CN105417547A - Method for converting polymeric chlorosilane under catalysis of liquid phase - Google Patents
Method for converting polymeric chlorosilane under catalysis of liquid phase Download PDFInfo
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- CN105417547A CN105417547A CN201510932802.0A CN201510932802A CN105417547A CN 105417547 A CN105417547 A CN 105417547A CN 201510932802 A CN201510932802 A CN 201510932802A CN 105417547 A CN105417547 A CN 105417547A
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- chlorosilane
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- loaded catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
Abstract
The invention relates to a method for converting polymeric chlorosilane under the catalysis of a liquid phase. The method comprises steps as follows: polymeric chlorosilane and a supported catalyst are added to a reactor firstly, then, the reactor is heated, and hydrogen chloride and polymeric chlorosilane are introduced into the reactor after the temperature of the inside of the reactor is higher than 180 DEG C; the reactor is continuously heated, a liquid phase material in the reactor is extracted after the temperature of the inside of the reactor reaches 200-280 DEG C, and the supported catalyst is added to the reactor; finally, a gas-phase product generated through the reaction is condensed and enters a fractionating tower, and chloro-substituted monosilane is obtained through tower top separation. The method for converting polymeric chlorosilane under the catalysis of the liquid phase has the benefits as follows: 1, the adaptability of raw materials is wide and the utilization rate is high; 2, the process that harmful industrial byproducts are converted into valuable industrial raw materials is realized; 3, the reaction efficiency and the catalyst efficiency are greatly improved due to utilization of mesoporous silica carriers, and besides, the probability that the carriers are chemically decomposed is avoided.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of method of liquid-phase catalysis inversion polymerization chlorosilane.
Background technology
Started from 2013, because technical progress China polysilicon industry generally implements cold hydrogenation transformation.Thus, polysilicon industry endures the by-product of censure to the fullest extent---and a difficult problem for silicon tetrachloride is able to basic solution, and the by-product quantity of polycrystalline silicon device silicon tetrachloride waste liquid is reduced to 0.5 ~ 2 ton by polysilicon per ton 10 ~ 20 tons before.This substantially change before the situation of polysilicon industry high pollution.
After cold hydrogenation transformation, the silicon tetrachloride component of effluent of polycrystalline silicon device by-product there occurs noticeable change, and the content being polymerized chlorosilane in waste liquid significantly rises.Polymerization chlorosilane produces the reaction of chlorosilane and Pure Silicon Metal in the polycrystalline silicon reducing furnace reaction of chlorosilane and silicon rod and cold hydrogenation process.
Obtain being polymerized the one-tenth of chlorosilane by Gc-ms to be grouped into---comprise chloro silicoethane, chloro Trisilicopropane etc.When adopting trichlorosilane to be the Siemens Method+silicon tetrachloride cold hydrogenation technique of raw material, the by-product amount of polymerization chlorosilane is approximately about the 50-150% of polysilicon output; The by-product amount of being polymerized chlorosilane when adopting silane fluidized bed process+silicon tetrachloride cold hydrogenation technique is less slightly; The by-product amount of being polymerized chlorosilane when adopting Siemens Method+hot hydrogenation process obviously increases.
The utilization of polysilicon producer both domestic and external to polymerization chlorosilane is still insufficient, nearly all polysilicon producer all adopts hydrolysis process (usual employing sodium hydroxide is neutralizing agent) by its harmless treatment, but processes a large amount of brine waste of final generation like this and polluted-water.
Based on the problems referred to above, the invention is intended to a kind of method that liquid-phase catalysis inversion polymerization chlorosilane is provided, polymerization chlorosilane is converted into have the chloro list silane of industrial value.
Summary of the invention
Goal of the invention: the present invention is directed to above-mentioned prior art Problems existing and make improvement, namely the invention discloses the method for liquid-phase catalysis inversion polymerization chlorosilane.
Technical scheme: the method for liquid-phase catalysis inversion polymerization chlorosilane, comprises the following steps:
(1) in reactor, polymerization chlorosilane and loaded catalyst is added, loaded catalyst accounts for 0.1 ~ 2% of polymerization chlorosilane add-on, the carrier of described loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(2) to reactor heat supply, temperature in question response device is higher than after 180 DEG C, hydrogenchloride is passed into by reactor bottom, and in reactor, add polymerization chlorosilane continuously by the mode of Liquid level, the liquid level of reaction system is 50% ~ 80% of reactor volume, and the pressure in reactor is 0.1 ~ 35.5bar;
(3) in the mode of indirect heating to reactor continuous heat supply, after in question response device, temperature reaches 200 ~ 280 DEG C, with mass rate M
outliquid phase material in continuous extraction device, wherein:
t is reactor temperature, M
infor being polymerized the feed rate of chlorosilane;
Simultaneously with A*M
outspeed in reactor, add loaded catalyst, A is between 0.001 ~ 0.02, and the carrier of described loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(4) gas-phase product that reaction generates is entered rectifying tower after condensation, tower top is separated and obtains chloro list silane.
A kind of preferred version as the method for liquid-phase catalysis inversion polymerization chlorosilane in the present invention: the chloro list silane in step (4) comprises trichlorosilane and silicon tetrachloride.
A kind of preferred version as the method for liquid-phase catalysis inversion polymerization chlorosilane in the present invention: the material in step (4) at the bottom of tower turns back to reactor and continues reaction.
A kind of preferred version as the method for liquid-phase catalysis inversion polymerization chlorosilane in the present invention: the general formula of described polymerization chlorosilane is H
xsi
ycl
z, wherein, x, y and z are nonnegative integer, y>=2, x>=0, x+z=2+2y.
A kind of preferred version as the method for liquid-phase catalysis inversion polymerization chlorosilane in the present invention: in polymerization chlorosilane, the content of silicon tetrachloride is less than 5wt%.
Further, the quality of being polymerized silicon tetrachloride in chlorosilane is less than 1wt%.
A kind of preferred version as the method for liquid-phase catalysis inversion polymerization chlorosilane in the present invention: the charge capacity of the elemental copper in loaded catalyst described in step (1) is 1 ~ 30%.
A kind of preferred version as the method for liquid-phase catalysis inversion polymerization chlorosilane in the present invention: the charge capacity of the elemental copper in loaded catalyst described in step (3) is 1 ~ 30%.
Beneficial effect: the method for the open liquid-phase catalysis inversion polymerization chlorosilane of the present invention, has following beneficial effect:
1, adopt Continuous Liquid Phase reaction, can to chloro silicoethane, the various polymerization chlorosilane such as chloro Trisilicopropane, chloro tetrasilane carries out catalyzed conversion, adaptability to raw material is wide, utilization ratio is high;
2, the process harmful industrial by-products being converted into valuable industrial raw materials is achieved---reaction product is trichlorosilane and silicon tetrachloride, and the two is all the valuable industrial raw material of tool;
3, meso-porous titanium dioxide silicon carrier can provide larger reaction channel, and the polymerization chlorosilane making molecular weight larger can enter catalyzer duct smoothly and react, and greatly improves the efficiency of reaction and the utilization ratio of catalyzer;
4, silica supports has very excellent chemical stability, avoids the possibility that carrier is chemically decomposed.
Embodiment:
Below the specific embodiment of the present invention is described in detail.
Specific embodiment 1
The method of liquid-phase catalysis inversion polymerization chlorosilane, comprises the following steps:
(1) in reactor, add polymerization chlorosilane and loaded catalyst, loaded catalyst accounts for 0.1% of polymerization chlorosilane add-on, and the carrier of loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(2) to reactor heat supply, temperature in question response device, higher than after 180 DEG C, passes into hydrogenchloride by reactor bottom, and in reactor, adds polymerization chlorosilane continuously by the mode of Liquid level, the liquid level of reaction system is 50% of reactor volume, and the pressure in reactor is 0.1bar;
(3) in the mode of indirect heating to reactor continuous heat supply, after in question response device, temperature reaches 200 DEG C, with mass rate M
outliquid phase material in continuous extraction device, wherein:
t is reactor temperature, M
infor being polymerized the feed rate of chlorosilane;
Simultaneously with A*M
outspeed in reactor, add loaded catalyst, A is 0.001, and the carrier of loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(4) gas-phase product that reaction generates is entered rectifying tower after condensation, tower top is separated and obtains chloro list silane.
Further, the chloro list silane in step (4) comprises trichlorosilane and silicon tetrachloride.
Further, the material in step (4) at the bottom of tower turns back to reactor and continues reaction.
Further, the general formula being polymerized chlorosilane is H
xsi
ycl
z, wherein, x, y and z are nonnegative integer, y>=2, x>=0, x+z=2+2y.
Further, the content being polymerized silicon tetrachloride in chlorosilane is 4.5wt%.
Further, the charge capacity of the elemental copper in step (1) in loaded catalyst is 1%.
Further, the charge capacity of the elemental copper in step (3) in loaded catalyst is 1%.
Specific embodiment 2
The method of liquid-phase catalysis inversion polymerization chlorosilane, comprises the following steps:
(1) in reactor, add polymerization chlorosilane and loaded catalyst, loaded catalyst accounts for 2% of polymerization chlorosilane add-on, and the carrier of loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(2) to reactor heat supply, temperature in question response device is higher than after 180 DEG C, hydrogenchloride is passed into by reactor bottom, and in reactor, add polymerization chlorosilane continuously by the mode of Liquid level, the liquid level of reaction system is 80% of reactor volume, and the pressure in reactor is 35.5bar;
(3) in the mode of indirect heating to reactor continuous heat supply, after in question response device, temperature reaches 280 DEG C, with mass rate M
outliquid phase material in continuous extraction device, wherein:
t is reactor temperature, M
infor being polymerized the feed rate of chlorosilane;
Simultaneously with A*M
outspeed in reactor, add loaded catalyst, A is 0.02, and the carrier of loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(4) gas-phase product that reaction generates is entered rectifying tower after condensation, tower top is separated and obtains chloro list silane.
Further, the chloro list silane in step (4) comprises trichlorosilane and silicon tetrachloride.
Further, the material in step (4) at the bottom of tower turns back to reactor and continues reaction.
Further, the general formula being polymerized chlorosilane is H
xsi
ycl
z, wherein, x, y and z are nonnegative integer, y>=2, x>=0, x+z=2+2y.
Further, the quality of being polymerized silicon tetrachloride in chlorosilane is 1.5wt%.
Further, the charge capacity of the elemental copper in step (1) in loaded catalyst is 30%.
Further, the charge capacity of the elemental copper in step (3) in loaded catalyst is 30%.
Specific embodiment 3
The method of liquid-phase catalysis inversion polymerization chlorosilane, comprises the following steps:
(1) in reactor, add polymerization chlorosilane and loaded catalyst, loaded catalyst accounts for 1% of polymerization chlorosilane add-on, and the carrier of loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(2) to reactor heat supply, temperature in question response device, higher than after 180 DEG C, passes into hydrogenchloride by reactor bottom, and in reactor, adds polymerization chlorosilane continuously by the mode of Liquid level, the liquid level of reaction system is 60% of reactor volume, and the pressure in reactor is 20bar;
(3) in the mode of indirect heating to reactor continuous heat supply, after in question response device, temperature reaches 250 DEG C, with mass rate M
outliquid phase material in continuous extraction device, wherein:
t is reactor temperature, M
infor being polymerized the feed rate of chlorosilane;
Simultaneously with A*M
outspeed in reactor, add loaded catalyst, A is 0.01, and the carrier of loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(4) gas-phase product that reaction generates is entered rectifying tower after condensation, tower top is separated and obtains chloro list silane.
Further, the chloro list silane in step (4) comprises trichlorosilane and silicon tetrachloride.
Further, the material in step (4) at the bottom of tower turns back to reactor and continues reaction.
Further, the general formula being polymerized chlorosilane is H
xsi
ycl
z, wherein, x, y and z are nonnegative integer, y>=2, x>=0, x+z=2+2y.
Further, the quality of being polymerized silicon tetrachloride in chlorosilane is 0.5wt%.
Further, the charge capacity of the elemental copper in step (1) in loaded catalyst is 10%.
Further, the charge capacity of the elemental copper in step (3) in loaded catalyst is 20%.
Above embodiments of the present invention are elaborated.But the present invention is not limited to above-mentioned embodiment, in the ken that art those of ordinary skill possesses, can also make a variety of changes under the prerequisite not departing from present inventive concept.
Claims (8)
1. the method for liquid-phase catalysis inversion polymerization chlorosilane, is characterized in that, comprises the following steps:
(1) in reactor, polymerization chlorosilane and loaded catalyst is added, loaded catalyst accounts for 0.1 ~ 2% of polymerization chlorosilane add-on, the carrier of described loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(2) to reactor heat supply, temperature in question response device is higher than after 180 DEG C, hydrogenchloride is passed into by reactor bottom, and in reactor, add polymerization chlorosilane continuously by the mode of Liquid level, the liquid level of reaction system is 50% ~ 80% of reactor volume, and the pressure in reactor is 0.1 ~ 35.5bar;
(3) in the mode of indirect heating to reactor continuous heat supply, after in question response device, temperature reaches 200 ~ 280 DEG C, with mass rate M
outliquid phase material in continuous extraction device, wherein:
t is reactor temperature, M
infor being polymerized the feed rate of chlorosilane;
Simultaneously with A*M
outspeed in reactor, add loaded catalyst, A is between 0.001 ~ 0.02, and the carrier of described loaded catalyst is the mesoporous silicon oxide that channel diameter is greater than 2nm, and active ingredient is elemental copper;
(4) gas-phase product that reaction generates is entered rectifying tower after condensation, tower top is separated and obtains chloro list silane.
2. the method for liquid-phase catalysis inversion polymerization chlorosilane according to claim 1, is characterized in that, the chloro list silane in step (4) comprises trichlorosilane and silicon tetrachloride.
3. the method for liquid-phase catalysis inversion polymerization chlorosilane according to claim 1, is characterized in that, the material in step (4) at the bottom of tower turns back to reactor and continues reaction.
4. the method for liquid-phase catalysis inversion polymerization chlorosilane according to claim 1, is characterized in that, the general formula of described polymerization chlorosilane is H
xsi
ycl
z, wherein, x, y and z are nonnegative integer, y>=2, x>=0, x+z=2+2y.
5. the method for liquid-phase catalysis inversion polymerization chlorosilane according to claim 1, is characterized in that, in polymerization chlorosilane, the content of silicon tetrachloride is less than 5wt%.
6. the method for liquid-phase catalysis inversion polymerization chlorosilane according to claim 1, is characterized in that, in polymerization chlorosilane, the quality of silicon tetrachloride is less than 1wt%.
7. the method for liquid-phase catalysis inversion polymerization chlorosilane according to claim 1, is characterized in that, the charge capacity of the elemental copper in loaded catalyst described in step (1) is 1 ~ 30%.
8. the method for liquid-phase catalysis inversion polymerization chlorosilane according to claim 1, is characterized in that, the charge capacity of the elemental copper in loaded catalyst described in step (3) is 1 ~ 30%.
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| CN201510932802.0A CN105417547A (en) | 2015-12-15 | 2015-12-15 | Method for converting polymeric chlorosilane under catalysis of liquid phase |
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| CN201510932802.0A CN105417547A (en) | 2015-12-15 | 2015-12-15 | Method for converting polymeric chlorosilane under catalysis of liquid phase |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106809840A (en) * | 2017-03-24 | 2017-06-09 | 亚洲硅业（青海）有限公司 | A kind of preparation method of silicon tetrachloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050113592A1 (en) * | 2003-08-05 | 2005-05-26 | Ge Bayer Silicones Gmbh & Co. | Method for preparing chlorosilane |
| CN102633827A (en) * | 2012-04-26 | 2012-08-15 | 江苏大学 | Method for preparing polychlorinated phenyl trichlorosilane through catalysis of ionic liquid |
| CN103180247A (en) * | 2010-11-09 | 2013-06-26 | 赢创德固赛有限公司 | Process for preparing trichlorosilane |
-
2015
- 2015-12-15 CN CN201510932802.0A patent/CN105417547A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050113592A1 (en) * | 2003-08-05 | 2005-05-26 | Ge Bayer Silicones Gmbh & Co. | Method for preparing chlorosilane |
| CN103180247A (en) * | 2010-11-09 | 2013-06-26 | 赢创德固赛有限公司 | Process for preparing trichlorosilane |
| CN102633827A (en) * | 2012-04-26 | 2012-08-15 | 江苏大学 | Method for preparing polychlorinated phenyl trichlorosilane through catalysis of ionic liquid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106809840A (en) * | 2017-03-24 | 2017-06-09 | 亚洲硅业（青海）有限公司 | A kind of preparation method of silicon tetrachloride |
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Effective date of registration: 20160912 Address after: 753600 Riverside Industrial District, Shizuishan, the Ningxia Hui Autonomous Region Applicant after: NINGXIA SHENGLAN CHEMICAL ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Address before: 315041 room 216, Ningbo Ningbo Court Hotel management, Jiangdong District, Zhejiang Applicant before: NINGBO SHENGYOU TECHNOLOGY SERVICES CO., LTD. |
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