CN103566955B - Catalyst for improving selectivity of dimethyldichlorosilance and application thereof - Google Patents
Catalyst for improving selectivity of dimethyldichlorosilance and application thereof Download PDFInfo
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- CN103566955B CN103566955B CN201210273344.0A CN201210273344A CN103566955B CN 103566955 B CN103566955 B CN 103566955B CN 201210273344 A CN201210273344 A CN 201210273344A CN 103566955 B CN103566955 B CN 103566955B
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Abstract
The invention relates to a catalyst for improving selectivity of dimethyldichlorosilance and application thereof. The catalyst is composed of cuprous chloride, zinc powder, stannous fluoride, silicon powder and copper powder in a mass ratio of 94-96:1.7-2.3:2-3:0.2-0.6:0.07-0.15; chloromethane and silicon powder are used for producing the dimethyldichlorosilance catalyst, production is carried out in a fluidized bed, the mass ratio of silicon powder to catalyst is 100:1, reaction temperature of chloromethane and silicon powder is 270-350 DEG C, reaction pressure is 0.15MPa-0.3MPa, and the mass ratio of silicon powder to chloromethane is 1:2.5. The catalyst can effectively improving the selectivity of dimethyldichlorosilance; therefore, quality and yield of dimethyldichlorosilance can be more steady, technology is simple and easy to control, and safety is good.
Description
Technical field
The present invention relates to the organosilyl catalyst of a kind of production, be specifically related to produce the catalyst used in dimethyldichlorosilane process, to the method for its main co-catalyst glass putty modification.
Background technology
In organosilicon manufacture, what generally adopt is under copper catalyst effect, react direct synthesizing methyl-chloro-silane technology by chloromethanes and silica flour.This method has that raw material is easy to get, operation is simple, efficiency is high, and is easy to realize the advantages such as continuous mass production, becomes the main method of industrial production methylchlorosilane at present.
The production of current most of Organic Silicon Plant methyl chlorosilane monomer is in fluid bed, and take stannous chloride as major catalyst, chloromethanes and silica flour react within the scope of 270-350 DEG C, mainly generate dimethyldichlorosilane.
Wherein conventional catalyst is constructed as follows:
(1) major catalyst stannous chloride: play considerable effect to raising dimethyldichlorosilane selective reduction reaction temperature, stannous chloride reaction useless is basic without any meaning.
(2) co-catalyst zinc powder: can improve dimethyldichlorosilane selective, reduces reaction temperature.
(3) co-catalyst glass putty: can dimethyldichlorosilane be improved selective, but use too much can make major catalyst poisoning.
The selective of dimethyldichlorosilane more than 85%, but should find in practical operation under normal circumstances, and it is selective changes greatly, and selective often lower than 85%, has a strong impact on the output of dimethyldichlorosilane.
Affect dimethyldichlorosilane optionally main cause have following two aspects:
(1) fluid bed inner catalyst contact poor quality, return catalytic component in bed contact and change, side reaction increases.
(2) fluidized-bed pressure is high, causes hot-spot, and side reaction increases, and the high product that causes of bed pressure leaves contact surface difficulty, and side reaction increases.
Can see from above, affect the selective chief reason of dimethyldichlorosilane and be catalyst and contact thereof, if effective modified catalyst, the selective of dimethyldichlorosilane can be improved.
Patent US5334738 proposition P Modification catalyst contact can improve the selective of dimethyldichlorosilane.US6211394 proposes to adopt CuO and CuCl composite catalyst to switch and uses, and whole course of reaction can be made to remain on high selective always, overcome the shortcoming of single catalyst at the handoff procedure of catalyst.US4895969 proposes to replace zinc with zinc compound also can improve the selective of dimethyldichlorosilane.US6175030 proposes in contact, introduce pyrogene silicic acid and allows to reduce Cu, Zn content, and does not reduce reaction selectivity.The composite catalyst that its Patent US6211394 proposes switches use, and through practical operation, the selective of dimethyldichlorosilane can reach 85%, but this kind of method catalyst switches comparatively frequent, more difficult grasp switching time.With the optionally method of zinc compound replacement zinc raising dimethyldichlorosilane, what patent US4895969 proposed requires that the conversion ratio of silica flour must between 79%-86%, just can effectively improve the selective of dimethyldichlorosilane, but for controlling the conversion ratio of silica flour in the more difficult control of 79%-86%.
No matter main organosilicon manufacturer domestic at present adopts which kind of method modified catalyst above, and effect is all undesirable, and the main organosilicon manufacturer data in the selective and world of its organosilicon product dimethyldichlorosilane produced is compared, and differs still larger.
Summary of the invention
The object of this invention is to provide a kind of raising dimethyldichlorosilane optionally catalyst, under the condition not changing existing apparatus production status, effectively can improve the selective of dimethyldichlorosilane.
One of the present invention improves dimethyldichlorosilane optionally catalyst, its component comprises: stannous chloride, zinc powder, stannous fluoride, silica flour, copper powder, and each constituent mass proportioning is: stannous chloride: zinc powder: stannous fluoride: silica flour: copper powder=94 ~ 96:1.7 ~ 2.3:2 ~ 3:0.2 ~ 0.6:0.07 ~ 0.15.
Catalyst preparation process: stannous chloride, zinc powder, stannous fluoride, silica flour, copper powder are mixed in proportion, then pass in drying oven, kiln temperatures was warmed up to 200 DEG C by normal temperature in 30 minutes, then passing into pressure is that the nitrogen of 0.5Mp is by catalyst fluidization, catalyst keeps nitrogen fluidisation 1 hour in the drying oven of 200 DEG C, then drops to normal temperature and keeps dry stand-by.
The production of organosilicon product dimethyldichlorosilane is carried out in fluid bed, the mass ratio of silica flour and catalyst is 100:1, and chloromethanes and silica flour reaction temperature are 270 DEG C ~ 350 DEG C, and preferable reaction temperature is 295 DEG C, reaction pressure is 0.15MPa ~ 0.3MPa, is preferably 0.2MPa.Synthesis quality is than silica flour/chloromethanes=1/2.5.
Method provided by the present invention compared with prior art tool has the following advantages:
(1) only need the co-catalyst in modified catalyst, requirement is not done to major catalyst;
(2) modified catalyst does not need to change original reaction condition of process units;
(3) the co-catalyst stannous fluoride of modification is simple and easy to get.
(4) use modified catalyst, can improve the selective of dimethyldichlorosilane significantly, average selectivity is 92%.
In sum, the present invention can effectively improve the selective of dimethyldichlorosilane, to solve in silicone industry about the selective difficult problem generally on the low side of dimethyldichlorosilane, makes the Quality and yield of dimethyldichlorosilane more stable.Method involved in the present invention easily controls, and technique is simple, and security is high.
Detailed description of the invention
Comparative example 1
Reaction unit is temperature 295 DEG C, and pressure 0.2MPa, the mass ratio of silica flour and catalyst, under the condition of 100:1, runs 2 months continuously, gets and wherein within any 15 days, analyzes data, and original catalytic component is in table 1, and original catalysts conditions analyzes data for lower 15 days in table 2.
The original catalytic component of table 1
| Old catalyst is formed | Stannous chloride | Zinc powder | Glass putty | Silica flour | Copper powder |
| Mass ratio (%) | 95 | 1.5 | 2.5 | 0.6 | 0.4 |
The original catalysts conditions of table 2 analyzes data in lower 15 days
In table 2, data are through calculating, and the original catalyst of visible employing, the average selectivity of dimethyldichlorosilane only has 80.8%.
Embodiment 1
Reaction unit temperature 295 DEG C, pressure 0.2MPa, the mass ratio of silica flour and catalyst is under the condition of 100:1, adopt new modified catalyst, in table 3, run 2 months continuously at organosilicon process units, get and wherein within any 15 days, analyze data, dimethyldichlorosilane selective as table 4.Quality is than silica flour/chloromethanes=1/2.5.
Table 3 raw catelyst component
| Old catalyst is formed | Stannous chloride | Zinc powder | Stannous fluoride | Silica flour | Copper powder |
| Mass ratio (%) | 95 | 2 | 2.5 | 0.4 | 0.1 |
Table 4 raw catelyst condition analyzes data in lower 15 days
In table 4, data are through calculating, and after obtaining adopting modified catalyst, the average selectivity of dimethyldichlorosilane reaches 92.8%.Visible, after adopting new catalyst, the selective of dimethyldichlorosilane significantly improves.
Claims (3)
1. improve a dimethyldichlorosilane optionally catalyst, it is characterized in that: catalyst is made up of stannous chloride, zinc powder, stannous fluoride, silica flour, copper powder; Each constituent mass proportioning is: stannous chloride: zinc powder: stannous fluoride: silica flour: copper powder=94 ~ 96:1.7 ~ 2.3:2 ~ 3:0.2 ~ 0.6:0.07 ~ 0.15.
2. the application of a raising dimethyldichlorosilane according to claim 1 optionally catalyst, it is characterized in that: produce dimethyldichlorosilane for chloromethanes and silica flour, produce and carry out in fluid bed, the mass ratio of silica flour and catalyst is 100:1, chloromethanes and silica flour reaction temperature are 270 DEG C ~ 350 DEG C, reaction pressure is 0.15MPa ~ 0.3MPa, silica flour/chloromethanes mass ratio 1/2.5.
3. the application of raising dimethyldichlorosilane according to claim 2 optionally catalyst, it is characterized in that: its reaction temperature is 295 DEG C, reaction pressure is 0.2MPa.
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| CN201210273344.0A CN103566955B (en) | 2012-08-02 | 2012-08-02 | Catalyst for improving selectivity of dimethyldichlorosilance and application thereof |
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| CN103566955B true CN103566955B (en) | 2015-05-13 |
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| CN104151343B (en) * | 2014-07-21 | 2016-09-07 | 鲁西化工集团股份有限公司硅化工分公司 | A kind of improve the additive of silica flour utilization rate in methylchlorosilane synthesis |
| CN108097274A (en) * | 2017-12-18 | 2018-06-01 | 苏州铜宝锐新材料有限公司 | Catalyst and its application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500724A (en) * | 1983-07-28 | 1985-02-19 | General Electric Company | Method for making alkylhalosilanes |
| US6005130A (en) * | 1998-09-28 | 1999-12-21 | General Electric Company | Method for making alkylhalosilanes |
| CN1437562A (en) * | 2000-04-20 | 2003-08-20 | 通用电气公司 | Method for preparing a contact mass |
| CN1806911A (en) * | 2004-10-19 | 2006-07-26 | 信越化学工业株式会社 | Making of contact mass for organohalosilane preparation and preparation of organohalosilanes |
-
2012
- 2012-08-02 CN CN201210273344.0A patent/CN103566955B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4500724A (en) * | 1983-07-28 | 1985-02-19 | General Electric Company | Method for making alkylhalosilanes |
| US6005130A (en) * | 1998-09-28 | 1999-12-21 | General Electric Company | Method for making alkylhalosilanes |
| CN1437562A (en) * | 2000-04-20 | 2003-08-20 | 通用电气公司 | Method for preparing a contact mass |
| CN1806911A (en) * | 2004-10-19 | 2006-07-26 | 信越化学工业株式会社 | Making of contact mass for organohalosilane preparation and preparation of organohalosilanes |
Non-Patent Citations (1)
| Title |
|---|
| 罗务习,等."甲基氯硅烷单体合成反应中CuCl催化剂改性研究".《化学工程》.2006,第34卷(第2期),全文. * |
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