be 97.9 percent.
Comparative example 1 (no preheating unit was provided)
This comparative example provides a system for preparing a trimethylrate silane comprising, in order: a feeding unit, a reaction unit and a light component removing unit. The feed unit was the same as in example 1.
The reaction unit comprises a fixed bed reactor 4, a recooler 5 and a reaction product intermediate buffer storage tank 6. The upper, middle and lower sections of the fixed bed reactor 4 are filled with inert porcelain balls, catalyst and inert porcelain balls, respectively. The filling amount of the inert porcelain balls of each layer is 1.5 times of the filling height of the catalyst, and the filling amount of the catalyst is determined by the residence time and a tetramethylsilane mixture feeding pump.
The raw materials enter a fixed bed reactor 4, and the obtained reaction product enters an intermediate buffer storage tank 6 through a recooler 5; further, the reaction product enters the light unit through an intermediate buffer tank 6.
The light unit is the same as in example 1.
The comparative example also provides a preparation method of trimethylchlorosilane, which is completed by using the system, and comprises the following steps:
(1) Feeding: the raw material hydrogen chloride gas is from a purification device 1, and the raw material tetramethylsilane mixture is from a TMS storage tank 2 of the tetramethylsilane mixture generated in the process of synthesizing the organosilicon monomer by a direct method;
(2) Preheating and mixing: the ratio of the mass of hydrogen chloride to the mass of tetramethylsilane is 0.954, and the mixture is preheated to 40 ℃ by a preheater 3 and then enters a fixed bed reactor;
(3) The reaction: the tetramethylsilane mixture and hydrogen chloride gas raw material enter a fixed bed reactor 4 to react in the presence of a catalyst to obtain a reaction product; after passing through the recooler 5, the product is fed to an intermediate buffer tank 6.
The reaction principle is as follows:
(CH3)4Si+HCl→(CH3)3SiCl+CH4
in the fixed bed reactor, the ratio of the mass of hydrogen chloride to the mass of tetramethylsilane is 0.954, the residence time is 60min, the reaction temperature is 140 ℃, the reaction pressure of the fixed bed is 40KPa.g, and the catalyst is gamma-Al 2 O 3 Load AlCl 3 The active component loading was 20%.
(4) Light separation: the same as in example 1.
After the light component removal tower 7 is extracted for 2 hours, sampling is carried out for gas chromatography analysis, and the content of trimethylchlorosilane in the liquid phase product of the tower kettle is 64.5 percent.
TABLE 1
It will be appreciated by those skilled in the art that the above embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the application. Other variations or modifications will be apparent to persons skilled in the art from the foregoing disclosure, and such variations or modifications are intended to be within the scope of the present invention.
Claims (10)
1. A system for preparing trimethylchlorosilane, comprising, in order: the device comprises a feeding unit, a preheating unit, a reaction unit and a light component removing unit;
1) The feeding unit comprises a hydrogen chloride purifying device and a tetramethylsilane mixture storage tank, wherein raw material hydrogen chloride gas is from the purifying device, hydrogen chloride of the purifying device is from hydrogen chloride generated by hydrolysis of methylchlorosilane, and tetramethylsilane mixture is from the tetramethylsilane mixture storage tank;
2) A preheating unit: the preheating unit comprises a preheater; the temperature of the preheater is 30-45 ℃, and raw material tetramethylsilane mixture and hydrogen chloride gas enter a reaction unit after being preheated by a preheating unit according to a certain proportion and flow;
3) And (3) a reaction unit: comprises a fixed bed reactor, wherein the preheated raw materials react in a reaction unit to obtain a product;
4) Light unit: the method comprises a light component removing tower, wherein a reaction product enters the light component removing tower, and is rectified and separated to obtain a light component removing mixture containing a target product trimethylchlorosilane.
2. The system of claim 1, wherein the preheating unit comprises a multi-stage preheater, preheater I and preheater II, for preheating the feed hydrogen chloride and tetramethylsilane mixture, respectively;
the preheating temperature of raw material hydrogen chloride is controlled by a preheater I, and the temperature range of the preheater I is 40-50 ℃;
the preheating temperature of the raw material tetramethylsilane mixture is controlled by a preheater II, and the temperature range of the preheater II is 32-45 ℃;
preferably, the temperature of the preheater I is higher than the temperature of the preheater II.
3. The system of claim 2, wherein the temperature of preheater I is 5-8 ℃ higher than the temperature of preheater II.
4. The system of claim 1, wherein the fixed bed reactor is a multitubular fixed bed reactor or a tubular reactor, and the upper, middle and lower sections of the fixed bed reactor are filled with inert porcelain spheres, catalyst and inert porcelain spheres, respectively;
the reaction unit also comprises a recooler and an intermediate buffer tank, and a reaction product obtained by the fixed bed reactor enters the intermediate buffer tank through the recooler after exchanging heat with raw materials through a preheater of the preheating unit; further, the reaction product enters the light unit through an intermediate buffer tank.
5. A preparation method of trimethylchlorosilane comprises the following steps: the method comprises the following steps:
(1) Feeding: the raw material 1 hydrogen chloride gas is from a purification device, the purification device hydrogen chloride is from a methylchlorosilane hydrolysis device, and the raw material 2 tetramethylsilane mixture is from a tetramethylsilane mixture generated in the process of synthesizing an organosilicon monomer by a direct method;
(2) Preheating and mixing: the tetramethylsilane mixture and hydrogen chloride gas enter a fixed bed reactor after being preheated by a preheater according to a certain proportion and flow; the temperature of the preheater is 30-45 ℃;
(3) The reaction: the preheated tetramethylsilane mixture and hydrogen chloride gas raw material react in a fixed bed reactor in the presence of a catalyst to obtain a reaction product; the product enters a preheater to exchange heat with the raw materials, and then passes through a recooler and is input into an intermediate buffer storage tank;
(4) Light separation: the product enters a light component removing tower through an intermediate buffer storage tank, and after rectification and separation, a liquid phase product containing trimethylchlorosilane of a tower bottom product is sent to a reaction product collecting tank for collection; and cooling the gas phase material at the top of the tower to obtain a liquid phase light component material containing TMS which is not completely reacted at a certain reflux ratio, wherein the liquid phase material obtained at the top of the tower is sent to a TMS storage tank, and the non-condensable gas containing methane at the top of the tower is sent to incineration.
6. The method of claim 5, wherein step (2) employs a multistage preheater, preheater I and sub-preheater II preheating the feed hydrogen chloride and tetramethylsilane mixture, respectively;
the temperature range of the preheater I is 40-50 ℃,
the temperature range of the preheater II is 32-45 ℃,
preferably, the temperature of the preheater I is higher than the temperature of the preheater II,
more preferably, the temperature of preheater I is 5-8 ℃ higher than the temperature of preheater II.
7. The method according to claim 5, which comprisesCharacterized in that the step (3) adopts a Lewis acid type solid or powder catalyst which is spherical or cylindrical or bar-shaped or powder-shaped and comprises and is not limited to gamma-Al 2 O 3 、AlCl 3 Molecular sieves, zeolites, or gamma-Al 2 O 3 Supported catalysts, preferably zeolite or gamma-Al 2 O 3 Loaded with active component AlCl 3 。
8. The method according to claim 7, wherein the catalyst is gamma-Al 2 O 3 Loaded with double active components AlCl 3 +MgCl 2 Wherein the mole ratio of Al to Mg is 1: (0.1-0.5), the loading of the active component of the catalyst is 5-40 wt%.
9. The process according to claim 5, wherein the fixed bed reaction pressure is from 0.01mpa.g to 0.8mpa.g, preferably from 10kpa.g to 50kpa.g; the reaction temperature is 55-280 ℃, preferably 90-140 ℃; the residence time in the reactor is measured by tetramethylsilane TMS and is 0.5min to 90min, preferably 50min to 70min.
10. The method of claim 5, wherein the light ends column operating conditions are: the tower operating pressure is 0.1 MPa.g-0.4 MPa.g; the temperature of the tower top is 40-60 ℃; column reflux ratio: 15-25.
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| CN117401685A (en) * | 2023-12-13 | 2024-01-16 | 唐山三孚硅业股份有限公司 | Method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride |
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| CN117401685A (en) * | 2023-12-13 | 2024-01-16 | 唐山三孚硅业股份有限公司 | Method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride |
| CN117401685B (en) * | 2023-12-13 | 2024-02-20 | 唐山三孚硅业股份有限公司 | Method for simultaneously producing high-purity trichlorosilane and silicon tetrachloride |
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