CN102286016A - Method for preparing methyl chlorosilane - Google Patents
Method for preparing methyl chlorosilane Download PDFInfo
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- CN102286016A CN102286016A CN2011102731328A CN201110273132A CN102286016A CN 102286016 A CN102286016 A CN 102286016A CN 2011102731328 A CN2011102731328 A CN 2011102731328A CN 201110273132 A CN201110273132 A CN 201110273132A CN 102286016 A CN102286016 A CN 102286016A
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Abstract
The invention discloses a method for preparing methyl chlorosilane. The method comprises the following steps of: charging CH3Cl and a SiCl4 side product obtained by separating azeotrope generated during (CH3)2SiCl2 production through a direct method or a vaporized waste liquid of SiCl4 generated by a polycrystalline silicon reduction production process through a siemens method into a fluidized bed reactor filled with aluminum powders, and reacting to obtain a methyl chlorosilane mixing product with general formula of (CH3)nSiCl4-n, wherein n is a natural number within 1-4. According to the method disclosed by the invention, the SiCl4 side product obtained by separating the azeotrope generated during organic silicon monomer production through the direct method or the waste liquid of SiCl4 generated by a polycrystalline silicon reduction production process through the siemens method is taken as a raw material, thus the influence of the side product on the environment is largely released; simultaneously, the production flow is simple, convenient and feasible, the operability is strong, the industrialization is easy to be realized, the equipment investment cost is low and the economic benefit is excellent.
Description
Technical field
The present invention relates to the silicoorganic compound synthesis technical field, relate in particular to a kind of preparation method of methyl chlorosilane.
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, wherein (CH
3)
2SiCl
2It is of paramount importance organosilane monomer.Since the method for directly synthesizing organochlorosilane under methyl chloride and the catalysis of silica flour at copper powder was used in nineteen forty-one American Luo Qiao (US 2380995) invention, the methyl chlorosilane synthetic technology became better and approaching perfection day by day through the development of over half a century.China's organosilicon industry is through the development of recent two decades, and industrial scale also constantly enlarges, and just progressively moves to maturity.
Produce in the industry of methyl chlorosilane monomer in " direct method ", because the restriction of factors such as catalyzer, processing condition removes target product (CH in the monomer crude product
3)
2SiCl
2Outward, silicon tetrachloride as by-product and trimethylchlorosilane since boiling point comparatively near (being 57 ℃), easily form azeotrope, production process route and level by present domestic methyl chlorosilane are calculated, general azeotrope massfraction is about 1～2wt% of monomer crude product, and wherein the massfraction of silicon tetrachloride in azeotrope is 40～50wt%.Be to obtain the trimethylchlorosilane monomer of high value, domestic organosilane monomer manufacturer generally all can carry out the rectifying deep processing to azeotrope, therefore also produces the silicon tetrachloride by product of equivalent in rectifying.
CN1634937 discloses a kind of method of synthesizing methyl-chloro-silane.It uses organosilane monomer (CH
3)
2SiCl
2The high boiling material that produces in the production process, low-boiling-point substance or high boiling material and low-boiling-point substance are main raw material, and synthesizing general formula with methyl chloride reaction in the agitated bed reactor of filling aluminium powder is (CH
3)
mSiCl
4-mThe methyl chlorosilane monomer of (m is 1～3 positive integer), the agitated bed temperature of reaction is 250～400 ℃, mixing speed is 60r/min～200r/min, the agitated bed reaction pressure is 0.1～1.0MPa, the coefficient of aluminium powder is 0.3～0.9 in the agitated bed, and methyl chloride is 1～10: 1 with high boiling material, low-boiling-point substance or high boiling material and low-boiling-point substance quality ratio.
CN1634935 discloses a kind of CH
3SiCl
3The 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 being filled with the agitated bed reactor of aluminium powder, react that obtaining general formula is (CH with the common vaporization of RCl
3)
mR
nSiCl
4-nThe silane product of (m is 0 or 1, and n is 1～4 positive integer), the coefficient of aluminium powder in agitated bed reactor is 0.3～0.9, the agitated bed temperature of reaction is 250～400 ℃, mixing speed is 60r/min～200r/min, and the agitated bed reaction pressure is 0.1～1.0MPa, RCl and CH
3SiCl
3The molar flow rate ratio be 1: 1～5: 1.
CN1465579 discloses a kind of CH of utilization
3SiCl
3Synthetic (CH
3)
2SiCl
2Method, be raw material with purity＞99% monomethyl trichlorosilane and purity＞98% methyl chloride, carry out vapor phase alkylation, adopt Al catalysts, purity 〉=97%, ball-type, median size is 1mm, its reactant is formed CH
3SiCl
3: CH
3Cl=1: 1～1: 0.4 (mol), 200～300 ℃ of control reaction temperature, 4～5 hours reaction times, CH
3SiCl
3Transformation efficiency can reach more than 50%, (CH
3)
2SiCl
2And (CH
3)
3SiCl one way total recovery can reach more than 50%.
US4158010 discloses a kind of method that adopts organic chloride aluminium catalytic preparation methyl chlorosilane.When adopting diethyl aluminum chloride to make catalyzer, at CH
3SiCl
3With feed HCl gas in the redistribution reaction system of low-boiling-point substance, reaction can be carried out under 20～45 ℃, product mainly is (CH
3)
2SiCl
2(CH
3)
3SiCl.As 219g low-boiling-point substance and CH are being housed
3SiCl
3, the 3g diethyl aluminum chloride reactor in, feed the HCl gas of 0.75mol with the form of bubbling, temperature of reaction is 20 ℃/720mmHg, contains 45.08% (CH in the sampling analysis product behind the reaction 6h
3)
3SiCl and 19.30% (CH
3)
2SiCl
2Because the catalyzer of this type of reaction system is slightly soluble in the methyl chlorosilane monomer and recycles relatively difficulty, also needs certain solvent sometimes in the catalyst preparation, has limited the industrial application of this technology.
US4946980, US49962219, US4985580 disclose a kind of CH
3SiCl
3The method of conversion reaction, it mainly is to adopt methyl chloride, CH in fixed-bed reactor
3SiCl
3With aluminium powder and Sn, Zn, ZnCl
2, SnCl
4Deng the influence of series compound as the whole conversion reaction of catalyzer.As being 0.75 inch at a diameter, insert the mixture of 43.3g Al powder and 0.17g Sn powder in long 6.0 inches the fixed-bed reactor, the feeding mol ratio is 3: 1 CH under 300 ℃
3Cl and CH
3SiCl
3, CH wherein
3The Cl flow is 8.7g/h, and reaction time is 5s.Added adsorption medium such as gac simultaneously to improve CH
3SiCl
3Transformation efficiency, (CH in the product
3)
2SiCl
2Content is 90%, CH
3SiCl
3Transformation efficiency reaches as high as 48.6%.And reducing to 250 ℃ when temperature of reaction, adding a certain proportion of CuCl, Cu and Sn make catalyzer, CH in the Al powder
3SiCl
3Transformation efficiency is up to 11.0%, and the adding of visible catalyzer can improve (CH in reactive activity and the product
3)
2SiCl
2Selectivity.
Domestic Shao Yue just (organo-metallic method synthesization of dimethyl dichlorosilane [J]. organosilicon material, 2000 (14): 10-11.) then in the single tube fixed-bed reactor of carbon steel material, adopt the Al ball particle to receive agent, in 300 ℃ of CH of feeding certain mol proportion in the reactor down as chlorine
3SiCl
3And CH
3Cl, sampling analysis behind the reaction 4h, the result shows CH when not using catalyzer
3SiCl
3Transformation efficiency is 21%, (CH in the product
3)
2SiCl
2Content is 15%; After using catalyzer, CH
3SiCl
3Transformation efficiency reaches 43%, (CH in the product
3)
2SiCl
2Content is 32%.
Along with large-scale developing and utilizing of sun power, the purposes of photovoltaic cell raw material polysilicon more and more widely, consumption is also increasing, China's polysilicon industry had presented the geometricprogression developing state in recent years.Producing polysilicon is a purification process, and existing method of producing polysilicon has a lot, as Siemens Method, silane decomposition etc.Siemens Method is produced polysilicon and was mainly comprised for three steps:
(1) silica flour and hydrogenchloride react on fluidized-bed and form HSiCl
3
(2) to HSiCl
3Shunt purification,, in step (1) reaction process, not only generate HSiCl to obtain the state of high-purity even ultrapure (ppb)
3, also generate by product, as SiCl
4, H
2SiCl
2And FeCl
3, BCl
3, PCl
3Deng impurity.
(3) with high-purity HSiCl
3Use H
2Be reduced into high purity polycrystalline silicon by chemical gaseous phase deposition, 25% HSiCl is arranged in this process approximately
3Be converted into polysilicon, all the other enter tail gas or thermolysis is SiCl
4, HCl and Si.According to statistics, 1 ton of polysilicon of every production will produce the waste liquid more than 4 tons.Except that containing a large amount of silicon tetrachlorides, also contain impurity such as a spot of trichlorosilane, HCl in this waste liquid, purity is lower thereby purposes is little.
By product SiCl in the production of polysilicon
4Be a kind of very unstable compounds, airborne aqueous vapor can be decomposed into it hydrogenchloride and silicon-dioxide, can not well utilize as a large amount of silicon tetrachlorides, not only has a strong impact on the production cost of polysilicon, and brings immense pressure to environment.Because these by products all are the polar compounds that is rich in the chlorine atom, thus store, in the discharge process all very easily with corrosive gases such as airborne reaction of moisture generation hydrogenchloride, standing storage has very big pressure to ecotope and production safety.
Treatment process about the silicon tetrachloride as by-product in the polysilicon industry, current domestic and international report mainly contain two big classes: the first kind is to utilize hydrogen that it is reduced to the main raw material trichlorosilane of polysilicon under High Temperature High Pressure, and its transformation efficiency is crucial (referring to patent of invention CN85107465, CN1436725, CN201136791, CN1946637, CN1946636, CN2547719 etc.); Second class is to utilize the thermal silica of silicon tetrachloride production high added value (Duan Xianjian etc., aerosil development new model and to the promoter action of polysilicon industry, " organic silicon-fluorine information ", 2008 (7): 45).In addition, also there is the lot of documents introduction silicon tetrachloride to be prepared the technology report of fine chemical products such as tetraethoxy, tetrem acyloxy silane, four Diacetylmonoxime base silanes, siloxane oligomer by esterification.
Summary of the invention
The invention provides a kind of preparation method of methyl chlorosilane, this method is separated the SiCl that obtains with the azeotrope of producing the organosilane monomer generation from " direct method "
4By product or " Siemens Method " are produced the SiCl that produces in the polysilicon reducing process
4Waste liquid is the methyl chlorosilane mix monomer of raw material by conversion reaction acquisition high value, has alleviated the influence of above-mentioned by product to environment.
A kind of preparation method of methyl chlorosilane comprises: with CH
3Cl and from direct method production (CH
3)
2SiCl
2The azeotrope that produces separates the SiCl that obtains
4By product or Siemens Method are produced the SiCl that produces in the polysilicon reducing process
4Waste liquid vaporization back feeds and is filled with in the fluidized-bed reactor of aluminium powder, and it is (CH that reaction obtains general formula
3)
nSiCl
4-nThe methyl chlorosilane mix products, wherein n is 1～4 natural number.
The reaction mechanism of aforesaid method is:
3CH
3Cl+2Al→(CH
3)
3Al
2Cl
3[CH
3AlCl
2+(CH
3)
2AlCl]
SiCl
4+(CH
3)
3Al
2Cl
3→CH
3SiCl
3+(CH
3)
2SiCl
2+(CH
3)
3SiCl+(CH
3)
4Si+AlCl
3
The coefficient of described aluminium powder in fluidized-bed reactor is 0.3～0.9, more preferably 0.4～0.7.
Described temperature of reaction is 250～350 ℃, more preferably 280～320 ℃.
Described SiCl
4By product or described SiCl
4SiCl in the waste liquid
4With CH
3The amount of substance ratio of Cl is 1: 1～1: 5, more preferably 1: 2～1: 4.
Described SiCl
4By product and CH
3Cl or described SiCl
4Waste liquid and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is 50～300L/h1kg aluminium powder, more preferably 100～200L/h1kg aluminium powder.
The azeotrope that the inventive method is produced the organosilane monomer generation with direct method separates the SiCl that obtains
4By product or Siemens Method are produced the SiCl that produces in the polysilicon reducing process
4Waste liquid is a raw material, has greatly alleviated the influence of above-mentioned by product to environment.Not only Production Flow Chart is simple and easy to do for this method simultaneously, and is workable, easily realizes industrialization, and equipment investment cost is low, and the operational safety performance is stable, and do not need to add any catalyzer and just can obtain higher feed stock conversion, (CH in the product
3)
2SiCl
2, (CH
3)
3SiCl selectivity height, economic benefit is good.
Description of drawings
Fig. 1 prepares the apparatus structure synoptic diagram of methyl chlorosilane for the present invention.
Embodiment
As shown in Figure 1, a kind of methyl chlorosilane preparation facilities, comprise the nitrogen steel cylinder 1, methyl chloride steel cylinder 2, silicon tetrachloride storage tank 3, preheater 5, fluidized-bed reactor 6, aluminum chloride separation and collection device 7, condenser 8 and the product receiving tank 9 that are communicated with by pipeline, wherein the pipeline between silicon tetrachloride storage tank 3 and the preheater 5 is provided with volume pump 4.
Fluidized-bed reactor 6 is made by carbon steel material, and the reactor bottom conversion zone is of a size of: internal diameter 250mm, and length 900mm, the reactor expanding reach is of a size of: internal diameter is 600mm, highly is 180mm; Adopt chuck oil bath heating, its bottom is selected the sparger of Stainless Steel Cloth as the gas mixing raw material for use.
Aluminum chloride separation and collection device 7 is conventional separating device, it will be cooled to below the aluminum chloride fusing point from the mixture of fluidized-bed reactor 6 outputs, be generally 90～100 ℃, and the solid-state aluminum chloride in the mixture separated, condenser 8 adopts universal architecture, mainly is that gaseous product (is comprised that general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane mix monomer and silicon tetrachloride, wherein n is 1～4 natural number) be condensed into liquid object, be stored in the product receiving tank 9.
During operation, load earlier the aluminium powder of certain coefficient in the fluidized-bed reactor 6, at N
2Stop logical N after under the purging condition temperature of preheater 5, fluidized-bed reactor 6, aluminum chloride trap 7 being risen to preset value
2, the CH in the high pressure storage tank
3Cl is added from equidirectional by the mass flowmeter metering after decompression, makes the aluminium powder fluidisation and activates for some time.And then with volume pump 4 with SiCl
4Squeezing into preheater 5 vaporizes, raw material after the vaporization reacts in fluidized-bed reactor 6 and generates methyl chlorosilane and aluminum chloride, product carries out the gas-solid sharp separation through aluminum chloride trap 7, after aluminum chloride is removed, remaining gas-phase product (comprising silicon tetrachloride and methyl chloride) is stored in the product receiving tank 9 CH after by condenser 8 condensations
3Cl then enters recovery system with gaseous form, and with mass flowmeter metering, gets in the crude monomer product receiving tank 9 liquid product after reaction finishes and analyzes.
Adopt GC marker method and GC-MS method to be produced the isolating SiCl of azeotrope that organosilane monomer produces from " direct method " to what adopt among following embodiment 1～embodiment 4
4By product is tested, and the result is as follows: SiCl
4(99.52%), (CH
3)
3SiCl (0.45%).
Adopt GC marker method and GC-MS method that " Siemens Method " that adopted among following embodiment 5～embodiment 8 produced the SiCl that produces in the polysilicon reducing process
4Waste liquid (hereinafter to be referred as waste liquid) is tested, and the result is as follows: SiCl
4(97.19%), HSiCl
3(1.89%), HCl (0.87%).
The aluminium powder that adopts among the following embodiment and the percentage composition of impurity thereof are as shown in the table.
| Form | Al | Sn | Zn | Cu |
| Content/% | 99.5 | 2.3×10 -3 | 1.6×10 -4 | 0.3×10 -4 |
With above-mentioned CH
3Cl and SiCl
4By product is a raw material, and adopting device shown in Figure 1 to produce general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane, the coefficient of aluminium powder is 0.4 in the fluidized-bed reactor, SiCl
4With CH
3The amount of substance ratio of Cl is 1: 2, and the fluidized-bed reaction temperature is 280 ℃, SiCl
4By product and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is the 200L/h1kg aluminium powder, gets liquid products in the receiving tank 9 after reaction finishes, and employing vapor-phase chromatography marker method is analyzed its composition.SiCl wherein
4Be 15.8%, CH
3SiCl
3Be 36.7%, (CH
3)
2SiCl
2Be 29.9%, (CH
3)
3SiCl is 15.2%, (CH
3)
4Si is 2.3%; SiCl in the entire reaction course
4Transformation efficiency is 84.2%, CH
3The Cl transformation efficiency is 78.2%.
With above-mentioned CH
3Cl and SiCl
4By product is a raw material, and adopting device shown in Figure 1 to produce general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane, the coefficient of aluminium powder is 0.7 in the fluidized-bed reactor, SiCl
4With CH
3The amount of substance ratio of Cl is 1: 3, and the fluidized-bed reaction temperature is 285 ℃, SiCl
4By product and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is the 100L/h1kg aluminium powder, gets 9 liquid products in the receiving tank after reaction finishes, and employing vapor-phase chromatography marker method is analyzed its composition.SiCl wherein
4Be 13.1%, CH
3SiCl
3Be 31.7%, (CH
3)
2SiCl
2Be 34.1%, (CH
3)
3SiCl is 16.2%, (CH
3)
4Si is 4.7%; SiCl in the entire reaction course
4Transformation efficiency is 86.8%, CH
3The Cl transformation efficiency is 67.2%.
With above-mentioned CH
3Cl and SiCl
4By product is a raw material, and adopting device shown in Figure 1 to produce general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane, the coefficient of aluminium powder is 0.7 in the fluidized-bed reactor, SiCl
4With CH
3The amount of substance ratio of Cl is 1: 4, and the fluidized-bed reaction temperature is 320 ℃, SiCl
4By product and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is the 160L/h1kg aluminium powder, gets collection receiving tank 9 interior liquid products after reaction finishes, and adopts the vapor-phase chromatography marker method to analyze its composition.SiCl wherein
4Be 10.9%, CH
3SiCl
3Be 23.1%, (CH
3)
2SiCl
2Be 37.3%, (CH
3)
3SiCl is 23.2%, (CH
3)
4Si is 5.3%; SiCl in the entire reaction course
4Transformation efficiency is 89.0%, CH
3The Cl transformation efficiency is 68.5%.
With above-mentioned CH
3Cl and SiCl
4By product is a raw material, and adopting device shown in Figure 1 to produce general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane, the coefficient of aluminium powder is 0.6 in the fluidized-bed reactor, SiCl
4With CH
3The amount of substance ratio of Cl is 1: 2, and the fluidized-bed reaction temperature is 300 ℃, SiCl
4By product and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is the 100L/h1kg aluminium powder, gets liquid products in the receiving tank 9 after reaction finishes, and employing vapor-phase chromatography marker method is analyzed its composition; SiCl wherein
4Be 15.1%, CH
3SiCl
3Be 37.9%, (CH
3)
2SiCl
2Be 32.1%, (CH
3)
3SiCl is 13.2%, (CH
3)
4Si is 1.6%; SiCl in the entire reaction course
4Transformation efficiency is 84.8%, CH
3The Cl transformation efficiency is 71.3%.
With above-mentioned CH
3Cl and SiCl
4Waste liquid is a raw material, and adopting device shown in Figure 1 to produce general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane, the coefficient of aluminium powder is 0.5 in the fluidized-bed reactor, SiCl
4With CH
3The amount of substance ratio of Cl is 1: 3, and the fluidized-bed reaction temperature is 300 ℃, SiCl
4Waste liquid and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is the 130L/h1kg aluminium powder, gets liquid products in the receiving tank 9 after reaction finishes, and employing vapor-phase chromatography marker method is analyzed its composition; SiCl wherein
4Be 12.6%, CH
3SiCl
3Be 35.9%, (CH
3)
2SiCl
2Be 34.3%, (CH
3)
3SiCl is 14.7%, (CH
3)
4Si is 2.3%; SiCl in the entire reaction course
4Transformation efficiency is 87.3%, CH
3The Cl transformation efficiency is 56.3%.
With above-mentioned CH
3Cl and SiCl
4Waste liquid is a raw material, and adopting device shown in Figure 1 to produce general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane, the coefficient of aluminium powder is 0.7 in the fluidized-bed reactor, SiCl
4With CH
3The amount of substance ratio of Cl is 1: 4, and the fluidized-bed reaction temperature is 320 ℃, SiCl
4Waste liquid and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is the 100L/h1kg aluminium powder, gets liquid products in the receiving tank 9 after reaction finishes, and employing vapor-phase chromatography marker method is analyzed its composition; SiCl wherein
4Be 13.1%, CH
3SiCl
3Be 36.1%, (CH
3)
2SiCl
2Be 32.8%, (CH
3)
3SiCl is 14.2%, (CH
3)
4Si is 2.1%; SiCl in the entire reaction course
4Transformation efficiency is 86.8%, CH
3The Cl transformation efficiency is 71.3%.
With above-mentioned CH
3Cl and SiCl
4Waste liquid is a raw material, and adopting device shown in Figure 1 to produce general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane, the coefficient of aluminium powder is 0.5 in the fluidized-bed reactor, SiCl
4With CH
3The amount of substance ratio of Cl is 1: 2, and the fluidized-bed reaction temperature is 310 ℃, SiCl
4Waste liquid and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is the 200L/h1kg aluminium powder, gets liquid products in the receiving tank 9 after reaction finishes, and employing vapor-phase chromatography marker method is analyzed its composition; SiCl wherein
4Be 17.3%, CH
3SiCl
3Be 37.1%, (CH
3)
2SiCl
2Be 30.2%, (CH
3)
3SiCl is 12.9%, (CH
3)
4Si is 2.3%; SiCl in the entire reaction course
4Transformation efficiency is 82.6%, CH
3The Cl transformation efficiency is 71.3%.
With above-mentioned CH
3Cl and SiCl
4Waste liquid is a raw material, and adopting device shown in Figure 1 to produce general formula is (CH
3)
nSiCl
4-nMethyl chlorosilane, the coefficient of aluminium powder is 0.4 in the fluidized-bed reactor, SiCl
4With CH
3The amount of substance ratio of Cl is 1: 4, and the fluidized-bed reaction temperature is 280 ℃, SiCl
4Waste liquid and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is the 100L/h1kg aluminium powder, gets liquid products in the receiving tank 9 after reaction finishes, and employing vapor-phase chromatography marker method is analyzed its composition; SiCl wherein
4Be 14.3%, CH
3SiCl
3Be 24.1%, (CH
3)
2SiCl
2Be 36.9%, (CH
3)
3SiCl is 21.2%, (CH
3)
4Si is 3.1%; SiCl in the entire reaction course
4Transformation efficiency is 85.6%, CH
3The Cl transformation efficiency is 68.5%.
Claims (9)
1. the preparation method of a methyl chlorosilane comprises: with CH
3Cl and from direct method production (CH
3)
2SiCl
2The azeotrope that produces separates the SiCl that obtains
4By product or Siemens Method are produced the SiCl that produces in the polysilicon reducing process
4Waste liquid vaporization back feeds and is filled with in the fluidized-bed reactor of aluminium powder, and it is (CH that reaction obtains general formula
3)
nSiCl
4-nThe methyl chlorosilane mix products, wherein n is 1～4 natural number.
2. preparation method according to claim 1 is characterized in that, the coefficient of described aluminium powder in fluidized-bed reactor is 0.3～0.9.
3. preparation method according to claim 2 is characterized in that, the coefficient of described aluminium powder in fluidized-bed reactor is 0.4～0.7.
4. preparation method according to claim 1 is characterized in that, described temperature of reaction is 250～350 ℃.
5. preparation method according to claim 4 is characterized in that, described temperature of reaction is 280～320 ℃.
6. preparation method according to claim 1 is characterized in that, described SiCl
4By product or described SiCl
4SiCl in the waste liquid
4With CH
3The amount of substance ratio of Cl is 1: 1～1: 5.
7. preparation method according to claim 6 is characterized in that, described SiCl
4By product or described SiCl
4SiCl in the waste liquid
4With CH
3The amount of substance ratio of Cl is 1: 2～1: 4.
8. preparation method according to claim 1 is characterized in that, described SiCl
4By product and CH
3Cl or described SiCl
4Waste liquid and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is 50～300L/h1kg aluminium powder.
9. preparation method according to claim 8 is characterized in that, described SiCl
4By product and CH
3Cl or described SiCl
4Waste liquid and CH
3The overall flow rate that feeds fluidized-bed reactor after Cl vaporizes jointly is 100～200L/h1kg aluminium powder.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104395236A (en) * | 2012-06-14 | 2015-03-04 | 信越化学工业株式会社 | Method for producing high-purity polycrystalline silicon |
| CN112940029A (en) * | 2019-12-11 | 2021-06-11 | 新特能源股份有限公司 | Methyl chlorosilane, preparation method and device |
| CN114247180A (en) * | 2021-12-24 | 2022-03-29 | 亚洲硅业(青海)股份有限公司 | Application of active carbon containing oxygen groups in removal of impurities in silicon tetrachloride |
| CN116082384A (en) * | 2023-04-12 | 2023-05-09 | 南京首开化工有限公司 | Process for synthesizing trimethylchlorosilane by utilizing organosilicon low-boiling byproducts |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2403370A (en) * | 1945-03-15 | 1946-07-02 | Gen Electric | Alkylation of halogenosilanes |
| GB825987A (en) * | 1956-08-28 | 1959-12-23 | Kali Chemie Ag | Method of alkylating silicon tetrachloride or alkyl-or aryl-chlorosilanes |
| US4888435A (en) * | 1989-06-22 | 1989-12-19 | Dow Corning Corporation | Integrated process for alkylation and redistribution of halosilanes |
| CN1634936A (en) * | 2004-11-17 | 2005-07-06 | 浙江大学 | Combined method for synthesizing methyl chlorosilane |
| CN101531674A (en) * | 2009-04-23 | 2009-09-16 | 嘉兴学院 | Preparation method of methyl chlorosilane |
-
2011
- 2011-09-15 CN CN2011102731328A patent/CN102286016A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2403370A (en) * | 1945-03-15 | 1946-07-02 | Gen Electric | Alkylation of halogenosilanes |
| GB825987A (en) * | 1956-08-28 | 1959-12-23 | Kali Chemie Ag | Method of alkylating silicon tetrachloride or alkyl-or aryl-chlorosilanes |
| US4888435A (en) * | 1989-06-22 | 1989-12-19 | Dow Corning Corporation | Integrated process for alkylation and redistribution of halosilanes |
| CN1634936A (en) * | 2004-11-17 | 2005-07-06 | 浙江大学 | Combined method for synthesizing methyl chlorosilane |
| CN101531674A (en) * | 2009-04-23 | 2009-09-16 | 嘉兴学院 | Preparation method of methyl chlorosilane |
Non-Patent Citations (1)
| Title |
|---|
| D.T.HURD: "The Vapor Phase Alkylation and Hydrogenation of Chlorosilanes", 《J. AM. CHEM. SOC.》 * |
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| CN104395236A (en) * | 2012-06-14 | 2015-03-04 | 信越化学工业株式会社 | Method for producing high-purity polycrystalline silicon |
| EP2862840A4 (en) * | 2012-06-14 | 2015-11-11 | Shinetsu Chemical Co | Method for producing high-purity polycrystalline silicon |
| US9355918B2 (en) | 2012-06-14 | 2016-05-31 | Shin-Etsu Chemical Co., Ltd. | Method for producing high-purity polycrystalline silicon |
| CN104395236B (en) * | 2012-06-14 | 2016-11-16 | 信越化学工业株式会社 | The manufacture method of high-purity polycrystalline silicon |
| CN112940029A (en) * | 2019-12-11 | 2021-06-11 | 新特能源股份有限公司 | Methyl chlorosilane, preparation method and device |
| CN114247180A (en) * | 2021-12-24 | 2022-03-29 | 亚洲硅业(青海)股份有限公司 | Application of active carbon containing oxygen groups in removal of impurities in silicon tetrachloride |
| CN116082384A (en) * | 2023-04-12 | 2023-05-09 | 南京首开化工有限公司 | Process for synthesizing trimethylchlorosilane by utilizing organosilicon low-boiling byproducts |
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