CN101531674B - Preparation method of methyl chlorosilane - Google Patents
Preparation method of methyl chlorosilane Download PDFInfo
- Publication number
- CN101531674B CN101531674B CN200910097929XA CN200910097929A CN101531674B CN 101531674 B CN101531674 B CN 101531674B CN 200910097929X A CN200910097929X A CN 200910097929XA CN 200910097929 A CN200910097929 A CN 200910097929A CN 101531674 B CN101531674 B CN 101531674B
- Authority
- CN
- China
- Prior art keywords
- sicl
- preparation
- low
- produced
- boiling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 229920005591 polysilicon Polymers 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000011946 reduction process Methods 0.000 claims abstract 3
- 238000009835 boiling Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011973 solid acid Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 22
- 229910000077 silane Inorganic materials 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 150000001282 organosilanes Chemical class 0.000 description 9
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 239000003550 marker Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
- DESGIDRJCLIWRS-UHFFFAOYSA-N [SiH]Cl Chemical compound [SiH]Cl DESGIDRJCLIWRS-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 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 4
- 239000007789 gas Substances 0.000 description 4
- 229940050176 methyl chloride Drugs 0.000 description 4
- 239000005049 silicon tetrachloride Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- -1 acyloxy silane Chemical compound 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
本发明公开了一种甲基氯硅烷的制备方法，将有机硅单体(CH3)2SiCl2生产过程中产生的低沸物和西门子法生产多晶硅还原工艺中产生的废液混合，以AlCl3为催化剂，在250～400℃下反应合成通式为(CH3)mSiCl4-m的甲基氯硅烷单体，其中m为1～3的正整数。本发明提供的方法不仅生产流程简便易行，易实现工业化，设备投资成本低，操作安全性能稳定，而且具有原料转化率高，产物中(CH3)2SiCl2、(CH3)3SiCl选择性高，产物与催化剂易于分离。
The invention discloses a method for preparing methylchlorosilane, which comprises mixing low boilers produced in the production process of organosilicon monomer (CH 3 ) 2 SiCl 2 and waste liquid produced in the polysilicon reduction process produced by the Siemens method, and using AlCl 3 is a catalyst, reacting at 250-400° C. to synthesize a methylchlorosilane monomer with the general formula (CH 3 ) m SiCl 4-m , wherein m is a positive integer of 1-3. The method provided by the invention is not only simple and easy to implement, easy to realize industrialization, low equipment investment cost, stable operation safety performance, but also has high conversion rate of raw materials, and the selection of (CH 3 ) 2 SiCl 2 and (CH 3 ) 3 SiCl in the product High stability, easy separation of product and catalyst.
Description
Technical field
The present invention relates to the synthetic technical field of compound, relate in particular to a kind of preparation method of methyl chlorosilane.
Background technology
It is main chain with the Si-O key that organosilicon material mainly is one type, on Si, introduces the macromolecular compound of organic group as side chain 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 an organosilane monomer.Since under nineteen forty-one American Luo Qiao (US 2380995) invents with methyl chloride and the catalysis of silica flour at copper powder, directly synthesizing the method for organochlorosilane, the methyl chlorosilane synthetic technology becomes 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 title product (CH3) in the monomer crude product
2SiCl
2Producing weight percent approximately outward, is that 1～2% boiling point is lower than 40 ℃ mixture (abbreviation low-boiling-point substance).Receive the influence of character and reaction conditions etc. of purity, the catalyzer of silica flour, the composition of low-boiling-point substance and content are not quite similar in the different batches of different production lines even same production line, and its staple is (CH
3)
4Si, CH
3HSiCl
2, (CH
3)
2SiHCl and a spot of hydrocarbon polymer.It is low and be rich in the polar compound of chlorine atom that these materials belong to boiling point; So in storage, discharge process, all very easily produce corrosive gasess such as hydrogenchloride with airborne reaction of moisture; Cause great potential safety hazard and environmental pollution, therefore how rationally to utilize low-boiling-point substance more and more to receive publicity.
CN1634937 discloses a kind of method of synthesizing methyl-chloro-silane.It is with an 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, and 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.
CN100999530 discloses the high and low thing preparation (CH that boils of a kind of organosilicon
3)
2SiCl
2Method.It is with activated carbon and γ-Al
2O
3Become the two-section type catalyzed reaction as catalyst combination, the mixture of high boiling material and low-boiling-point substance and hydrogenchloride or methyl chloride splitting gas through preheating are mixed back feeding reactor drum, the sample rate 11～40g/h of mixing raw material; Reaction pressure≤0.2MPa; 200～400 ℃ of temperature of reaction, through rectifying, carry heat up in a steamer, condensation collection product, the cleavage rate of high boiling material is greater than 85%; The monomer total recovery can reach 80%, (CH in single silane
3)
2SiCl
2Selectivity is more than 40%.
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 drum 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 need certain solvent sometimes in the catalyst preparation, limited the industrial application of this technology.
US4297500 discloses a kind of method that methyl chlorosilane monomer low-boiling-point substance is converted into single silane.It is with low-boiling-point substance and HCl acting in conjunction under-30 ℃～20 ℃, normal pressure or high pressure, with (the CH in the low-boiling-point substance
3)
4Si changes into (CH
3)
3SiCl, (CH
3)
2SiHCl changes into (CH
3)
2SiCl
2The low-boiling-point substance transformation efficiency can reach 90～100%, wherein (CH
3)
4Si changes into (CH
3)
3The SiCl selectivity is 90～100%; (CH
3)
2SiHCl changes into (CH
3)
2SiCl
2Selectivity is 90～98%, and the catalyzer that can select has AlCl
3, ZnCl
2, AlOCl and AlBr
3Deng, wherein with AlCl
3Best results.
US45529730 discloses a kind of with the high boiling material in the methyl chlorosilane monomer, low-boiling-point substance and CH
3SiCl
3Method through the single silane of catalytic disproportionation prepared in reaction.Specifically be the richest in basic high boiling material, 55g CH as in the 0.5L autoclave, adding 45g
3SiCl
3, 5g is the richest in basic low-boiling-point substance and 4g NaAlCl
4The double salt catalyzer at 300 ℃ of following reaction 4h, has 57.6% component below 80 ℃, wherein (CH in the crude product
3)
2SiCl
2Account for 66.4%, (CH
3)
3SiCl accounts for 6.4%, CH
3SiCl
3Account for 24.3%.This reaction is generally carried out under the pressure more than the 3MPa.
The new grade of Liao Le discloses a kind of method (Liao Lexin that the high and low thing that boils of an organosilane monomer is passed through the single silane of catalytic disproportionation prepared in reaction; Chen Yu; Fan Hongfang etc. the cracking organosilicon high-boiling product disproportionation is converted into the research [A] of single silane. the 11st Chinese organosilicon seminar collection of thesis [C]. Hangzhou; 2002,74-76.).Concrete as in the stainless steel cauldron of 1L, disilane content 50～60% in the high boiling material in the reactant, silicon methyl support content 15～25%, low-boiling-point substance is mainly (CH
3)
4Si and (CH
3)
2SiHCl, catalyzer is generally AlCl
3, add-on is between 5～7%, and temperature of reaction is between 250～400 ℃, and reaction pressure self produces in reaction process, finally can reach 4.0MPa～7.0MPa, reaction times 4～64h.(CH in the reaction product
3)
2SiCl
2Selectivity is 55.16%, (CH
3)
3SiCl selectivity 10.78%, the height transformation efficiency 79.11% that boils, the low transformation efficiency 84.28% that boils.
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, like 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, like 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 through chemical gaseous phase deposition, 25% HSiCl is arranged in this process approximately
3Be converted into polysilicon, all the other get into 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.
Silicon tetrachloride is a kind of very unstable compounds, and airborne aqueous vapor can be decomposed into hydrogenchloride and silicon-dioxide with it, can not good use like a large amount of silicon tetrachlorides, and not only have a strong impact on the production cost of polysilicon, and bring immense pressure to environment.
Treatment process about the silicon tetrachloride as by-product in the polysilicon industry; Current domestic and international report mainly contain two big types: the first kind is under HTHP, to utilize hydrogen that it is reduced to the main raw material trichlorosilane of polysilicon, and its transformation efficiency is crucial (referring to patent of invention CN85107465, CN1436725, CN201136791, CN1946637, CN1946636, CN2547719 etc.); Second type is thermal silica (Duan Xianjian etc., aerosil development new model and the promoter action industrial to polysilicon thereof, " organic silicon-fluorine information ", 2008 (7): 45) that utilize silicon tetrachloride production high added value.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 through esterification.
Summary of the invention
The invention provides a kind of preparation method of methyl chlorosilane; This method can utilize the by-product low-boiling-point substance and the Siemens Method that produce in an organosilane monomer production process to produce the by product that produces in the polysilicon reducing process simultaneously, helps to solve above-mentioned two kinds of pressure that by product causes environmental protection.
A kind of preparation method of methyl chlorosilane is with an organosilane monomer (CH
3)
2SiCl
2Low-boiling-point substance that produces in the production process and Siemens Method are produced the waste liquid that produces in the polysilicon reducing process and are mixed, with AlCl
3Be catalyzer, reacting synthetic general formula down at 250～400 ℃ is (CH
3)
mSiCl
4-mThe methyl chlorosilane monomer, wherein m is 1～3 positive integer.
Siemens Method of the present invention is produced the waste liquid that produces in the polysilicon reducing process and is meant high-purity HSiCl
3Use H
2Be reduced into the waste liquid that produces in the high purity polycrystalline silicon process through chemical gaseous phase deposition, this waste liquid also contains impurity such as a spot of trichlorosilane, HCl except that containing a large amount of silicon tetrachlorides.
An organosilane monomer (CH of the present invention
3)
2SiCl
2The low-boiling-point substance that produces in the production process is meant the disclosed low-boiling-point substance of CN1634937 in the background technology.
The weight ratio of described low-boiling-point substance and described waste liquid is preferably 2: 1～and 6: 1, most preferably be 2: 1～4: 1.
Described temperature of reaction is preferably 280～350 ℃.
Above-mentioned preparation process preferably adopts fixed-bed reactor, in fixed-bed reactor, preferably adopts AlCl
3Load-type solid acid catalyst, the mass ratio of the feed volume flow velocity of raw material and catalyzer (reactant liquid hourly space velocity) is preferably 50～500L/hKg catalyzer in the fixed-bed reactor.
Described AlCl
3Load-type solid acid catalyst adopts the preparation of dipping calcination method, and its active ingredient is an aluminum chloride, and carrier can be selected gac, γ-Al
2O
3, molecular sieve, zeyssatite, SiO
2In one or more.
By-product low-boiling-point substance in the production of the inventive method comprehensive utilization an organosilane monomer and Siemens Method are produced the waste liquid that produces in the polysilicon reducing process and are prepared methyl chlorosilane; Whole technology not only Production Flow Chart is simple and easy to do, and is workable, is prone to realize industriallization; Equipment investment cost is low; The operational safety performance is stable, and has the feed stock conversion height, (CH in the product
3)
2SiCl
2, (CH
3)
3The SiCl selectivity is high, and product is easy to separate with catalyzer.
Description of drawings
Fig. 1 is the synthesizer synoptic diagram of methyl chlorosilane of the present invention.
Embodiment
As shown in Figure 1, a kind of device of synthesizing methyl-chloro-silane is made up of the storage tank 1, volume pump 2, preheater 3, fixed-bed reactor 5, condensing surface 7 and the product receiving tank 8 that connect successively.Wherein, Fixed-bed reactor 5 adopt the stainless steel manufacturing; Its internal diameter is 45mm; Long 150cm adopts three sections heating of open-type Reaktionsofen temperature control, and its bottom centre is inserted with a stainless steel thermocouple sheath 6
that axially is provided with in order to measure the temperature of fixed-bed reactor 5 bed different positionss; Reactor head is equipped with tensimeter 4, falls in order to the pressure of measuring bed in the fixed-bed reactor 5; Fixed-bed reactor 5 inside are filled with solid acid catalyst.
Said system concrete operations step is: earlier will be in the load weighted an organosilane monomer (CH of predetermined quality ratio
3)
2SiCl
2Low-boiling-point substance that produces in the production process and Siemens Method are produced the waste liquid that produces in the polysilicon reducing process and are put into reactant feed storage tank 1 respectively; Then with preheater 3, be filled with solid acid catalyst fixed-bed reactor 5 respectively heat temperature raisings to predetermined temperature value; Begin to fixed-bed reactor 5 chargings with volume pump 2; Product gets into condensing surface 7 from fixed-bed reactor 5 outlets and collects; Reaction feed finishes back sampling from product receiving tank 8, adopts GC marker method and GC-MS method that product is formed and carries out qualitative, quantitative analysis.Following embodiment 1～5 adopts said apparatus to produce.
The composition of used an organosilane monomer low-boiling-point substance and content are measured it through GC marker method and GC-MS method and are consisted of among the following embodiment: (CH
3)
4Si (41.65%), 2-methylbutane (3.89%), C
5H
10(isopentene) (2.55%), (CH
3)
2HSiCl (28.65%), CH
3HSiCl
2(22.88%).
Adopt GC marker method and GC-MS method that the Siemens Method that is adopted among the following embodiment is produced the waste liquid (hereinafter to be referred as waste liquid) that produces in the polysilicon reducing process and test, the result is following: SiCl
4(95.77%), HSiCl
3(3.21%), HCl (1.03%).
Reaction unit is as shown in Figure 1; 100 ℃ of control preheater temperature, the mass ratio of low-boiling-point substance and waste liquid is 2: 1 in the reaction raw materials, temperature of reactor is controlled to be 290 ℃; The reactant liquid hourly space velocity is 200L/ (a hKg catalyzer); Reaction feed finishes the back and collects product, adopts GC marker method and GC-MS method that product is formed and carries out qualitative, quantitative analysis, wherein (CH
3)
2SiCl
2Mass content is 33.52%, (CH
3)
3The SiCl mass content is 38.72%, CH
3SiCl
3Mass content is 11.34%.Remaining is a spot of methyl hydrogen silane and silicon hydride chlorid low boiling mixture.
Reaction unit is as shown in Figure 1; 100 ℃ of control preheater temperature, the mass ratio of low-boiling-point substance and waste liquid is 2: 1 in the reaction raw materials, temperature of reactor is controlled to be 350 ℃; The reactant liquid hourly space velocity is 400L/ (a hKg catalyzer); Reaction feed finishes the back and collects product, adopts GC marker method and GC-MS method that product is formed and carries out qualitative, quantitative analysis, wherein (CH
3)
2SiCl
2Mass content is 27.15%, (CH
3)
3The SiCl mass content is 31.63%, CH
3SiCl
3Mass content is 18.64%.Remaining is a spot of methyl hydrogen silane and silicon hydride chlorid low boiling mixture.
Reaction unit is as shown in Figure 1; 100 ℃ of control preheater temperature, the mass ratio of low-boiling-point substance and waste liquid is 4: 1 in the reaction raw materials, temperature of reactor is controlled to be 290 ℃; The reactant liquid hourly space velocity is 200L/ (a hKg catalyzer); Reaction feed finishes the back and collects product, adopts GC marker method and GC-MS method that product is formed and carries out qualitative, quantitative analysis, wherein (CH
3)
2SiCl
2Mass content is 38.55%, (CH
3)
3The SiCl mass content is 42.68%, CH
3SiCl
3Mass content is 11.35%.Remaining is a spot of methyl hydrogen silane and silicon hydride chlorid low boiling mixture.
Reaction unit is as shown in Figure 1; 100 ℃ of control preheater temperature, the mass ratio of low-boiling-point substance and waste liquid is 4: 1 in the reaction raw materials, temperature of reactor is controlled to be 350 ℃; The reactant liquid hourly space velocity is 400L/ (a hKg catalyzer); Reaction feed finishes the back and collects product, adopts GC marker method and GC-MS method that product is formed and carries out qualitative, quantitative analysis, wherein (CH
3)
2SiCl
2Mass content is 36.63%, (CH
3)
3The SiCl mass content is 39.27%, CH
3SiCl
3Mass content is 10.33%.Remaining is a spot of methyl hydrogen silane and silicon hydride chlorid low boiling mixture.
Reaction unit is as shown in Figure 1; 100 ℃ of control preheater temperature, the mass ratio of low-boiling-point substance and waste liquid is 3: 1 in the reaction raw materials, temperature of reactor is controlled to be 320 ℃; The reactant liquid hourly space velocity is 300L/ (a hKg catalyzer); Reaction feed finishes the back and collects product, adopts GC marker method and GC-MS method that product is formed and carries out qualitative, quantitative analysis, wherein (CH
3)
2SiCl
2Mass content is 31.32%, (CH
3)
3The SiCl mass content is 35.58%, CH
3SiCl
3Mass content is 14.87%.Remaining is a spot of methyl hydrogen silane and silicon hydride chlorid low boiling mixture.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910097929XA CN101531674B (en) | 2009-04-23 | 2009-04-23 | Preparation method of methyl chlorosilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910097929XA CN101531674B (en) | 2009-04-23 | 2009-04-23 | Preparation method of methyl chlorosilane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101531674A CN101531674A (en) | 2009-09-16 |
| CN101531674B true CN101531674B (en) | 2012-02-15 |
Family
ID=41102551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910097929XA Active CN101531674B (en) | 2009-04-23 | 2009-04-23 | Preparation method of methyl chlorosilane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101531674B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276641A (en) * | 2011-09-15 | 2011-12-14 | 江苏弘博新材料有限公司 | Method for producing methylchlorosilane |
| CN102286016A (en) * | 2011-09-15 | 2011-12-21 | 江苏弘博新材料有限公司 | Method for preparing methyl chlorosilane |
| CN102659829B (en) * | 2012-04-27 | 2014-10-08 | 泸州北方化学工业有限公司 | Recycling method of by-products in direct method production of methyl chlorosilane |
| JP5909153B2 (en) * | 2012-06-14 | 2016-04-26 | 信越化学工業株式会社 | Method for producing high-purity polycrystalline silicon |
| CN103613608B (en) * | 2013-12-09 | 2016-02-24 | 内蒙古恒业成有机硅有限公司 | A kind of method of comprehensive treating process organic silicon byproduct |
| CN104945428B (en) * | 2015-05-22 | 2019-06-21 | 嘉兴学院 | A kind of method for preparing dimethyldichlorosilane |
| CN110372740B (en) * | 2019-08-23 | 2021-10-08 | 珠海国佳凝胶研究院有限公司 | Method for preparing trimethylchlorosilane from dimethylchlorosilane |
| CN113651844B (en) * | 2021-08-20 | 2023-09-12 | 唐山偶联硅业有限公司 | Process for preparing dimethylhydrochlorosilane by continuous method |
| CN116119672B (en) * | 2023-03-06 | 2024-11-29 | 洛阳中硅高科技有限公司 | Silicon tetrachloride purification system and method |
| CN116396320A (en) * | 2023-03-07 | 2023-07-07 | 江西蓝星星火有机硅有限公司 | Method for cracking methyl organosilicon high-boiling-point substances by using catalytic cracking catalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2380995A (en) * | 1941-09-26 | 1945-08-07 | Gen Electric | Preparation of organosilicon halides |
| US4158010A (en) * | 1977-06-23 | 1979-06-12 | Wacker-Chemie Gmbh | Process for preparing organosilanes |
| US4297500A (en) * | 1979-12-14 | 1981-10-27 | Bayer Aktiengesellschaft | Conversion of low-boiling constituents from alkyl-chlorosilane synthesis |
| US4552973A (en) * | 1984-03-23 | 1985-11-12 | Bayer Aktiengesellschaft | Process for the preparation of dimethyldichlorosilane |
| US4762938A (en) * | 1986-10-10 | 1988-08-09 | Bayer Aktiengesellschaft | Process for the preparation of alkoxysilanes |
| CN1631533A (en) * | 2004-11-04 | 2005-06-29 | 浙江大学 | Preparation method and application of solid acid catalyst for synthesizing methylchlorosilane |
| CN1634937A (en) * | 2004-11-17 | 2005-07-06 | 浙江大学 | Method for synthesizing methyl chlorosilane |
| CN100999530A (en) * | 2006-12-28 | 2007-07-18 | 南昌大学 | Process of preparing dimethyl dichloro silicane by organosilicon high and low boiling matter |
-
2009
- 2009-04-23 CN CN200910097929XA patent/CN101531674B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2380995A (en) * | 1941-09-26 | 1945-08-07 | Gen Electric | Preparation of organosilicon halides |
| US4158010A (en) * | 1977-06-23 | 1979-06-12 | Wacker-Chemie Gmbh | Process for preparing organosilanes |
| US4297500A (en) * | 1979-12-14 | 1981-10-27 | Bayer Aktiengesellschaft | Conversion of low-boiling constituents from alkyl-chlorosilane synthesis |
| US4552973A (en) * | 1984-03-23 | 1985-11-12 | Bayer Aktiengesellschaft | Process for the preparation of dimethyldichlorosilane |
| US4762938A (en) * | 1986-10-10 | 1988-08-09 | Bayer Aktiengesellschaft | Process for the preparation of alkoxysilanes |
| CN1631533A (en) * | 2004-11-04 | 2005-06-29 | 浙江大学 | Preparation method and application of solid acid catalyst for synthesizing methylchlorosilane |
| CN1634937A (en) * | 2004-11-17 | 2005-07-06 | 浙江大学 | Method for synthesizing methyl chlorosilane |
| CN100999530A (en) * | 2006-12-28 | 2007-07-18 | 南昌大学 | Process of preparing dimethyl dichloro silicane by organosilicon high and low boiling matter |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101531674A (en) | 2009-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101531674B (en) | Preparation method of methyl chlorosilane | |
| CN101955187B (en) | Method and apparatus for preparing trichlorosilane through rectification by using proportionate reaction | |
| KR101819262B1 (en) | Process for selective cleavage of higher silanes | |
| CN104945428B (en) | A kind of method for preparing dimethyldichlorosilane | |
| CN212315556U (en) | Cracking system for byproduct chlorosilane high-boiling residues in polycrystalline silicon production | |
| CN103709187B (en) | A kind of new technology of synthesis dimethyldichlorosilane | |
| CN103052595A (en) | Method for preparing trihalosilane | |
| JPH08337588A (en) | Production of alkylhydrogenchlorosilane | |
| CN103253676B (en) | Preparation method of trichlorosilane | |
| CN102140107B (en) | Method for disproportionating methyl chlorosilane | |
| CN100999530A (en) | Process of preparing dimethyl dichloro silicane by organosilicon high and low boiling matter | |
| CN101195634B (en) | Method for synthesizing vinyl group containing chlorosilane | |
| CN116272684A (en) | System and method for preparing trimethylchlorosilane | |
| CN102250133B (en) | Method for preparing dimethyl dichlorosilane by using disproportionation method | |
| CN102286016A (en) | Method for preparing methyl chlorosilane | |
| CN103183701B (en) | The preparation method of vinyl chlorine-containing silane | |
| CN102850388A (en) | A preparation method of silane coupling agent | |
| CN102516285A (en) | Method for continuous catalytic cracking of organosilicon high-boiling component | |
| CN107207267A (en) | The method that disilicone hexachloride is obtained by contained chlorosilane mixture in process exhaust stream | |
| JP2648615B2 (en) | Simple production method of monosilane | |
| CN109503646B (en) | Method for treating high-boiling point polymer as byproduct of polysilicon and organic silicon | |
| CN103613608A (en) | Method for comprehensively processing organic silicon byproduct | |
| CN102276641A (en) | Method for producing methylchlorosilane | |
| CN105732692A (en) | Synthetic method of methyl phenyl dimethoxysilane | |
| CN1285599C (en) | One-step synthesizing cyclohexyl methyl dimethoxy silane without solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 314000 No. 56 South Yuexiu Road, Zhejiang, Jiaxing Patentee after: JIAXING University Patentee after: HOSHINE SILICON INDUSTRY CO.,LTD. Address before: 314000 No. 56 South Yuexiu Road, Zhejiang, Jiaxing Patentee before: Jiaxing University Patentee before: ZHEJIANG HESHENG SILICON INDUSTRY Co.,Ltd. Address after: 314000 No. 56 South Yuexiu Road, Zhejiang, Jiaxing Patentee after: JIAXING University Patentee after: ZHEJIANG HESHENG SILICON INDUSTRY Co.,Ltd. Address before: 314000 No. 56 South Yuexiu Road, Zhejiang, Jiaxing Patentee before: Jiaxing University Patentee before: Zhejiang Hesheng Group |