CN103668324B - A kind of technique of zinc sulfate electrolysis waste solution dechlorination - Google Patents
A kind of technique of zinc sulfate electrolysis waste solution dechlorination Download PDFInfo
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- CN103668324B CN103668324B CN201310651729.0A CN201310651729A CN103668324B CN 103668324 B CN103668324 B CN 103668324B CN 201310651729 A CN201310651729 A CN 201310651729A CN 103668324 B CN103668324 B CN 103668324B
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- dechlorination
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of zinc sulfate electrolysis waste solution dechlorination technique, comprise the following steps: a, in reactor zinc sulfate electrolysis waste solution add Lead oxide brown dechlorinate, stirring and dissolving；B, with sodium hydroxide solution in dechlorination process produce chlorine absorb；The dechlorination slag that c, the process that dechlorinated by step a produce is put in the solution after absorbing chlorine in step b, and stirring and dissolving filters, and filtering residue is regeneration Lead oxide brown, and filtrate is liquid after regeneration.The technique adopting the present invention, dechlorination rate is high, after dechlorination, liquid is chloride up to about 85mg/l, dechlorination rate is up to 96%, and in present invention process, regeneration Lead oxide brown returns dechlorination step cycle and utilizes, after regeneration, liquid returns the utilization of chlorine absorption step cycle after adding sodium hydroxide, achieve closed cycle, improve raw material availability, promote recycling economy development.
Description
Technical field
The invention belongs to non-ferrous metal field of hydrometallurgy, the technique being specifically related to the dechlorination of a kind of zinc sulfate electrolysis waste solution.
Background technology
At present, the zinc of China more than 75% adopts Zinc hydrometallurgy process to produce, and in Zinc Hydrometallurgy Process, the purification of solution of zinc sulfate is most important, and the objectionable impurities such as copper therein, cadmium, cobalt, nickel, fluorine, chlorine must purify to allowing under content；Wherein, the existence of chloride ion affects being normally carried out of Zinc electrolysis process, not only makes lead anode corrosion aggravation, causes electrodeposition operation stripping zinc difficulty；And lead anode power consumption increases, and also results in the leaded rising of cathode zinc；Slot electrode overhead chlorine raises, operating condition is made to worsen, have a strong impact on the healthy of workman, according to its technological requirement, during electrolysis, the chloride ion content in solution of zinc sulfate should control at below 200mg/l, can ensure that what produce is smoothed out, bring inconvenience otherwise can to the electrodeposition of zinc, have a strong impact on Zinc electrolysis electricity effect and the quality of electricity zinc product.
In chloride solution of zinc sulfate, the purification separation of chloride ion mainly adopts several method for a long time:
1, the silver sulfate sedimentation method
The silver sulfate sedimentation method are toward containing adding silver sulfate in solutions of chlorine so that it is with chloride ion effect, the silver nitride precipitation of generation indissoluble；Although the method is simple to operate, dechlorinate effective, but because silver salt is expensive, the regeneration response rate of silver is low, relatively costly, is not suitable for large-scale application.
2, chlorine removal from copper residue method
Chlorine removal from copper residue method is based on the chloride ion in copper and copper ion and solution and interacts, form the Cu-lyt. precipitation of indissoluble, but to make the chloride ion in solution generate Cu-lyt. precipitation and copper and copper ion must be made to set up an equilibrium point, in actual production copper ashes because of the time stacked different in size, cause the balance of copper point of the copper of sponge state and oxidation state to be difficult to set up.Copper (the Cu of sponge state in copper ashes0) content higher time, dechlorination process just need to add oxidant, oxidant makes Cu0It is oxidized to Cu2+While, part Cu2Cl2CuCl can be oxidized to2, ferric ion (Fe in solution in addition3+) existence also can make Cu2Cl2It is oxidized to CuCl2, make that solution is chloride, cupric raises, reduce dechlorination effect, cause bigger copper loss to lose, therefore to improve dechlorination rate and be necessary for the copper ashes that addition is excessive；In copper ashes, the copper content of oxidation state is higher, just need to add reducing agent in dechlorination process, as made reducing agent, Cu with zinc powder2+It is reduced to Cu0While Cu+It is also reduced to Cu0, make chloride ion reenter in solution, make the chloride rising of solution, reduce dechlorination effect, improve dechlorination rate to still need to add excessive copper ashes, between above-mentioned reason, chlorine removal from copper residue method, the excess coefficient of copper is bigger, inventory is relatively big, and copper loss rate is higher, and copper ashes regeneration cycle uses comparatively difficulty, relatively costly, technique is difficult to manipulate.
3, ion exchange
Ion exchange dechlorination is to utilize the exchangeable ion of ion exchange resin and the chloride ion generation cross reaction to be removed in solution, chloride ion to be removed in solution is made to be adsorbed on resin, and corresponding exchangeable ion enters solution on resin, this method chlorine removal rate is low, it is only about 50%, and the regeneration water consumption of resin is relatively big, after regeneration, liquid chloride ion-containing is relatively low, brings bigger financial burden to the process of liquid after next step regeneration.
Summary of the invention
For the deficiencies in the prior art, the technique that the present invention provides the zinc sulfate electrolysis waste solution dechlorination that a kind of technique is simple, chlorine removal rate is high, cost is low.
Technical scheme: the technique of a kind of zinc sulfate electrolysis waste solution dechlorination, comprises the following steps:
A, in reactor zinc sulfate electrolysis waste solution add Lead oxide brown dechlorinate, stirring and dissolving；
B, with sodium hydroxide solution in dechlorination process produce chlorine absorb；
The dechlorination slag that c, the process that dechlorinated by step a produce is put in the solution after absorbing chlorine in step b, and stirring and dissolving filters, and filtering residue is regeneration Lead oxide brown, and filtrate is liquid after regeneration.
As preferably, in described step a, Lead oxide brown addition is that per kilogram chlorine consumes 3.36～13.44kg Lead oxide brown.
As it is preferred that, in described step a Lead oxide brown addition be per kilogram chlorine consume 6.72～10.08kg Lead oxide brown.
Further, stirring and dissolving 30～60 minutes in described step a, reaction temperature 50～60 DEG C.
Further, preferred 200～300g/l sodium hydroxide solution in described step b.
Further, the dechlorination slag that the process that dechlorinated by step a in described step c produces is put in the solution after absorbing chlorine in step b according to liquid-solid ratio 5～10:1.
Further, stirring and dissolving 30～45 minutes in described step c, reaction temperature 85～90 DEG C.
Further, described step c regenerates in Lead oxide brown return step a and dechlorinate, recycle.
Further, in described step c, after regeneration, liquid is added sodium hydroxide and is returned in step b to 200～300g/l and carry out chlorine absorption, recycles.
The dominant response equation that the present invention relates to:
PbO2+2HCl+H2SO4=PbSO4+Cl2+2H2O
Cl2+2NaOH=2NaClO+H2O
PbSO4+NaClO+2NaOH=PbO2+NaCl+Na2SO4+H2O
Beneficial effects of the present invention:
(1) technique adopting the present invention, dechlorination rate is high, and after dechlorination, liquid is chloride up to about 85mg/l, and dechlorination rate is up to 96%.
(2) in present invention process, regeneration Lead oxide brown returns dechlorination step cycle and utilizes, and after after regeneration, liquid adds sodium hydroxide, return chlorine absorption step cycle utilizes, it is achieved that closed cycle, improves raw material availability, promotes recycling economy development.
(3) present invention process is greatly reduced the chlorine in zinc sulphate electrolyte, hence it is evident that improve working environment, improves zinc metal sheet quality, reduces electrolysis cost.
Detailed description of the invention
For making those skilled in the art understand production technology and the technique effect of the present invention in detail, it is further described application and the technique effect of the present invention below with concrete production instance.
Embodiment 1
The technique of a kind of zinc sulfate electrolysis waste solution dechlorination, comprises the following steps:
A, taking the zinc sulfate electrolysis waste solution 1000ml of chloride 2.5g/l, add 8.4g Lead oxide brown, 50 DEG C of reactions dechlorinate for 30 minutes；
B, take 200g/l sodium hydroxide solution 500ml in dechlorination process produce chlorine absorb；
The dechlorination slag that c, the process that dechlorinated by step a produce is put into and is absorbed in the solution after chlorine in step b under 85 DEG C of conditions, react 30 minutes, filters, and filtering residue is regeneration Lead oxide brown, and filtrate is liquid after regenerating；
D, regeneration Lead oxide brown return in step a, dechlorinate；
After e, regeneration, liquid adds sodium hydroxide to 200g/l, returns step b and is used for absorbing chlorine.
After measured, dechlorination rate reaches 44.99% to this embodiment.
Embodiment 2
The technique of a kind of zinc sulfate electrolysis waste solution dechlorination, comprises the following steps:
A, taking the zinc sulfate electrolysis waste solution 1000ml of chloride 2.5g/l, add 16.8g Lead oxide brown, 60 DEG C of reactions dechlorinate for 40 minutes；
B, take 250g/l sodium hydroxide solution 500ml in dechlorination process produce chlorine absorb；
The dechlorination slag that c, the process that dechlorinated by step a produce is put into and is absorbed in the solution after chlorine in step b under 90 DEG C of conditions, react 40 minutes, filters, and filtering residue is regeneration Lead oxide brown, and filtrate is liquid after regenerating；
D, regeneration Lead oxide brown return in step a, dechlorinate；
After e, regeneration, liquid adds sodium hydroxide to 250g/l, returns and is used for absorbing chlorine.
After measured, dechlorination rate reaches 92.25% to this embodiment.
Embodiment 3
The technique of a kind of zinc sulfate electrolysis waste solution dechlorination, comprises the following steps:
A, taking the zinc sulfate electrolysis waste solution 1000ml of chloride 2.5g/l, add 25.2g Lead oxide brown, 50 DEG C of reactions dechlorinate for 50 minutes；
B, take 300g/l sodium hydroxide solution 500ml in dechlorination process produce chlorine absorb；
The dechlorination slag that c, the process that dechlorinated by step a produce is put into and is absorbed in the solution after chlorine in step b under 85 DEG C of conditions, react 45 minutes, filters, and filtering residue is regeneration Lead oxide brown, and filtrate is liquid after regenerating；
D, regeneration Lead oxide brown return in step a, dechlorinate；
After e, regeneration, liquid adds sodium hydroxide to 300g/l, returns and is used for absorbing chlorine.
After measured, dechlorination rate reaches 94.35% to this embodiment.
Embodiment 4
The technique of zinc sulfate electrolysis waste solution dechlorination, comprises the following steps:
A, taking the zinc sulfate electrolysis waste solution 1000ml of chloride 2.5g/l, add 33.6g Lead oxide brown, 60 DEG C of reactions dechlorinate for 60 minutes；
B, take 200g/l sodium hydroxide solution 500ml in dechlorination process produce chlorine absorb；
The dechlorination slag that c, the process that dechlorinated by step a produce is put into and is absorbed in the solution after chlorine in step b under 90 DEG C of conditions, react 30 minutes, filters, and filtering residue is regeneration Lead oxide brown, and filtrate is liquid after regenerating；
D, regeneration Lead oxide brown return in step a, dechlorinate；
After e, regeneration, liquid adds sodium hydroxide to 200g/l, returns and is used for absorbing chlorine.
After measured, dechlorination rate reaches 96.60% to this embodiment.
The technical scheme above embodiment of the present invention provided is described in detail, principle and the embodiment of the embodiment of the present invention are set forth by specific case used herein, and the explanation of above example is only applicable to help to understand the principle of the embodiment of the present invention；Simultaneously for one of ordinary skill in the art, according to the embodiment of the present invention, all will change in detailed description of the invention and range of application, in sum, this specification content should not be construed as limitation of the present invention.
Claims (8)
1. the technique of a zinc sulfate electrolysis waste solution dechlorination, it is characterised in that comprise the following steps:
A, in reactor zinc sulfate electrolysis waste solution add Lead oxide brown dechlorinate, stirring and dissolving；
B, with sodium hydroxide solution in dechlorination process produce chlorine absorb；
The dechlorination slag that c, the process that dechlorinated by step a produce is put in the solution after absorbing chlorine in step b, and stirring and dissolving filters, and filtering residue is regeneration Lead oxide brown, and filtrate is liquid after regeneration.
2. the technique of zinc sulfate electrolysis waste solution according to claim 1 dechlorination, it is characterised in that: in described step a, Lead oxide brown addition is that per kilogram chlorine consumes 3.36～13.44kg Lead oxide brown.
3. the technique of zinc sulfate electrolysis waste solution according to claim 1 dechlorination, it is characterised in that: in described step a, Lead oxide brown addition is that per kilogram chlorine consumes 6.72～10.08kg Lead oxide brown.
4. the technique of zinc sulfate electrolysis waste solution according to claim 1 dechlorination, it is characterised in that: stirring and dissolving 30～60 minutes in described step a, reaction temperature 50～60 DEG C.
5. the technique of zinc sulfate electrolysis waste solution according to claim 1 dechlorination, it is characterised in that: sodium hydroxide solution described in described step b is 200～300g/l sodium hydroxide solution.
6. the technique of zinc sulfate electrolysis waste solution according to claim 1 dechlorination, it is characterised in that: stirring and dissolving 30～45 minutes in described step c, reaction temperature 85～90 DEG C.
7. the technique of zinc sulfate electrolysis waste solution according to claim 1 dechlorination, it is characterised in that: described step c regenerates in Lead oxide brown return step a and dechlorinate, recycle.
8. the technique of zinc sulfate electrolysis waste solution according to claim 1 dechlorination, it is characterised in that: in described step c, after regeneration, liquid is added sodium hydroxide and is returned in step b to 200～300g/l and carry out chlorine absorption, recycles.
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| CN104399430B (en) * | 2014-09-26 | 2016-05-25 | 中南大学 | A kind of preparation method who is applied to the compound defluorination material of defluorination in electrolysis solution of zinc sulfate |
| CN107245574A (en) * | 2017-05-12 | 2017-10-13 | 李家祥 | A kind of technique dechlorinated in zinc electrolyte |
| CN114314928B (en) * | 2022-01-04 | 2023-09-08 | 湖南烯富环保科技有限公司 | Integrated production line and method for chloride ion removal and chlorine removal slag regeneration chlorine removal agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0066024A1 (en) * | 1981-06-02 | 1982-12-08 | Sherritt Gordon Mines Limited | Process for the removal of manganese and chloride ions from aqueous acidic zinc sulphate solutions and process for the recovery of zinc |
| CN1046761A (en) * | 1989-04-29 | 1990-11-07 | 化工部天津化工研究院 | Zinc hydrometallurgy |
| RU2075524C1 (en) * | 1993-03-10 | 1997-03-20 | Научно-производственный кооператив "Доминион" | Method of processing of zinc-containing solutions |
| CN101285119A (en) * | 2008-05-23 | 2008-10-15 | 祥云县飞龙实业有限责任公司 | Dechlorination process from zinc electrolytic solution |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60228628A (en) * | 1984-04-25 | 1985-11-13 | Mitsui Mining & Smelting Co Ltd | Method for removing chlorine in wet refining |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0066024A1 (en) * | 1981-06-02 | 1982-12-08 | Sherritt Gordon Mines Limited | Process for the removal of manganese and chloride ions from aqueous acidic zinc sulphate solutions and process for the recovery of zinc |
| CN1046761A (en) * | 1989-04-29 | 1990-11-07 | 化工部天津化工研究院 | Zinc hydrometallurgy |
| RU2075524C1 (en) * | 1993-03-10 | 1997-03-20 | Научно-производственный кооператив "Доминион" | Method of processing of zinc-containing solutions |
| CN101285119A (en) * | 2008-05-23 | 2008-10-15 | 祥云县飞龙实业有限责任公司 | Dechlorination process from zinc electrolytic solution |
Non-Patent Citations (2)
| Title |
|---|
| 湿法炼锌中氯的危害及控制;王文录;《湖南有色金属》;20070228;第23卷(第1期);第22-24,50页 * |
| 湿法系统除氯工艺技术研究及应用;王锦鸿;《湖南有色金属》;20131031;第29卷(第5期);第37-40页 * |
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