CN100404131C - Method for preparing silicon-copper touch body in use for synthesizing organic chlorsilane - Google Patents
Method for preparing silicon-copper touch body in use for synthesizing organic chlorsilane Download PDFInfo
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- CN100404131C CN100404131C CNB2005100904789A CN200510090478A CN100404131C CN 100404131 C CN100404131 C CN 100404131C CN B2005100904789 A CNB2005100904789 A CN B2005100904789A CN 200510090478 A CN200510090478 A CN 200510090478A CN 100404131 C CN100404131 C CN 100404131C
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Abstract
A Si-Cu contact body used for synthesizing organic chlorosilane is prepared through mixing copper sulfate with sodium chloride, heating to reaction temp, adding sodium sulfite, and reductive reaction while adding silicon powder to generate the cuprous chloride crystals on the surface of silicon particle.
Description
Technical field
The present invention relates to a kind of organic silicon monomer synthetic technology, particularly a kind of preparation method of polymolecularity silicon-copper touch body.
Background technology
At present, the methylchlorosilane synthesis technique is to make silica flour and catalyst fluidization in fluid bed, catalyst is to comprise major catalyst that contains cuprous oxide or stannous chloride and the co-catalyst of being made up of other metal, realize the catalyzed chemical reaction of silica flour and chlorohydrocarbon (as chloromethanes) gas, generate methylchlorosilane mix monomer (is main organic silicon monomer as dimethyldichlorosilane).
Because 1. the powdery mixed catalyst contacts bad in course of reaction with silica flour, be difficult to give full play to activity of such catalysts, 2. exist fluidisation to take out of etc., therefore, when this technology is produced continuously, need when adding the raw material silica flour, constantly append the powdery mixed catalyst, just can keep normally carrying out of methylchlorosilane catalytic synthesis.
US 2380996 adopts fluid bed, is the catalyst synthesizing methyl-chloro-silane with copper, has started the beginning of organochlorosilane industrialization synthetic reaction, has epoch making significance.Along with the organosilicon industrial expansion, the control of fluid bed synthetic reaction process is more and more important, and people are also more and more clearer to the understanding of methylchlorosilane synthetic reaction mechanism.
As everyone knows, the reaction carried out under the effect of powdery mixed catalyst of chlorinated hydrocabon and silica flour is the gas-solid catalytic reaction of a complexity.In the course of reaction, solid-state silica flour carries out solid-solid reaction with solid-state powdery mixed catalyst earlier, at the contact surface generation silicon copper (η is Cu3Si mutually) of silicon and Cu-contained catalyst.Silicon atom in this silicon copper has high reaction activity and high, can directly react the generation organic silicon monomer with the gas phase chlorination hydrocarbon under the certain reaction temperature, thereby constitute the main reaction in this reaction system.Fail to contact the powdery mixed catalyst that forms silicon copper with silicon under reaction temperature, wherein contained copper is called as free copper.It has advantages of high catalytic activity to the cracking of gas phase chlorination hydrocarbon.The chlorinated hydrocabon cracking obtains H
2, undesirable products such as C, HCl.The chlorinated hydrocabon cracking reaction is the main side reaction of this reaction system.For quickening main reaction, suppressing side reaction, must optimize reaction condition (temperature, pressure, gas speed etc.), screening silica flour (impurity content, granularity etc.), and screening powdery mixed catalyst (chemical constituent compatibility, crystal formation, granularity etc.).As US 4504596, US 4503165, and US 4450282, and US 4487950 is described, and cuprous oxide that filters out at present or cuprous chloride catalyst are all very thin, and particle diameter is below 3 microns.Have agglomeration in these fine powders under surface action power, the size of aggregate is about about 20 microns.In existing technology, silica flour and powdery mixed catalyst carry out drying and mixing at one in the fluid bed of nitrogen fluidisation.Under this fluidization conditions, aggregate is difficult to be disperseed.The existence of aggregate has hindered silicon and has contacted with the tight of copper, and the formation of silicon copper, also causes having a large amount of free copper in the reaction system, produces more side reaction.
US 5250716 discloses a kind of method for preparing active silicon-copper touch body of Dow Corning company.The approach that comprises a plurality of preparation Cu-series catalysts in the new method, top-priority is cuprous chloride vapor or the aerosol be made up of the superfine copper particulate that the steam rapid crystallization obtains.Cupric steam or aerosol directly enter various mechanical mixing equipments, fully contact with the silica flour of certain grain size distribution, and under normal reaction temperature, they are adsorbed on the metallic silicon surface and form active contact.Because the aerocolloidal particle diameter of copper catalyst is especially little by (10
-2～10
-1Micron), final making is used for preparing the needed copper of active silicon-copper touch body, wants much less (be approximately 1/10 or still less) than former technology.This has just saved the expense that is used for the production of copper catalyst and the post processing expense of inactivation copper greatly.In addition, the active silicon-copper touch body of this method preparation can also improve the yield of dimethyldichlorosilane.
CN 1343670A discloses the method for a kind of cuprous chloride catalyst and the dispersion of silica flour ultrasonic wave.Be characterized in the mixed process of silica flour and catalyst, adopting the liquid phase ultrasonic blender, under the effect of ultrasonic energy, destroy the catalyst agglomeration body, and be dispersed in about about the 100 microns silicon powder surface of particle diameter.Solid through ultrasonic wave solid-the raw material silica flour and the mixture of catalysts of dispersion treatment, after removing solvent, directly as reacting contact.This technology can improve the contact area of silica flour and catalyst, quickens the gas-solid catalytic reaction of direct method synthesizing organosilicon monomer, thereby improves course of reaction efficient and reduce catalyst consumption.
In the prior art, preparing " copper catalyst aerosol " and they are sprayed on the metallic silicon particle surface, is a suitable complicated technology, and cost is higher.As the activity of such catalysts stannous chloride is superfine powder, has very big surface area, thereby has the reunion behavior.Can brokenly not disperse when mixing with silica flour as this aggregate, silica flour just can not fully contact with copper catalyst.Therefore the fine powder agglomeration traits will directly influence the selectivity of resulting contact, gas chloromethanes reactive activity and dimethyldichlorosilane.Though ultrasonic scattering method can broken stannous chloride aggregate, makes stannous chloride be evenly dispersed in silicon powder surface, will use a large amount of organic solvents in processing procedure, technological process is also very complicated, is difficult to realize industrial applications.
Summary of the invention
The purpose of this invention is to provide a kind ofly, prepare the method for silicon-copper touch body with polymolecularity by control stannous chloride crystallization processes, and with the silicon-copper touch body that this method is prepared be applied to organic silicon monomer synthetic in.
The primary particle diameter of stannous chloride is about 3 microns, and aggregation size is more than tens microns.The key of the silicon-copper touch body of preparation polymolecularity is the reunion of control stannous chloride, to realize the high degree of dispersion of stannous chloride at silicon powder surface, reduce the primary particle diameter of stannous chloride, increase the contact area of stannous chloride and silica flour, and in suitability for industrialized production, reduce the use amount of stannous chloride significantly.
For reaching goal of the invention, the method for preparing the polymolecularity silicon-copper touch body provided by the invention is: copper sulphate is mixed with sodium chloride, after being heated to reaction temperature, add sodium sulfite solution again, synthesizing chlorinated cuprous through reduction reaction, in building-up process, introduce silica flour, making stannous chloride is nucleus or crystal surface with the silica flour, evenly disperse at silicon powder surface, thereby make the polymolecularity silicon-copper touch body.
Alleged reaction temperature is generally 60～150 ℃ in this method, preferably is controlled at 80～100 ℃.When reaction temperature was lower than 60 ℃, crystalline particle was big, and aggregate increases, and temperature is crossed and low can't be guaranteed to react completely.But when temperature is higher than 150 ℃, a lot of crystallization nucleis of instantaneous generation, crystalline particle is thin, and the crystal precipitating is too slow, and washing the time is difficult to remove the moisture that the surface is comprised, very easily oxidation and reunion once more when dry.
The present invention introduces the silica flour of certain grain size distribution in building-up process, the crystallization of control stannous chloride makes that stannous chloride is nucleus or crystal surface with the silica flour, evenly disperses at silicon powder surface, thereby makes the polymolecularity silicon-copper touch body.The silica flour particle diameter of introducing is distributed between 30～500 microns, is preferably between 50～150 microns.Silicon particle size excessive (greater than 500 microns), specific area is too little, causes the contact activity little.Silicon particle size too small (less than 30 microns), then easily poly-group, and easily be blown in the course of reaction.For reaching better effect, preferred 50～150 microns of silica flour particle diameter of the present invention.
The prepared silicon-copper touch body of method provided by the invention can be applicable to organic silicon monomer synthetic in.In organic silicon monomer is synthetic, use the silicon bronze body contacts of method preparation provided by the invention to compare with using cuprous chloride catalyst, the dimethyldichlorosilane selectivity improves 5% or more (near 90%), and reaction rate improves 40%, reaches 150 grams (chloromethanes)/kilogram (contact) hour.
Method provided by the present invention compared with prior art has following advantage:
1) adopts special crystallization control technology, guarantee that the primary particle diameter of stannous chloride is reduced to sub-micron degree (less than 5 microns); 2) the present invention can make stannous chloride realize the high degree of dispersion crystallization at silicon powder surface, reduces the primary particle diameter of stannous chloride, increases the contact area of stannous chloride and silica flour; 3) this technology maturation, simple, raw material is easy to get, and reaction condition not harsh (can carry out under normal pressure) is easy and simple to handle, is easy to large-scale industrialization and uses; 4) silicon-copper touch body of the inventive method preparation be applied to organic silicon monomer synthetic in, can reduce the use amount of stannous chloride significantly, improve dimethyldichlorosilane selectivity and reaction rate.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1:
Take by weighing copper sulphate 100g, sodium chloride 50g adds in the there-necked flask, and heating is stirred.Be warming up to 85 ℃ of reaction temperatures, constant temperature.Logical nitrogen fluidisation is got up (100～120 microns of silica flour particle diameters) in the silica flour fluid bed, opens nitrogen band material valve, to the logical nitrogen of synthesis reactor.Drip Na
2SO
3In the time of solution, the band material is introduced silica flour.Dropwise, stop to add silica flour.Continue to stir 15 minutes, stop to stir.Add a certain amount of water in there-necked flask, cooling was left standstill 15 minutes.Remove the upper strata light green solution, bottom precipitation through pickling, alcohol wash, suction filtration, vacuum drying get final product.Product silicon powder surface stereoscan photograph is seen accompanying drawing 1 (100～120 microns of silica flour particle diameters, the stannous chloride particle diameter is less than 2 microns), raw material silica flour stereoscan photograph is seen accompanying drawing 2 (100～120 microns of silica flour particle diameters), and pure cuprous chloride crystal stereoscan photograph is seen accompanying drawing 3 (20～110 microns of pure cuprous chloride crystal particle diameters).
Embodiment 2:
Experimentation is with embodiment 1, and reaction temperature is 95 ℃, and changing the silica flour particle diameter is 60～80 microns.Product silicon powder surface stereoscan photograph is seen accompanying drawing 4 (the silica flour particle diameter is 60～80 microns, and the stannous chloride particle diameter is less than 3 microns).
Embodiment 3:
Estimating bed is the stainless steel agitated bed, and helical-ribbon type stirs, 80 rev/mins of mixing speeds, 40 millimeters of diameters, 400 millimeters of the height of bed, electric jacket heating, on-line chromatograph analysis (GC-7890T).
The contact prescription is:
Silica flour: stannous chloride: zinc: tin=50: 5: 0.25: 0.0025 (mass ratio)
Contact is mixed the back move in the evaluation bed, be warming up to 150 ℃, stir, logical high-purity nitrogen (0.2L/min) oven dry, purging two hours continue to be warming up to 310 ℃, change logical methyl chloride gas (0.60L/min), overhead pressure is controlled at 0.2MPa, every 1 hour online sample analysis once.
It is very fast that reaction starts, and the monomer peak is obvious, monomethyl trichlorosilane content height during beginning, but very fast dimethyldichlorosilane content just reaches peak value, and process is more steady, and afterreaction speed descended in 12 hours.
Comparative Examples 1:
The contact prescription is: silica flour: the silicon-copper touch body of embodiment 1 preparation: zinc: tin=50: 10: 0.25: 0.0025 (mass ratio)
Experimental implementation is with Comparative Examples 1.(maintenance stannous chloride consumption is constant)
Compare with Comparative Examples 1, it is very fast that reaction starts, and reaction rate obviously improves, silica flour conversion ratio very high (reaction carry out 12 hours after, reaction rate still can keep).Comparing result such as following table 1:
Table 1 catalytic activity contrast table
Claims (4)
1. the preparation method of a silicon-copper touch body: copper sulphate is mixed with sodium chloride, after being heated to reaction temperature, add sodium sulfite solution again, synthesizing chlorinated cuprous through reduction reaction, in building-up process, introduce silica flour, making stannous chloride is nucleus or crystal surface with the silica flour, evenly disperse at silicon powder surface, make the polymolecularity silicon-copper touch body, described reaction temperature is 60～150 ℃, and the silica flour particle diameter is 30～500 microns.
2. according to the method for claim 1, it is characterized in that reaction temperature wherein is 80～100 ℃.
3. according to the method for claim 1, it is characterized in that silica flour particle diameter wherein is 50～150 microns.
4. according to the application of silicon-copper touch body in organochlorosilane is synthetic of the method for claim 1 preparation.
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| CN106187823B (en) * | 2016-07-04 | 2018-06-22 | 江苏省原子医学研究所 | A kind of method for preparing meta iodobenzyl guanidine |
| CN108097274A (en) * | 2017-12-18 | 2018-06-01 | 苏州铜宝锐新材料有限公司 | Catalyst and its application |
| CN108043430A (en) * | 2017-12-18 | 2018-05-18 | 苏州铜宝锐新材料有限公司 | Catalyst and its application |
| CN109607543A (en) * | 2018-12-11 | 2019-04-12 | 中科廊坊过程工程研究院 | A kind of nano silicon particles and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250716A (en) * | 1992-05-28 | 1993-10-05 | Mui Jeffrey Y P | Method for making a silicon/copper contact mass suitable for direct reaction |
| CN1343670A (en) * | 2001-10-19 | 2002-04-10 | 清华大学 | Process and system for synthesizing organosilicon monomer by direct method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250716A (en) * | 1992-05-28 | 1993-10-05 | Mui Jeffrey Y P | Method for making a silicon/copper contact mass suitable for direct reaction |
| CN1343670A (en) * | 2001-10-19 | 2002-04-10 | 清华大学 | Process and system for synthesizing organosilicon monomer by direct method |
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