CN104151343A - Additive capable of improving utilization rate of silicon power in synthesis of methyl chlorosilane - Google Patents
Additive capable of improving utilization rate of silicon power in synthesis of methyl chlorosilane Download PDFInfo
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- CN104151343A CN104151343A CN201410347595.8A CN201410347595A CN104151343A CN 104151343 A CN104151343 A CN 104151343A CN 201410347595 A CN201410347595 A CN 201410347595A CN 104151343 A CN104151343 A CN 104151343A
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- silica flour
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Abstract
The invention discloses an additive capable of improving utilization rate of silicon power in synthesis of methyl chlorosilane. The additive is characterized by being prepared from the following components in parts by weight through mixing: 30-70 parts of an oxide, 25-50 parts of silicon powder, 4.5-15 parts of copper powder and 0.5-5 parts of zinc powder, wherein the average particle size of the additive is 70-100mm and the weight ratio of silicon oxide to aluminum oxide to calcium oxide in the oxides is (82-87) to (7-13) to (3-7). At the later stage of a reaction between silicon powder and chloromethane in a fluidized bed, by adopting the reaction additive disclosed by the invention, the intensity of the reaction in the fluidized bed is effectively controlled and thus the quality of the reaction product can be ensured, and meanwhile, since silicon powder is in full contact with chloromethane, the conversion rate of silicon powder is improved, the generation of waste silicon powder is reduced and therefore the production benefits are further increased.
Description
Technical field
The present invention relates to a kind of additive that improves the synthetic middle silica flour utilization ratio of methyl chlorosilane.
Background technology
Organosilicon material (silicones) is a class excellent performance, function uniqueness, broad-spectrum type material, belongs to one of three industries of industry size maximum in New Chemical Materials with engineering plastics, organic fluorine material.Main products comprises promoting agent, coating, foam stabilizer of silicone oil, silicon rubber, silicone resin, silane coupling agent and silicon face etc.Organosilane monomer is mainly used in the manufacturing of organosilicon material, is the basic and crucial of whole organosilicon industry.
The complex manufacturing of organosilane monomer, long flow path, with high content of technology.Methyl chlorosilane monomer synthetic catalyst system is mainly divided into cupric chloride and the large class of copper two.The domestic copper catalyst system that all adopts.Cuprous chloride catalyst system has advantages of that diformazan selectivity is high, and shortcoming is that space-time yield is low.Copper catalyst system has advantages of that activity is high, space-time yield is higher, but diformazan selectivity is unstable.
Organosilane monomer production equipment mainly comprises: silica flour processing unit (plant), monomer synthesizer, monomer separating device, methyl chloride synthesizer, diformazan hydrolysis, cracking and ring body water distilling apparatus etc.The processing unit (plant) of silica flour, before system feeds intake, the air in the nitrogen replacement system that is 99.5% by purity, after nitrogen content >=93% in system, production can feed intake.For ensureing that whole scratch system operates under negative pressure, extract a part of gas out, after cyclonic separator and bag collector two-stage are gathered dust, the gas that makes to be discharged in atmosphere reaches state environmental emissioning standard.
At present, organosilane monomer production technique mainly adopts silica flour and methyl chloride at fluidized-bed reaction synthesizing methyl-chloro-silane, wherein silica flour participates in reaction after adopting raw material silico briquette processing grinding to become certain particle size, its with methyl chloride reaction process in granularity diminish gradually, in normal productive process by adding silica flour adjustment, make the rational mean particle size of maintenance and fluidized state in fluidized-bed, along with the prolongation of the cycle of operation, in fluidized-bed, silica flour impurity increases gradually, affect quality product, need restart reaction, for saving silica flour consumption, most enterprises can drain utilization by the fine powder of collecting in operational process, but draining in process because powder particle size is little, foreign matter content is high, usually drain not thorough, produce the outer processing of selling of reducing the price of a large amount of silica flour contacts.
Existing silica flour and methyl chloride mainly contain ternary copper in the catalyst system of fluidized-bed reaction, and granularity is less, in 2 μ m left and right, this class catalyzer uses in the fluidized-bed reaction later stage drains process, can make methyl chlorosilane reaction more violent, quality product is difficult to control.
Summary of the invention
The object of this invention is to provide a kind of additive that improves the synthetic middle silica flour utilization ratio of methyl chlorosilane.
To achieve these goals, the present invention adopts following technical scheme:
A kind of additive that improves the synthetic middle silica flour utilization ratio of methyl chlorosilane, mix and form by oxide compound, silica flour, copper powder, zinc powder, each component is counted as follows by weight, oxide compound: 30～70 parts, silica flour: 25～50 parts, copper powder: 4.5～15 parts, zinc powder: 0.5～5 part, additive mean particle size 70～100mm, the each components by weight of described oxide compound is: silicon oxide: aluminum oxide: calcium oxide=(82～87): (7～13): (3～7), and preferably: silicon oxide: aluminum oxide: calcium oxide=85:10:5.
During above-mentioned raising methyl chlorosilane is synthetic, the preparation method of the additive of silica flour utilization ratio, mixes each component of described weight part.
The using method of the additive of silica flour utilization ratio during above-mentioned raising methyl chlorosilane is synthetic: silica flour and copper-based catalysts are placed in to fluidized-bed reaction, adjusting pressure is 0.1～0.3Mpa, temperature is 300～350 DEG C, the weight ratio of described silica flour and copper-based catalysts is 20:0.8～1.2, chlorosilane flow is 25～30g/h, in described copper-based catalysts, the mass ratio of each component is: elemental copper: cupric oxide: Red copper oxide=95～97:1～3:1～3, when in methyl chlorosilane when diformazan content≤75%, stop adding copper-based catalysts, add above-mentioned additive, described additive weight used and silica flour part by weight are that 0.8～1.2:1.3～1.7 are (preferred: 1:1.5), regulating fluidized-bed interior reaction temperature is 240 DEG C～350 DEG C, reaction pressure is 0.2MPa～0.4Mpa.
Beneficial effect of the present invention:
(1) additive of the present invention can make the fine powder in fluidized-bed keep good fluidized state, and foreign matter content is little, can dilute the impurity component in waste silicon powder, improve dimethyldichlorosilane(DMCS) content in methyl chlorosilane, and the silica flour that granularity is less sticks to weighting material surface, increase the contact area of silica flour and methyl chloride, improved silica flour transformation efficiency, reached the object that makes full use of silica flour.
(2) compared with prior art, silica flour rate of utilization is improved in process of production in the present invention, reduces the generation of waste silicon powder, has improved the quality of product methyl chlorosilane simultaneously.
(3) the present invention at silica flour and methyl chloride in the fluidized-bed reaction later stage, use reaction additives of the present invention instead, can effectively control the severe degree of reaction in fluidized-bed, thereby the quality of the reactor product that can ensure, raw material silica flour fully contacts with methyl chloride simultaneously, improve silica flour transformation efficiency, reduced the generation of waste silicon powder, further increased productivity effect.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
A kind of additive that improves the synthetic middle silica flour utilization ratio of methyl chlorosilane, mix and form by silicon oxide compound, silica flour, copper powder, zinc powder, each constituent mass is as follows, oxide compound: 30kg, silica flour: 25kg, copper powder: 4.5kg, zinc powder: 0.5kg, additive mean particle size 70mm, described oxide mass ratio, silicon oxide: aluminum oxide: calcium oxide=85:10:5.
Above-mentioned each component is mixed and can be used.
60kg silica flour is positioned in material storing tank, add copper-based catalysts (each constituent mass ratio: elemental copper: cupric oxide: Red copper oxide=95:1:1) 3kg, adjusting pressure is 0.1Mpa, temperature is 300 DEG C, the mass ratio of described silica flour and copper-based catalysts is 20:1, chlorosilane flow is 25g/h, in the time that in methyl chlorosilane, diformazan content is down to below 75%, stop adding copper-based catalysts, regulating temperature of reaction is 240 DEG C, pressure is 0.2MPa, and utilize nitrogen by the additive delivery of above-mentioned preparation to fluidized-bed, when interpolation, silica flour adds according to 3kg/h, additive adds according to adding with silica flour quality 1:1.5 ratio, and to control fluidized-bed reaction temperature be 240 DEG C, pressure is 0.2MPa, until reaction finishes.
Test example
60kg silica flour is positioned in material storing tank, add copper-based catalysts (elemental copper: cupric oxide: Red copper oxide=95:1:1) 3kg, adjusting pressure is 0.1Mpa, temperature is 300 DEG C, the mass ratio of described silica flour and copper-based catalysts is 20:1, chlorosilane flow is 25g/h, until reaction finishes.
The contrast of embodiment 1 and the test example operation effect data of 3 days, as table 1.
Table 1
| Project | Silica flour addition | Silica flour residual content | Average diformazan dichlorosilane content | Methyl chlorosilane output |
| Embodiment 1 | 180kg | 40kg | 87.18％ | 846kg |
| Test example | 180kg | 120kg | 78.75％ | 500kg |
After can obviously finding out use additive of the present invention by Data Comparison, silica flour rate of utilization is improved, and reduces the generation of waste silicon powder, has improved the quality of product methyl chlorosilane simultaneously.
Embodiment 2
A kind of additive that improves the synthetic middle silica flour utilization ratio of methyl chlorosilane, mix and form by silicon oxide compound, silica flour, copper powder, zinc powder, each constituent mass is as follows, oxide compound: 70kg, silica flour: 50kg, copper powder: 15kg, zinc powder: 5kg, additive mean particle size 100mm, described oxide mass mark ratio is, silicon oxide: aluminum oxide: calcium oxide=82:7:3.
Above-mentioned each component is mixed and can be used.
50kg silica flour is positioned in material storing tank, add copper-based catalysts (each constituent mass ratio: elemental copper: cupric oxide: Red copper oxide=95:1:1) 2.5kg, adjusting pressure is 0.3Mpa, temperature is 350 DEG C, the mass ratio of described silica flour and copper-based catalysts is 20:0.8, chlorosilane flow is 30g/h, in the time that in methyl chlorosilane, diformazan content is down to below 75%, stop adding copper-based catalysts, regulating temperature of reaction is 350 DEG C, pressure is 0.4MPa, and utilize nitrogen by the additive delivery of above-mentioned preparation to fluidized-bed, when interpolation, silica flour adds according to 3kg/h, additive adds according to adding with silica flour quality 1:1.5 ratio, and to control fluidized-bed reaction temperature be 350 DEG C, pressure is 0.4MPa, until reaction finishes.
Embodiment 3
A kind of additive that improves the synthetic middle silica flour utilization ratio of methyl chlorosilane, mix and form by silicon oxide compound, silica flour, copper powder, zinc powder, each constituent mass is as follows, oxide compound: 30kg, silica flour: 25kg, copper powder: 4.5kg, zinc powder: 0.5kg, additive mean particle size 70mm, described oxide mass mark ratio is, silicon oxide: aluminum oxide: calcium oxide=87:13:7.
Above-mentioned each component is mixed and can be used.
60kg silica flour is positioned in material storing tank, add copper-based catalysts (each constituent mass ratio: elemental copper: cupric oxide: Red copper oxide=97:3:3) 3kg, adjusting pressure is 0.1Mpa, temperature is 300 DEG C, the mass ratio of described silica flour and copper-based catalysts is 20:1, chlorosilane flow is 25g/h, in the time that in methyl chlorosilane, diformazan content is down to below 75%, stop adding copper-based catalysts, regulating temperature of reaction is 240 DEG C, pressure is 0.2MPa, and utilize nitrogen by the additive delivery of above-mentioned preparation to fluidized-bed, when interpolation, silica flour adds according to 3kg/h, additive adds according to adding with silica flour quality 1:1.5 ratio, and to control fluidized-bed reaction temperature be 240 DEG C, pressure is 0.2MPa, until reaction finishes.
Embodiment 4
A kind of additive that improves the synthetic middle silica flour utilization ratio of methyl chlorosilane, mix and form by silicon oxide compound, silica flour, copper powder, zinc powder, each constituent mass is as follows, oxide compound: 45kg, silica flour: 35kg, copper powder: 8kg, zinc powder: 2kg, additive mean particle size 00mm, described oxide mass mark ratio is, silicon oxide: aluminum oxide: calcium oxide=87:13:7.
Above-mentioned each component is mixed and can be used.
60kg silica flour is positioned in material storing tank, add copper-based catalysts (each constituent mass ratio: elemental copper: cupric oxide: Red copper oxide=97:3:3) 3kg, adjusting pressure is 0.1Mpa, temperature is 300 DEG C, the mass ratio of described silica flour and copper-based catalysts is 20:1, chlorosilane flow is 25g/h, in the time that in methyl chlorosilane, diformazan content is down to below 75%, stop adding copper-based catalysts, regulating temperature of reaction is 240 DEG C, pressure is 0.2MPa, and utilize nitrogen by the additive delivery of above-mentioned preparation to fluidized-bed, when interpolation, silica flour adds according to 3kg/h, additive adds according to adding with silica flour quality 1:1.5 ratio, and to control fluidized-bed reaction temperature be 300 DEG C, pressure is 0.3MPa, until reaction finishes.
Embodiment 5
A kind of additive that improves the synthetic middle silica flour utilization ratio of methyl chlorosilane, mix and form by silicon oxide compound, silica flour, copper powder, zinc powder, each constituent mass is as follows, oxide compound: 60kg, silica flour: 40kg, copper powder: 10kg, zinc powder: 4kg, additive mean particle size 90mm, described oxide mass mark ratio is, silicon oxide: aluminum oxide: calcium oxide=82:7:3.
50kg silica flour is positioned in material storing tank, add copper-based catalysts (each constituent mass ratio: elemental copper: cupric oxide: Red copper oxide=95:1:1) 2.5kg, adjusting pressure is 0.3Mpa, temperature is 350 DEG C, the mass ratio of described silica flour and copper-based catalysts is 20:0.8, chlorosilane flow is 30g/h, in the time that in methyl chlorosilane, diformazan content is down to below 75%, stop adding copper-based catalysts, regulating temperature of reaction is 350 DEG C, pressure is 0.4MPa, and utilize nitrogen by the additive delivery of above-mentioned preparation to fluidized-bed, when interpolation, silica flour adds according to 3kg/h, additive adds according to adding with silica flour quality 1:1.5 ratio, and to control fluidized-bed reaction temperature be 350 DEG C, pressure is 0.4MPa, until reaction finishes.
The specific embodiment of the present invention is described although above-mentioned in conjunction with the embodiments; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendments that creative work can make or distortion still in protection scope of the present invention.
Claims (9)
1. one kind is improved the additive of the synthetic middle silica flour utilization ratio of methyl chlorosilane, it is characterized in that, mix and form by oxide compound, silica flour, copper powder, zinc powder, each component is counted as follows by weight, oxide compound: 30～70 parts, silica flour: 25～50 parts, copper powder: 4.5～15 parts, zinc powder: 0.5～5 part, additive mean particle size 70～100mm, the each components by weight of described oxide compound is: silicon oxide: aluminum oxide: calcium oxide=(82～87): (7～13): (3～7).
2. the additive of the synthetic middle silica flour utilization ratio of raising methyl chlorosilane as claimed in claim 1, is characterized in that described silicon oxide: aluminum oxide: calcium oxide=85:10:5.
3. the additive of the synthetic middle silica flour utilization ratio of raising methyl chlorosilane as claimed in claim 1, it is characterized in that, the each component of described interpolation is counted as follows by weight, oxide compound: 45～60 parts, silica flour: 35～40 parts, copper powder: 8～10 parts, zinc powder: 2～4 parts, additive mean particle size 80～90mm.
4. during raising methyl chlorosilane as described in as arbitrary in claim 1-3 is synthetic, the preparation method of the additive of silica flour utilization ratio, is characterized in that, each component of described weight part is mixed.
5. the preparation method of the additive of silica flour utilization ratio during raising methyl chlorosilane as described in as arbitrary in claim 1-3 is synthetic, it is characterized in that, silica flour and copper-based catalysts are placed in to fluidized-bed reaction, adjusting pressure is 0.1～0.3Mpa, temperature is 300～350 DEG C, the weight ratio of described silica flour and copper-based catalysts is 20:0.8～1.2, chlorosilane flow is 25～30g/h, in described copper-based catalysts, the mass ratio of each component is: elemental copper: cupric oxide: Red copper oxide=95～97:1～3:1～3, when in methyl chlorosilane when diformazan content≤75%, stop adding copper-based catalysts, add above-mentioned additive, described additive weight used and silica flour part by weight are 0.8～1.2:1.3～1.7, regulating fluidized-bed interior reaction temperature is 240 DEG C～350 DEG C, reaction pressure is 0.2MPa～0.4Mpa.
6. the preparation method of the additive of the synthetic middle silica flour utilization ratio of raising methyl chlorosilane as claimed in claim 5, is characterized in that, described additive weight used and silica flour part by weight are 1:1.5.
7. the preparation method of the additive of the synthetic middle silica flour utilization ratio of raising methyl chlorosilane as claimed in claim 6, is characterized in that, described adjusting fluidized-bed interior reaction temperature is 300 DEG C.
8. the preparation method of the additive of the synthetic middle silica flour utilization ratio of raising methyl chlorosilane as claimed in claim 7, is characterized in that, described reaction pressure is 0.3Mpa.
Raising methyl chlorosilane as claimed in claim 7 synthetic in the preparation method of additive of silica flour utilization ratio, it is characterized in that, when the above-mentioned additive of described interpolation, use nitrogen to be delivered in fluidized-bed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218222A (en) * | 2019-05-30 | 2019-09-10 | 鲁西化工集团股份有限公司 | A method of extending fluidized bed cycle of operation raising running quality |
| CN114409695A (en) * | 2022-01-26 | 2022-04-29 | 云南能投硅材科技发展有限公司 | Comprehensive utilization method of waste silicon powder in organic silicon monomer synthesis process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043112A (en) * | 1988-12-08 | 1990-06-20 | 埃尔凯姆公司 | Silica flour and production method thereof |
| US5427952A (en) * | 1993-01-11 | 1995-06-27 | Dow Corning Corporation | Analytical method for nonmetallic contaminates in silicon |
| CN1437562A (en) * | 2000-04-20 | 2003-08-20 | 通用电气公司 | Method for preparing a contact mass |
| CN101456877A (en) * | 2008-12-08 | 2009-06-17 | 江苏宏达新材料股份有限公司 | Contact masses processing method during methylchlorosilane synthesis |
| CN103566955A (en) * | 2012-08-02 | 2014-02-12 | 中国石油天然气股份有限公司 | Catalyst for improving selectivity of dimethyldichlorosilane and application thereof |
-
2014
- 2014-07-21 CN CN201410347595.8A patent/CN104151343B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043112A (en) * | 1988-12-08 | 1990-06-20 | 埃尔凯姆公司 | Silica flour and production method thereof |
| US5427952A (en) * | 1993-01-11 | 1995-06-27 | Dow Corning Corporation | Analytical method for nonmetallic contaminates in silicon |
| CN1437562A (en) * | 2000-04-20 | 2003-08-20 | 通用电气公司 | Method for preparing a contact mass |
| CN101456877A (en) * | 2008-12-08 | 2009-06-17 | 江苏宏达新材料股份有限公司 | Contact masses processing method during methylchlorosilane synthesis |
| CN103566955A (en) * | 2012-08-02 | 2014-02-12 | 中国石油天然气股份有限公司 | Catalyst for improving selectivity of dimethyldichlorosilane and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218222A (en) * | 2019-05-30 | 2019-09-10 | 鲁西化工集团股份有限公司 | A method of extending fluidized bed cycle of operation raising running quality |
| CN114409695A (en) * | 2022-01-26 | 2022-04-29 | 云南能投硅材科技发展有限公司 | Comprehensive utilization method of waste silicon powder in organic silicon monomer synthesis process |
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