CN1281612C - Combination method for CH3SiCl3 conversion reaction - Google Patents
Combination method for CH3SiCl3 conversion reaction Download PDFInfo
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- CN1281612C CN1281612C CN 200410084348 CN200410084348A CN1281612C CN 1281612 C CN1281612 C CN 1281612C CN 200410084348 CN200410084348 CN 200410084348 CN 200410084348 A CN200410084348 A CN 200410084348A CN 1281612 C CN1281612 C CN 1281612C
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Abstract
The present invention discloses a combination method for CH3SiCl3 conversion reaction. The combination method adopts byproducts CH3SiCl3 produced in the process of producing (CH3)2SiCl2 monomers as raw materials, and CH3SiCl3 and RCI are gasified together and have reaction in an agitated bed-fixed bed combination reactor to obtain silicane products with the general formula of (CH3)mRnSiCl<4-n> (m is 0 or 1, and n is a positive integer from 1 to 4). The agitated bed reactor is filled with aluminium powder, the coefficient of charge is from 0.3 to 0.8, the reaction temperature of the agitated bed reactor is from 250 to 400 DEG C, the agitation speed is from 60 r/min to 200 r/min, and the reaction pressure of the agitated bed reactor is from 1 to 1.0Mpa. The fixed bed reactor is filled with solid lewis acid catalysts, the reaction temperature of the fixed bed reactor is from 250 to 400 DEG C, and the reaction pressure is from 0.1 to 1.5MPa; the molar flow rate of RCI and CH3SiCl3 is from 1: 1 to 5: 1. The present invention has the advantages that the agitated bed reactor of the agitated bed-fixed bed combination reactor can obtain high reactivity without adding other adjuvant catalysts. Meanwhile, products from the agitated bed reactor has further redistribution reaction in the fixed bed reactor connected with the agitated bed reactor in series, and unreacted RCI tail gas can be circularly used by subzero fractionation. Therefore, the conversion rate of CH3SiCl3 and RCI is increased.
Description
Technical field
The byproduct comprehensive that the present invention relates to produce in the organosilane monomer production process utilizes research field, relates in particular to a kind of CH
3SiCl
3The combined method of conversion reaction.
Background technology
Organosilicon material mainly is that a class is a main chain with the Si-O key, introduces the macromolecular compound of organic group as side chain on Si again, and its excellent performance, function uniqueness are widely used in fields such as military project, space flight, medical treatment, chemical industry.Methyl chlorosilane is an important source material of making organosilicon material, and (CH
3)
2SiCl
2Be wherein have the call a kind of.Generally adopt U.S. Pat 2380995 described methods both at home and abroad at present, methyl chloride and silica flour are produced (CH at fluidized-bed reactor through heterogeneous catalytic reaction
3)
2SiCl
2
Produce (CH in " direct method "
3)
2SiCl
2Process in, produce 5～20% CH approximately
3SiCl
3, this by product boiling point is 66 ℃, on producing, separate by rectifying tower and obtain (the loose people of good fortune, Wang Yilu. " organosilicon synthesis technique and product application ", 60～128).Along with the scale of China's methyl chlorosilane monomer production constantly enlarges CH
3SiCl
3Absolute quantity also increase rapidly because its application market is limited, formed a large amount of overstocking, and with CH
3SiCl
3The general formula that is converted into high value is (CH
3)
mR
nSiCl
4-n-mThe silane product of (m is 0 or 1, and n is 1～4 positive integer) is a feasible method.
Patent documentation USP672044 discloses a kind of with CH
3SiCl
3With Cl
2Optical chlorinating reaction takes place prepare Cl
nCH
3-nSiCl
3The method of (n=1～3), the product of generation are mainly used to synthetic α-type silane coupling agent.Patent documentation USP6384257 discloses a kind of CH
3SiCl
3Add H
2The method of reaction, CH in this process
3SiCl
3Transformation efficiency is lower, and product is mainly CH
3HSiCl
2
Summary of the invention
The purpose of this invention is to provide a kind of CH
3SiCl
3The combined method of conversion reaction.
It is with (CH
3)
2SiCl
2The by product CH that produces in the monomer production process
3SiCl
3Be main raw material, in agitated bed-fixed bed composite reaction device, react that obtaining general formula is (CH with the common gasification of RCl
3)
mR
nSiCl
4-n-mThe silane product of (m is 0 or 1, and n is 1～4 positive integer); Filling aluminium powder in the agitated bed reactor, its coefficient is 0.3～0.8, and the agitated bed temperature of reaction is 250～400 ℃, and mixing speed is 60r/min～200r/min, and the agitated bed reaction pressure is 0.1～1.0MPa; Be filled with the solid Lewis acid catalyst in the fixed-bed reactor, the fixed bed reaction actuator temperature is 250～400 ℃, and reaction pressure is 0.1～1.5MPa; RCl and CH
3SiCl
3The molar flow rate ratio be 1: 1～5: 1.
Agitated bed reactor in the combined reactor of the present invention is by preferred combined impeller form, can make the heat and mass transport of reaction obtain good improvement, because of of the influence of aluminium powder coking deactivation, need not add other auxiliary catalyzer in the reaction process and can obtain high reaction activity and high yet in the minimizing reaction process speed of reaction and product content; Utilization simultaneously is connected in the fixed-bed reactor behind the agitated bed, and redistribution reaction further takes place in fixed-bed reactor the product that allows agitated bed reactor come out; Unreacted RCl tail gas can recycle by subzero fractionation.
Method provided by the invention can effectively improve raw material CH
3SiCl
3With the utilization ratio of RCl, can produce (CH at lower cost
3)
mR
nSiCl
4-n-mSilane product.
Description of drawings
Fig. 1 is ribbon-raker stirrer structural representation;
Fig. 2 is screw rod-raker stirrer structural representation;
Fig. 3 is ribbon-screw rod-scraper plate combined impeller structural representation;
Fig. 4 is a process flow diagram of the present invention.
Embodiment
Agitated bed provided by the invention-fixed bed composite reaction device carries out CH
3SiCl
3The combined method of conversion reaction, its process is as follows: CH
3SiCl
3Adopt the high-pressure metering pump charging, behind 150 ℃ of preheating mixing gasifyings, enter agitated bed reactor with RCl (R is methyl or ethyl) gas through the metering of high pressure mass flowmeter, load aluminium powder in the agitated bed reactor, the coefficient of aluminium powder in agitated bed reactor is 0.3～0.8, agitated bed reactor adopts the combined impeller form, the agitated bed temperature of reaction is 280～320 ℃, mixing speed is 70r/min～150r/min, wherein mixing speed is that 80r/min～170r/min is good, the agitated bed reaction pressure is 0.3～0.8MPa, filling solid lewis acid catalyst in the placed in-line fixed-bed reactor behind the agitated bed reactor, the fixed bed reaction actuator temperature is 300～350 ℃; Fixed bed reaction pressure is 0.3～1.0MPa, RCl and CH
3SiCl
3The molar flow rate ratio be 1: 1～3: 1, pressure-controlling in two reactors is regulated by regulating agitated bed reactor and fixed-bed reactor gas-phase product outlet valve respectively, product carries out gas solid separation through aluminum chloride trap, condenser, unreacted RCl tail gas can recycle by subzero fractionation, and concrete technical process can be with reference to figure 4.The agitator of agitated bed reactor is helical-ribbon type, screw or ribbon-screw rod group mould assembly, and is welded with scraper plate in the agitator bottom.
The solid Lewis acid catalyst of filling in the fixed-bed reactor among the present invention is aluminum chloride/activated carbon supported type catalyzer, its active ingredient is an aluminum chloride, carrier is a gac, and the solvent of employing is methyl alcohol, anhydrous methanol, ethanol, dehydrated alcohol, ether, anhydrous diethyl ether or diethyl ether; Catalyzer adopts the preparation of dipping evaporation calcination method, its process is as follows: the active ingredient aluminum chloride is dissolved in wiring solution-forming in the solvent, the proportioning of aluminum chloride and solvent is 10%～60%, the solution, the carrier that add active ingredient more successively, temperature of reaction is 20～90 ℃, reaction times is 2～8h, reaction finishes after filtration, washs, get solid matter at 100～200 ℃ of down dry 2～10h, calcine 2～10h down at 400～600 ℃ then, the mass ratio of active ingredient and carrier is 20%～80%, and its physical and chemical performance is as shown in table 1.
The physical and chemical performance of table 1 catalyzer
| Profile | Strip |
| Size/mm | 0.5～1.0 |
| Charge capacity/% | 23 |
| Specific surface area/m 2·g -1 | 1485 |
| Specific pore volume/mlg -1 | 0.85 |
| Bulk density/gml -1 | 0.87 |
The aluminium powder that adopts in the embodiment of the invention and the percentage composition of impurity thereof are as shown in table 2.
The quality percentage composition of table 2 aluminium powder and impurity thereof
| Form | Al | Sn | Zn | Cu |
| Content/% | 99.3 | 3.4×10 -3 | 1.5×10 -4 | 0.2×10 -4 |
Agitated bed, fixed-bed reactor are made by stainless material in the embodiment of the invention, the agitated bed reactor useful volume is 8L, internal diameter 320mm, high 1050mm, adopt chuck oil bath heating, its bottom is selected the sparger of Stainless Steel Cloth as the gas mixing raw material for use; Fixed-bed reactor external diameter 57mm, long 1m, interior filling 500g solid Lewis acid catalyst adopts the heating of folder electrically heated cover.
The present invention describes with following embodiment, but can not limit content of the present invention.
Embodiment 1
The aluminium powder stacking factor is 0.5 in the agitated bed reactor, and stirring velocity is 80r/min, and the agitated bed temperature of reaction is 280 ℃, and the agitated bed reaction pressure is 0.3MPa; The fixed bed reaction actuator temperature is controlled to be 300 ℃, and fixed bed reaction pressure is 0.4MPa, CH
3Cl and CH
3SiCl
3The molar flow rate ratio be 1: 1, collect behind the reaction 4h that liquid product adopts the vapor-phase chromatography marker method to analyze its composition, wherein CH in the condenser
3SiCl
3Be 22.73%, (CH
3)
2SiCl
2Be 46.91%, (CH
3)
3SiCl is 27.24%, (CH
3)
4Si is 2.19%; CH in the entire reaction course
3SiCl
3Transformation efficiency is 77.1%, CH
3The Cl transformation efficiency is 89.2%.
Embodiment 2
The aluminium powder stacking factor is 0.7 in the agitated bed reactor, and stirring velocity is 170r/min, and the agitated bed temperature of reaction is 300 ℃, and the agitated bed reaction pressure is 0.8MPa; The fixed bed reaction actuator temperature is controlled to be 350 ℃, and fixed bed reaction pressure is 0.8MPa, CH
3Cl and CH
3SiCl
3The molar flow rate ratio be 1.5: 1, collect behind the reaction 4h that liquid product adopts the vapor-phase chromatography marker method to analyze its composition, wherein CH in the condenser
3SiCl
3Be 13.73%, (CH
3)
2SiCl
2Be 51.21%, (CH
3)
3SiCl is 33.24%, (CH
3)
4Si is 1.31%; CH in the entire reaction course
3SiCl
3Transformation efficiency is 86.7%, CH
3The Cl transformation efficiency is 81.6%.
Embodiment 3
The aluminium powder stacking factor is 0.7 in the agitated bed reactor, and stirring velocity is 170r/min, and the agitated bed temperature of reaction is 320 ℃, and the agitated bed reaction pressure is 0.8MPa; The fixed bed reaction actuator temperature is controlled to be 350 ℃, and fixed bed reaction pressure is 0.8MPa, CH
3Cl and CH
3SiCl
3The molar flow rate ratio be 3: 1, collect behind the reaction 4h that liquid product adopts the vapor-phase chromatography marker method to analyze its composition, wherein CH in the condenser
3SiCl
3Be 10.03%, (CH
3)
2SiCl
2Be 42.31%, (CH
3)
3SiCl is 44.24%, (CH
3)
4Si is 3.31%; CH in the entire reaction course
3SiCl
3Transformation efficiency is 89.8%, CH
3The Cl transformation efficiency is 72.5%.
Embodiment 4
The aluminium powder stacking factor is 0.5 in the agitated bed reactor, and stirring velocity is 80r/min, and the agitated bed temperature of reaction is 320 ℃, and the agitated bed reaction pressure is 0.8MPa; The fixed bed reaction actuator temperature is controlled to be 300 ℃, and fixed bed reaction pressure is 0.8MPa, CH
3Cl and CH
3SiCl
3The molar flow rate ratio be 3: 1, collect behind the reaction 5h that liquid product adopts the vapor-phase chromatography marker method to analyze its composition, wherein CH in the condenser
3SiCl
3Be 12.03%, (CH
3)
2SiCl
2Be 46.17%, (CH
3)
3SiCl is 38.24%, (CH
3)
4Si is 3.22%; CH in the entire reaction course
3SiCl
3Transformation efficiency is 87.8%, CH
3The Cl transformation efficiency is 67.5%.
Embodiment 5
The aluminium powder stacking factor is 0.5 in the agitated bed reactor, and stirring velocity is 80r/min, and the agitated bed temperature of reaction is 300 ℃, and the agitated bed reaction pressure is 0.3MPa; The fixed bed reaction actuator temperature is controlled to be 320 ℃, and fixed bed reaction pressure is 0.4MPa, C
2H
5Cl and CH
3SiCl
3The molar flow rate ratio be 1: 1, collect behind the reaction 5h that liquid product adopts gas chromatography-mass spectrography that its composition is carried out qualitative and quantitative analysis, wherein CH in the condenser
3SiCl
3Be 33.03%, (CH
3) C
2H
5SiCl
2Be 26.43%, (CH
3) (C
2H
5)
2SiCl is 30.24%, (CH
3) (C
2H
5)
3Si is 9.04%, (C
2H
5)
4Si is 1.83%; CH in the entire reaction course
3SiCl
3Transformation efficiency is 66.7%, C
2H
5The Cl transformation efficiency is 67.5%.
Embodiment 6
The aluminium powder stacking factor is 0.7 in the agitated bed reactor, and stirring velocity is 170r/min, and the agitated bed temperature of reaction is 330 ℃, and the agitated bed reaction pressure is 0.8MPa; The fixed bed reaction actuator temperature is controlled to be 320 ℃, and fixed bed reaction pressure is 0.8MPa, C
2H
5Cl and CH
3SiCl
3The molar flow rate ratio be 3: 1, collect behind the reaction 5h that liquid product adopts gas chromatography-mass spectrography that its composition is carried out qualitative and quantitative analysis, wherein CH in the condenser
3SiCl
3Be 28.23%, (CH
3) C
2H
5SiCl
2Be 27.43%, (CH
3) (C
2H
5)
2SiCl is 31.24%, (CH
3) (C
2H
5)
3Si is 10.15%, (C
2H
5)
4Si is 3.13%; CH in the entire reaction course
3SiCl
3Transformation efficiency is 71.8%, C
2H
5The Cl transformation efficiency is 53.5%.
Claims (5)
1. CH
3SiCl
3The combined method of conversion reaction is characterized in that, with (CH
3)
2SiCl
2The by product CH that produces in the monomer production process
3SiCl
3Be raw material, react in agitated bed-fixed bed composite reaction device with the common gasification of RCl that wherein R is methyl or ethyl, obtaining general formula is (CH
3)
mR
nSiCl
4-n-mSilane product, wherein m is 0 or 1, n is 1～4 positive integer; Filling aluminium powder in the agitated bed reactor, its coefficient is 0.3～0.8, and the agitated bed temperature of reaction is 250～400 ℃, and mixing speed is 60r/min～200r/min, and the agitated bed reaction pressure is 0.1～1.0MPa; Be filled with the solid Lewis acid catalyst in the fixed-bed reactor, the fixed bed reaction actuator temperature is 250～400 ℃, and reaction pressure is 0.1～1.5MPa; RCl and CH
3SiCl
3The molar flow rate ratio be 1: 1～5: 1.
2. a kind of CH according to claim 1
3SiCl
3The combined method of conversion reaction is characterized in that, said agitated bed temperature of reaction is 280～320 ℃; Mixing speed is 80r/min～170r/min, and the agitated bed reaction pressure is 0.3～0.8MPa.
3. a kind of CH according to claim 1
3SiCl
3The combined method of conversion reaction is characterized in that, said fixed bed reaction actuator temperature is 300～350 ℃; Fixed bed reaction pressure is 0.3～1.0MPa.
4. a kind of CH according to claim 1
3SiCl
3The combined method of conversion reaction is characterized in that, said RCl and CH
3SiCl
3The molar flow rate ratio be 1: 1～3: 1.
5. a kind of CH according to claim 1
3SiCl
3The combined method of conversion reaction is characterized in that, the agitator of said agitated bed reactor is helical-ribbon type, screw or ribbon-screw rod group mould assembly, and is welded with scraper plate in the agitator bottom.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410084348 CN1281612C (en) | 2004-11-16 | 2004-11-16 | Combination method for CH3SiCl3 conversion reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410084348 CN1281612C (en) | 2004-11-16 | 2004-11-16 | Combination method for CH3SiCl3 conversion reaction |
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|---|---|
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| CN1281612C true CN1281612C (en) | 2006-10-25 |
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