CN105236414A - Silicon tetrachloride recycling method - Google Patents
Silicon tetrachloride recycling method Download PDFInfo
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- CN105236414A CN105236414A CN201510601662.9A CN201510601662A CN105236414A CN 105236414 A CN105236414 A CN 105236414A CN 201510601662 A CN201510601662 A CN 201510601662A CN 105236414 A CN105236414 A CN 105236414A
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Abstract
The invention relates to a silicon tetrachloride recycling method. The method comprises the following steps: vaporizing silicon tetrachloride, introducing vaporized silicon tetrachloride into a reaction kettle, and carrying out subsurface bubbling hydrolysis at 30-80DEG C until silicon tetrachloride is completely hydrolyzed; introducing 0.3-0.5MPa steam into a reaction kettle, and reacting at 80-170DEG C for 2-6h; sending the above obtained compound into a liquid separator, separating out an upper layer oily matter; continuously conveying a lower layer water phase into the reaction kettle to hydrolyze silicon tetrachloride until the mass concentration of HCl in the obtained filtrate reaches 20-30% in order to obtain hydrochloric acid; and washing the oily matter in the liquid separator with an alkali solution until neutrality, continuously washing with water three times, settling for 20-48h to obtain a solid, grinding, washing with water, sending the washed solid into a drying machine, and drying to obtain silica hydrate. The method has the advantages of production cost reduction, simple operation, small influences on environment, and environmental protection.
Description
Technical field
The present invention relates to chemical field, particularly a kind of recoverying and utilizing method of silicon tetrachloride.
Background technology
Silicon tetrachloride is the middle by product of production of polysilicon, and polysilicon is electronic industry and the main raw material required for photovoltaic industry, and in the production of polysilicon, often produce one ton of polysilicon, just need the silicon tetrachloride of process 15 tons, treatment capacity is very large.Undressed silicon tetrachloride is a kind of chemical substance with severe corrosive, is heated or meets water decomposition heat release, releasing poisonous corrosive fume, very big to environmental hazard.
Along with the theCourse of PV Industry of the world and China, solar cell demand is increasing, and polysilicon output increases year by year, the environmental problem that silicon tetrachloride as by-product brings and resource utilization issue mouth benefit outstanding.There is no good solution and approach in industry all the time.The harmless treatment of silicon tetrachloride becomes one of bottleneck of restriction polysilicon development.
Provide a kind of method of gas phase treatment silicon tetrachloride in prior art, the silicon tetrachloride of gaseous state and a certain amount of hydrogen and oxygen (or air) are carried out vapor phase hydrolysis under the high temperature of about 1800 DEG C, generate nano-scale white carbon black.Because nano-scale white carbon black added value is high, be therefore the better method effectively utilizing silicon tetrachloride, more employing abroad.But because the method service temperature is too high, very high to equipment requirements, investment is large, and process cost is high; In addition because nano-scale white carbon black market capacity is limited, the simple silicon tetrachloride adopting vapor phase process cannot digest substantial amounts.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of recoverying and utilizing method of silicon tetrachloride, and the feature of the method is to reclaim the hydrate and hydrochloric acid that obtain silicon-dioxide.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of recoverying and utilizing method of silicon tetrachloride, and step is:
(1) silicon tetrachloride liquid is joined in vaporizer, obtain the silicon tetrachloride of vaporizing with heat-conducting oil heating vaporizer;
(2) passed in reactor by the silicon tetrachloride of described vaporization and carry out bubbling hydrolysis under liquid, complete to hydrolyzing silicon tetrachloride, hydrolysis temperature is 30-80 DEG C;
(3) in reactor, pass into 0.3-0.5MPa steam further and carry out polycondensation, the reaction times is 2-6h, and temperature of reaction is 80-170 DEG C;
(4) with pump, described compound is sent in skimmer, separate upper strata oily matter; Lower floor's aqueous phase can continue on in the reactor described in step (2) and be hydrolyzed to silicon tetrachloride, until the mass concentration of HCl reaches 20-30% in gained filtrate, obtains hydrochloric acid;
(5) oily matter continues to be washed till neutrality with alkali lye in skimmer, then continues to wash three times with water, and then obtains solid through 20-48h sedimentation, and finally by solid abrasive, washing, sends into drying machine dry, obtain the hydrate of silicon-dioxide.
In a preferred embodiment of the present invention, described silicon tetrachloride is the silicon tetrachloride as by-product of suitability for industrialized production, and content is at 60%-90%, and purity is greater than 95%.
In a preferred embodiment of the present invention, the hydrolysis reaction described in step (2) is entirely the reaction times at 5-12h.
In a preferred embodiment of the present invention, the temperature of reaction described in step (2) is 30-50 DEG C.
In a preferred embodiment of the present invention, the reaction times described in step (3) is 3-4h, and temperature of reaction is 100-120 DEG C.
In a preferred embodiment of the present invention, the alkali lye described in step (5) is aqueous sodium hydroxide solution, potassium hydroxide aqueous solution or ammoniacal liquor.
In a preferred embodiment of the present invention, the time of the drying machine drying described in step (5) is 1-2h.
Beneficial effect of the present invention is: silicon tetrachloride byproduct is transformed into Silicon dioxide, hydrate and hydrochloric acid by the present invention, realizes recycle, reduces production cost, simultaneously simple to operate, little to environmental influence, is environmental protection technique.
Embodiment
The specific embodiment of the present invention is described in detail as follows, but for illustrative purposes only instead of restriction the present invention.
Embodiment 1
(1) content is joined in vaporizer in 60% silicon tetrachloride liquid, obtain the silicon tetrachloride of vaporizing with heat-conducting oil heating vaporizer;
(2) silicon tetrachloride of described vaporization is passed in reactor carry out bubbling hydrolysis under liquid, complete to hydrolyzing silicon tetrachloride, reaction times 5h, hydrolysis temperature is 30-80 DEG C;
(3) in reactor, pass into 0.3-0.5MPa steam further and carry out polycondensation, the reaction times is 2h, and temperature of reaction is 170 DEG C;
(4) with pump, described compound is sent in skimmer, separate upper strata oily matter; Lower floor's aqueous phase can continue on in the reactor described in step (2) and be hydrolyzed to silicon tetrachloride, until the mass concentration of HCl reaches 20% in gained filtrate, obtains hydrochloric acid;
(5) oily matter continues to be washed till neutrality with alkali lye in skimmer, then continues to wash three times with water, and then obtains solid through 48h sedimentation, and finally by solid abrasive, washing, sends into drying machine dry, obtain the hydrate of silicon-dioxide.
Embodiment 2
(1) content is joined in vaporizer in 80% silicon tetrachloride liquid, obtain the silicon tetrachloride of vaporizing with heat-conducting oil heating vaporizer;
(2) silicon tetrachloride of described vaporization is passed in reactor carry out bubbling hydrolysis under liquid, complete to hydrolyzing silicon tetrachloride, reaction times 8h, hydrolysis temperature is 50 DEG C;
(3) in reactor, pass into 0.3-0.5MPa steam further and carry out polycondensation, the reaction times is 4h, and temperature of reaction is 130 DEG C;
(4) with pump, described compound is sent in skimmer, separate upper strata oily matter; Lower floor's aqueous phase can continue on in the reactor described in step (2) and be hydrolyzed to silicon tetrachloride, until the mass concentration of HCl reaches 25% in gained filtrate, obtains hydrochloric acid;
(5) oily matter continues to be washed till neutrality with alkali lye in skimmer, then continues to wash three times with water, and then obtains solid through 30h sedimentation, and finally by solid abrasive, washing, sends into drying machine dry, obtain the hydrate of silicon-dioxide.
Embodiment 3
(1) content is joined in vaporizer in 00% silicon tetrachloride liquid, obtain the silicon tetrachloride of vaporizing with heat-conducting oil heating vaporizer;
(2) silicon tetrachloride of described vaporization is passed in reactor carry out bubbling hydrolysis under liquid, complete to hydrolyzing silicon tetrachloride, reaction times 12h, hydrolysis temperature is 30 DEG C;
(3) in reactor, pass into 0.3-0.5MPa steam further and carry out polycondensation, the reaction times is 6h, and temperature of reaction is 80 DEG C;
(4) with pump, described compound is sent in skimmer, separate upper strata oily matter; Lower floor's aqueous phase can continue on in the reactor described in step (2) and be hydrolyzed to silicon tetrachloride, until the mass concentration of HCl reaches 30% in gained filtrate, obtains hydrochloric acid;
(5) oily matter continues to be washed till neutrality with alkali lye in skimmer, then continues to wash three times with water, and then obtains solid through 20h sedimentation, and finally by solid abrasive, washing, sends into drying machine dry, obtain the hydrate of silicon-dioxide.
Claims (7)
1. a recoverying and utilizing method for silicon tetrachloride, is characterized in that, step is:
(1) silicon tetrachloride liquid is joined in vaporizer, obtain the silicon tetrachloride of vaporizing with heat-conducting oil heating vaporizer;
(2) passed in reactor by the silicon tetrachloride of described vaporization and carry out bubbling hydrolysis under liquid, complete to hydrolyzing silicon tetrachloride, hydrolysis temperature is 30-80 DEG C;
(3) in reactor, pass into 0.3-0.5MPa steam further and carry out polycondensation, the reaction times is 2-6h, and temperature of reaction is 80-170 DEG C;
(4) with pump, described compound is sent in skimmer, separate upper strata oily matter; Lower floor's aqueous phase can continue on in the reactor described in step (2) and be hydrolyzed to silicon tetrachloride, until the mass concentration of HCl reaches 20-30% in gained filtrate, obtains hydrochloric acid;
(5) oily matter continues to be washed till neutrality with alkali lye in skimmer, then continues to wash three times with water, and then obtains solid through 20-48h sedimentation, and finally by solid abrasive, washing, sends into drying machine dry, obtain the hydrate of silicon-dioxide.
2. the recoverying and utilizing method of silicon tetrachloride according to claim 1, is characterized in that, described silicon tetrachloride is the silicon tetrachloride as by-product of suitability for industrialized production, and content is at 60%-90%, and purity is greater than 95%.
3. the recoverying and utilizing method of silicon tetrachloride according to claim 1, is characterized in that, the hydrolysis reaction described in step (2) is entirely the reaction times at 5-12h.
4. the recoverying and utilizing method of silicon tetrachloride according to claim 1, is characterized in that, the temperature of reaction described in step (2) is 30-50 DEG C.
5. the recoverying and utilizing method of silicon tetrachloride according to claim 1, is characterized in that, the reaction times described in step (3) is 3-4h, and temperature of reaction is 100-120 DEG C.
6. the recoverying and utilizing method of silicon tetrachloride according to claim 1, is characterized in that, the alkali lye described in step (5) is aqueous sodium hydroxide solution, potassium hydroxide aqueous solution or ammoniacal liquor.
7. the recoverying and utilizing method of silicon tetrachloride according to claim 1, is characterized in that, the time of the drying machine drying described in step (5) is 1-2h.
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| CN201510601662.9A CN105236414A (en) | 2015-09-21 | 2015-09-21 | Silicon tetrachloride recycling method |
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| CN201510601662.9A CN105236414A (en) | 2015-09-21 | 2015-09-21 | Silicon tetrachloride recycling method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536326A (en) * | 2016-01-22 | 2016-05-04 | 峨眉山长庆化工新材料有限公司 | Liquid silicon tetrachloride filter structure and cleaning method |
Citations (5)
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| CN101863480A (en) * | 2010-06-25 | 2010-10-20 | 应城市东诚有机硅有限公司 | Preparation method for silicon dioxide aerogel |
| CN101863479A (en) * | 2010-06-25 | 2010-10-20 | 应城市东诚有机硅有限公司 | Method for preparing silica aerogel by supercritical drying with high-pressure liquid medium |
| CN102198941A (en) * | 2010-03-26 | 2011-09-28 | 中国石油天然气股份有限公司 | Method for preparing white carbon black by hydrolyzing silicon tetrachloride |
| CN102275940A (en) * | 2011-07-28 | 2011-12-14 | 河北东明中硅科技有限公司 | Method for low-temperature hydrolysis of silicon tetrachloride |
| CN103043610A (en) * | 2011-10-12 | 2013-04-17 | 北京华宇同方化工科技开发有限公司 | Method and system for treating silicon tetrachloride by hydrolysis method |
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- 2015-09-21 CN CN201510601662.9A patent/CN105236414A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198941A (en) * | 2010-03-26 | 2011-09-28 | 中国石油天然气股份有限公司 | Method for preparing white carbon black by hydrolyzing silicon tetrachloride |
| CN101863480A (en) * | 2010-06-25 | 2010-10-20 | 应城市东诚有机硅有限公司 | Preparation method for silicon dioxide aerogel |
| CN101863479A (en) * | 2010-06-25 | 2010-10-20 | 应城市东诚有机硅有限公司 | Method for preparing silica aerogel by supercritical drying with high-pressure liquid medium |
| CN102275940A (en) * | 2011-07-28 | 2011-12-14 | 河北东明中硅科技有限公司 | Method for low-temperature hydrolysis of silicon tetrachloride |
| CN103043610A (en) * | 2011-10-12 | 2013-04-17 | 北京华宇同方化工科技开发有限公司 | Method and system for treating silicon tetrachloride by hydrolysis method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536326A (en) * | 2016-01-22 | 2016-05-04 | 峨眉山长庆化工新材料有限公司 | Liquid silicon tetrachloride filter structure and cleaning method |
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