CN102086526A - Method for preparing zinc by electrolyzing ZnC12 molten salt - Google Patents
Method for preparing zinc by electrolyzing ZnC12 molten salt Download PDFInfo
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- CN102086526A CN102086526A CN200910200121XA CN200910200121A CN102086526A CN 102086526 A CN102086526 A CN 102086526A CN 200910200121X A CN200910200121X A CN 200910200121XA CN 200910200121 A CN200910200121 A CN 200910200121A CN 102086526 A CN102086526 A CN 102086526A
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- zncl
- fused salt
- salt electrolysis
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- system zinc
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Abstract
The invention provides a method for preparing zinc by electrolyzing ZnC12 molten salt. The method is implemented through a set of devices for preparing the zinc by electrolyzing the ZnC12 molten salt; a molten salt electrolysis method is adopted; a heating device is utilized to keep ZnCl2 in a molten state, and the ZnC12 molten salt is directly electrolyzed under the condition of not adding any auxiliary electrolyte; and an electrolysate is molten Zn and gaseous Cl2. By the method, a byproduct, namely the Znc12 obtained from the production of polycrystalline silicon by reducing SiCl4 by the Zn can be recycled, and the closed loop of the whole production technology for the production of the polycrystalline silicon by reducing the SiCl4 by the Zn can be realized. The method has low operating and economic cost, is not required to add other auxiliary electrolytes, and is less in introduced impurities, and simple and convenient in operation.
Description
Technical field
The present invention relates to a kind of electrolysis process, particularly a kind of method of ZnCl2 fused salt electrolysis system zinc.
Background technology
Present domestic major part has been built and in the polysilicon project of building, to technology such as tail gas recycle and by product processing not on top of as yet, developed country carries out blockade on new techniques to China again, and this has buried hidden danger for following benign development.China relies on now be import some be not that the production of polysilicon is carried out in complete technology and equipment, enhance production capacities.Its technological line mainly is to adopt chlorosilane (Siemens Method or improvement Siemens Method) to make polysilicon, causes 1 mole of polysilicon of every production will produce 3.26 moles SiCl
4, promptly produce the SiCl that 1 ton of polysilicon will produce 19.44 tons
4If more than the technological cycle to four time, about 4 tons of SiCl are arranged still
4Need to handle, the round-robin number of times is not The more the better certainly, and the consideration of a balance various factors is arranged.Because external technology to China all is through the technology after filtering, do not reach the final 4 tons of SiCl of generation of one ton of polysilicon of every production far away
4State of the art.Therefore the polysilicon output sum data of announcing according to many companies such as Chinese Cheng Da 85250 tons/year (2010) is calculated, and there is 1657260 tons SiCl in annual so when the time comes China to the major general
4Discharging, so many SiCl
4To environment is a potential harm, and it is the urgent problem that present each polysilicon manufacturer faces that its flood tide stores.
In emerging production polysilicon method, reduce SiCl with Zn
4Producing polysilicon becomes focus just gradually, and developed countries such as Japan have begun in recent years to pay attention to that " Zn reduces SiCl
4" this environment protection method produces solar cell starting material polysilicon, and planned its industrialization.According on September 17th, 2008 " daily magazine news ", new Japanese sun silicon company has planned to begin in April, 2010 to produce solar cell starting material polysilicon with " Zn reduction method ".
The raw material that the Zn reduction method is used is SiCl
4, different with traditional " Siemens Method " material therefor, have that production technique is brief, speed of response is fast, constant product quality, can realize advantage such as cost control.Its principal reaction is:
SiCl
4(g)+2Zn(g)→Si(s)+2ZnCl
2(g)
Yet thisly reduce SiCl with Zn
4Produce the method for polysilicon, according to reaction formula SiCl
4(g)+2Zn (g) → Si (s)+2ZnCl
2(g) calculate, the silicon of one times of amount of every production will produce the ZnCl of ten times of amounts
2By product, how economically effective recycling ZnCl
2In Zn become a big problem.
Summary of the invention
Purpose of the present invention is exactly in order to provide a kind of energy efficient recovery Zn reduction SiCl
4Produce the by product ZnCl that produces in the polysilicon method
2In the ZnCl of Zn
2The method of fused salt electrolysis system zinc.
Technical scheme of the present invention is: a kind of ZnCl
2The method of fused salt electrolysis system zinc is by a cover ZnCl
2Fused salt electrolysis system zinc device is implemented, and this device comprises the electrolyzer of be with heating unit, is connected the mist eliminator of electrolyzer top and is arranged on the interior Graphite Electrodes of electrolyzer; Be characterized in, adopt fused salt electrolysis process, utilize heating unit ZnCl
2Remain on melted state, under the situation that does not add any assisted electrolysis matter, directly with ZnCl
2Fused salt electrolysis, electrolysate are the Zn and the gasiform Cl of molten state
2
The processing condition of described fused salt electrolysis are: electrolysis temperature 500-600 ℃, and interelectrode distance 2-8mm, current density 40-80A/dm
2
Described Graphite Electrodes is immersed in ZnCl fully
2In the fused salt, submergence is 50-150mm.
The Zn of electrolysate molten state directly supplies reduction SiCl after purifying
4Reaction usefulness, thus realize Zn reduction SiCl
4Produce the closed loop of polysilicon whole production technology.
Described mist eliminator is with the ZnCl that is heated in the electrolyzer and evaporates
2The smog cooling is condensed and is regained in the electrolyzer.
ZnCl of the present invention
2The method of fused salt electrolysis system zinc compared with prior art has following advantage and characteristics:
1, method of the present invention can realize Zn reduction SiCl
4Produce polysilicon loop production technology, thereby make Zn reduction SiCl
4Produce polysilicon process and reach high-level efficiency, less energy-consumption, zero release, reduce the production of polysilicon cost better.
2, ZnCl among the present invention
2Fused salt electrolysis need not to add other assisted electrolysis matter, and the impurity effect that is brought is little.
3, ZnCl among the present invention
2The steam output of fused salt and ZnCl
2The growing amount of smog remains on lower level, can not block pipeline.
4, method of the present invention has advantages such as the economical operation cost is low, working method is simple and convenient.
Description of drawings
The ZnCl of Fig. 1 for adopting among the present invention
2The basic structure synoptic diagram of fused salt electrolysis system zinc device.
Embodiment
The ZnCl that adopts among the present invention
2Fused salt electrolysis system zinc device as shown in Figure 1, it comprises heating unit 1, electrolyzer 2, mist eliminator 3, Graphite Electrodes 4, current conducting rod 5, thermopair 6, electrolysis power 7 and chlorine gas absorption tower 8.
Electrolyzer 2 is inlaid in the heating unit 1 and is suitable with heating unit, and this electrolyzer 2 is made by the stupalith of quartz or corrosion-and high-temp-resistant such as zirconia ceramics or silicon nitride ceramics, and its external diameter is 150～300mm, highly is 300～600mm.
Mist eliminator 3 is connected the top of electrolyzer 2, is made by the stupalith of quartz or corrosion-and high-temp-resistant such as zirconia ceramics or silicon nitride ceramics.Be connected with ZnCl on the cover plate 31 of mist eliminator 3
2Fused salt opening for feed 32, chlorine outlet 33 and Zn liquid discharging siphon pipe 36.The outside surface of mist eliminator 3 directly contacts with air, diameter 150～300mm, and height 300～600mm, the bottom is connected with electrolyzer 2 flanges, is provided with ceramic sealing material at flange connections and seals.
Graphite Electrodes 4 is arranged in pairs in the electrolyzer, Graphite Electrodes 4 is the acyclic type electrode, and the monolithic thickness of electrode is that 20～40mm, width are 50～100mm, highly are 100～200mm that two cube electrodes vertically are oppositely arranged, interelectrode distance 2～10mm, top of electrodes is threaded with current conducting rod 5.
The upper end of current conducting rod 5 is connected on the mist eliminator cover plate and protrudes upward, and the lower end is stretched in the electrolyzer 2 and is threaded with Graphite Electrodes 4, and the part of current conducting rod 5 below the mist eliminator cover plate is with porcelain bushing, is corroded to prevent current conducting rod 5.
The upper end of thermopair 6 is connected on the mist eliminator cover plate and protrudes upward, and the lower end is stretched in the electrolyzer 2, is used to measure the internal temperature of electrolyzer 2.
Electrolysis power 7 links to each other with current conducting rod 5 by lead.
Chlorine gas absorption tower 8 links to each other with the chlorine outlet of mist eliminator by gas piping 9.
The upper end of Zn liquid discharging siphon pipe 36 is connected on the mist eliminator cover plate and outwards draws, and the bottom of electrolyzer 2 is goed deep in the lower end.Siphon pipe 36 is made as zirconia ceramics, silicon nitride ceramics by quartz or corrosion-and high-temp-resistant pottery.Utilize siphon principle directly the high temperature Zn liquid that electrolysis generated to be incorporated into Zn reduction SiCl
4Zn steam feeder system in the preparation polysilicon can realize Zn reduction SiCl
4Produce the close loop maneuver of the whole technology of polysilicon.
ZnCl of the present invention
2The method of fused salt electrolysis system zinc is by above-mentioned ZnCl
2Fused salt electrolysis system zinc device is implemented, and the concrete practice is: Zn reduction legal system polysilicon by product ZnCl
2Behind equipment for purifying removal impurity, be passed into described ZnCl
2In the electrolyzer, utilize heating unit again with ZnCl
2Insulation is at 500-600 ℃.
The spacing of regulating Graphite Electrodes is to 2-8mm, and holding current density is at 40-80A/dm
2After begin electrolytic reaction.
After the reaction beginning, the Cl of generation
2Gas is discharged from the top vapor pipe, is passed into Cl
2Be absorbed in the absorption tower, the Zn that reaction generates falls to ZnCl
2Bottom of electrolytic tank is waited to assemble the back and reclaimed, and is recycling in Zn reduction SiCl
4In the reaction.
In reaction process, ZnCl
2ZnCl in the electrolyzer
2The volatilization of being heated when rising through mist eliminator, is condensed and is fallen back to ZnCl through cooling
2In the electrolyzer.Being provided with of this mist eliminator reduced ZnCl
2Volatilization loss amount and ZnCl
2The growing amount of smog, thus the possibility of significant loss and pipeline obstruction reduced.
In addition, will be incorporated into Zn reduction SiCl again after the Zn process purification that be generated
4In the Zn steam feeder system, can realize Zn reduction SiCl in the preparation polysilicon
4Produce the close loop maneuver of the whole technology of polysilicon.
Claims (5)
1. ZnCl
2The method of fused salt electrolysis system zinc is by a cover ZnCl
2Fused salt electrolysis system zinc device is implemented, and this device comprises the electrolyzer of be with heating unit, is connected the mist eliminator of electrolyzer top and is arranged on the interior Graphite Electrodes of electrolyzer; It is characterized in that: adopt fused salt electrolysis process, utilize heating unit ZnCl
2Remain on melted state, under the situation that does not add any assisted electrolysis matter, directly with ZnCl
2Fused salt electrolysis, electrolysate are the Zn and the gasiform Cl of molten state
2
2. ZnCl according to claim 1
2The method of fused salt electrolysis system zinc is characterized in that: the processing condition of described fused salt electrolysis are: electrolysis temperature 500-600 ℃, and interelectrode distance 2-8mm, current density 40-80A/dm
2
3. ZnCl according to claim 1
2The method of fused salt electrolysis system zinc is characterized in that: described Graphite Electrodes is immersed in ZnCl fully
2In the fused salt, submergence is 50-150mm.
4. ZnCl according to claim 1
2The method of fused salt electrolysis system zinc is characterized in that: the Zn of electrolysate molten state directly supplies reduction SiCl after purifying
4Reaction usefulness, thus realize Zn reduction SiCl
4Produce the closed loop of polysilicon whole production technology.
5. ZnCl according to claim 1
2The method of fused salt electrolysis system zinc is characterized in that: described mist eliminator is with the ZnCl that is heated in the electrolyzer and evaporates
2The smog cooling is condensed and is regained in the electrolyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910200121XA CN102086526A (en) | 2009-12-08 | 2009-12-08 | Method for preparing zinc by electrolyzing ZnC12 molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910200121XA CN102086526A (en) | 2009-12-08 | 2009-12-08 | Method for preparing zinc by electrolyzing ZnC12 molten salt |
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| Publication Number | Publication Date |
|---|---|
| CN102086526A true CN102086526A (en) | 2011-06-08 |
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|---|---|---|---|
| CN200910200121XA Pending CN102086526A (en) | 2009-12-08 | 2009-12-08 | Method for preparing zinc by electrolyzing ZnC12 molten salt |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616784A (en) * | 2011-10-27 | 2012-08-01 | 内蒙古神舟硅业有限责任公司 | Method of reducing silicon tetrachloride with zinc powder in organic solvent to prepare solar grade polysilicon |
| CN105378149A (en) * | 2013-05-08 | 2016-03-02 | 木野科技太阳能股份有限公司 | Zinc production method |
| CN105585255A (en) * | 2016-03-07 | 2016-05-18 | 秦皇岛玻璃工业研究设计院 | Passivation device and method capable of preventing lead ions in lead containing glass from being dissolved out |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200759A (en) * | 2004-01-15 | 2005-07-28 | Takayuki Shimamune | Electrolyzer |
| CN101484613A (en) * | 2006-07-07 | 2009-07-15 | 木野科技太阳能股份有限公司 | Electrolysis system and method |
| CN101522953A (en) * | 2006-09-22 | 2009-09-02 | 诺尔斯海德公司 | A method and an electrolysis cell for production of a metal from a molten chloride |
-
2009
- 2009-12-08 CN CN200910200121XA patent/CN102086526A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200759A (en) * | 2004-01-15 | 2005-07-28 | Takayuki Shimamune | Electrolyzer |
| CN101484613A (en) * | 2006-07-07 | 2009-07-15 | 木野科技太阳能股份有限公司 | Electrolysis system and method |
| CN101522953A (en) * | 2006-09-22 | 2009-09-02 | 诺尔斯海德公司 | A method and an electrolysis cell for production of a metal from a molten chloride |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616784A (en) * | 2011-10-27 | 2012-08-01 | 内蒙古神舟硅业有限责任公司 | Method of reducing silicon tetrachloride with zinc powder in organic solvent to prepare solar grade polysilicon |
| CN102616784B (en) * | 2011-10-27 | 2016-05-04 | 内蒙古神舟硅业有限责任公司 | In organic solvent, zinc powder reduction silicon tetrachloride is prepared the method for solar-grade polysilicon |
| CN105378149A (en) * | 2013-05-08 | 2016-03-02 | 木野科技太阳能股份有限公司 | Zinc production method |
| CN105585255A (en) * | 2016-03-07 | 2016-05-18 | 秦皇岛玻璃工业研究设计院 | Passivation device and method capable of preventing lead ions in lead containing glass from being dissolved out |
| CN105585255B (en) * | 2016-03-07 | 2017-12-19 | 秦皇岛玻璃工业研究设计院 | A kind of paralysis facility and passivating method for preventing flint glass lead ion dissolution |
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Application publication date: 20110608 |