CN108220599A - A kind of method of solution of zinc sulfate auto purification dechlorination - Google Patents
A kind of method of solution of zinc sulfate auto purification dechlorination Download PDFInfo
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- CN108220599A CN108220599A CN201810050240.0A CN201810050240A CN108220599A CN 108220599 A CN108220599 A CN 108220599A CN 201810050240 A CN201810050240 A CN 201810050240A CN 108220599 A CN108220599 A CN 108220599A
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- copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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Abstract
The invention belongs to the liquid waste disposal technique fields of non-ferrous metal metallurgy industry, disclose a kind of method of solution of zinc sulfate auto purification dechlorination, and by the way that zinc electrolyte is added in reactive tank, copper ashes generation auto purification dechlorination reaction, Mn are added in into reactive tank7+Not only cupric is generated as oxidizing copper simple substance, but also serves as catalyst and accelerate copper simple substance and cupric and react generation monovalence copper, then by dechlorination reaction, generated stannous chloride precipitation, achieve the purpose that auto purification dechlorination.This method effectively reduces the content of chlorion in zinc electrolyte, simple for process, is not required to add in special reagent, without the use of special installation, operating cost is low.
Description
Technical field
The invention belongs to the liquid waste disposal technique fields of non-ferrous metal metallurgy industry, are related to a kind of solution of zinc sulfate auto purification
The method of dechlorination.
Background technology
In Zinc Hydrometallurgy Process, chlorinity not only makes electrolytic anode rotten up to that can influence process in zinc electrolyzing afterwards to a certain degree
Erosion consumption aggravation causes stripping zinc difficult, and electrolytic cell overhead chloride ion content increases, and deteriorates site work environment, seriously
Influence the health of worker.
At present, the purification removing of chlorion is mainly the following method in Zinc Hydrometallurgy Process：
1st, silver salt precipitation method
Silver salt precipitation method is to utilize Ag-With Cl-AgCl precipitations are generated, realize the purpose of chlorion removing, although this method operates
Simply, dechlorination effect is good, but because silver salt is expensive, recovery utilization rate is low, and financial cost is unreasonable, is not suitable for extensive
It promotes the use of.
2nd, traditional chlorine removal from copper residue method
Chlorine removal from copper residue method is elemental copper, Cu in the presence of having elemental copper in solution+、Cl-The CuCl of reaction generation indissoluble sinks
It forms sediment, so as to fulfill the purpose of chlorion removing, but needs to additionally incorporate oxidant, cost is higher.
3rd, ion-exchange
Ion-exchange is that cross reaction occurs using exchangeable ion in ion exchange resin and the chlorion in solution, makes chlorine
For ionic adsorption on resin, chlorine removal rate is relatively low, and ion-exchange resin regenerated waste water amount is very big, and chlorion contains in regenerative wastewater
It measures low, is subsequently further processed relatively difficult.
Invention content
The purpose of the present invention is to provide a kind of methods of solution of zinc sulfate auto purification dechlorination, reduce chlorion in electrolyte
Content, this method is simple for process, and rear liquid chlorine ion concentration is low, is not required to add in special reagent, without the use of special installation, operation
It is at low cost.
To achieve the above object, the present invention uses following technical scheme：
The present invention provides a kind of method of solution of zinc sulfate auto purification dechlorination, includes the following steps：Zinc electrolyte is added to instead
It answers in slot, copper ashes is added in into reactive tank, auto purification dechlorination reaction, reaction time 2.5h are carried out at 15 DEG C ~ 80 DEG C；The zinc
Mn in electrolyte7+Content be 0.4 ~ 0.5g/l；The molar ratio of chlorion and copper in copper ashes is 1 in the zinc electrolyte：（2~
10）, the feed postition of copper ashes is to size mixing to be uniformly added into or do not size mixing to be uniformly added into, and add in and finish in 10min.
Further, the granularity of the copper ashes is 180 ~ 325 mesh, and wherein granularity accounts for more than 60% for the copper ashes of 325 mesh.
Further, the content of copper is 45 ~ 65% in the copper ashes, and the content of copper oxide is no more than 5% in copper ashes.
Further, the content of suspended matter is less than 50mg/l in the zinc electrolyte.
Further, the auto purification dechlorination reaction carries out the zinc electrolyte after reaction press filtration, reaction after starting 0.3h
Terminate press filtration also to terminate.
Compared with prior art, the beneficial effects of the present invention are：
1. by controlling the total manganese content of the new liquid of wet zinc-making system, Faradaic current lifting, electrolytic anode plate replacement cycle, make zinc electric
Solve Mn in liquid7+Content is in 0.4 ~ 0.5kg/m3In the range of, generation auto purification dechlorination reaction after copper ashes is added in zinc electrolyte
In the process, Mn7+Not only cupric is generated as oxidizing copper simple substance, but also serves as catalyst and accelerate copper simple substance and cupric generation
Reaction generation monovalence copper then by dechlorination reaction, generates stannous chloride precipitation, achievees the purpose that auto purification dechlorination.
2. auto purification dechlorination method of the present invention is with traditional dechlorination method, the difference lies in copper oxide is not involved in reacting, can
It is substantially reduced in copper ashes to the content requirement of copper oxide, and Mn7+Presence copper simple substance is made repeatedly to participate in reacting, can reduce dechlorination after
Copper ion loses in liquid, dechlorination rate up to more than 80%, in rear liquid containing chlorine in 100mg/l hereinafter, effectively reducing in zinc electrolyte
The content of chlorion, this method is simple for process, is not required to add in special reagent, without the use of special installation, operating cost is low.
Specific embodiment
Following embodiment is not used to limit protection scope of the present invention for illustrating the present invention.It is unless otherwise specified, real
Apply the conventional means that technological means used in example is well known to those skilled in the art.Test method in following embodiments, such as
It is conventional method without special instruction.
Embodiment one
A kind of method of solution of zinc sulfate auto purification dechlorination, includes the following steps：By 1m3Zinc electrolyte is added in reactive tank,
Zn in zinc electrolyte2+A concentration of 57.1g/l, Mn7+A concentration of 0.43g/l, Cl-A concentration of 0.41g/l, suspended matter it is a concentration of
0.05g/l, other is impurity or water.The copper ashes that granularity is 180 ~ 325 mesh is chosen, wherein granularity accounts for 60% for the copper ashes of 325 mesh,
The content of copper is 45.03% in copper ashes, and the content of copper oxide is 5% in copper ashes, is uniformly added into after the fresh copper ashes of 8.5kg is sized mixing anti-
It answers in slot, adds in and finish in 10min, for the control of reactive tank temperature at 30 DEG C, the auto purification dechlorination reaction time is 2.5h；Auto purification takes off
Chlorine reaction starts press filtration after starting 0.3h, and reaction terminates press filtration and also terminates, and chloride ion content is 63.23mg/L in filtrate, chlorine from
The removal rate of son is 84.58%.
Occur after addition copper ashes in auto purification dechlorination reaction process in zinc electrolyte, Mn7+Both as oxidizing
Copper simple substance generates cupric, and serves as catalyst and accelerate copper simple substance and cupric and react generation monovalence copper, then by de-
Chlorine reacts, and generates stannous chloride precipitation, achievees the purpose that auto purification dechlorination.Copper oxide is not involved in reacting in this method, can be apparent
It reduces in conventional method copper ashes to the content requirement of copper oxide, and Mn7+Presence copper simple substance is made repeatedly to participate in reacting, can reduce and remove
Copper ion loses in liquid after chlorine, can effectively reduce the content of chlorion in zinc electrolyte, and this method is simple for process, is not required to add in special
Different reagent, without the use of special installation, operating cost is low.
Embodiment two
A kind of method of solution of zinc sulfate auto purification dechlorination, includes the following steps：By 1m3Zinc electrolyte is added in reactive tank,
Zn in zinc electrolyte2+A concentration of 67.48g/l, Mn7+A concentration of 0.21g/l, Cl-A concentration of 0.39g/l, suspended matter it is a concentration of
0.04g/l, other is impurity or water.The copper ashes that granularity is 180 ~ 325 mesh is chosen, wherein granularity accounts for 70% for the copper ashes of 325 mesh,
The content of copper is 53.06% in copper ashes, and the content of copper oxide is 3% in copper ashes, and reaction is uniformly added into after the fresh copper ashes of 8kg is sized mixing
It adds in and finishes in slot, in 10min, for the control of reactive tank temperature at 70 DEG C, the auto purification dechlorination reaction time is 2.5h；Auto purification dechlorination
Reaction starts press filtration after starting 0.3h, and reaction terminates press filtration and also terminates, and chloride ion content is 72.56mg/L in filtrate, chlorion
Removal rate be 81.39%.
Embodiment three
A kind of method of solution of zinc sulfate auto purification dechlorination, includes the following steps：By 1m3Zinc electrolyte is added in reactive tank,
Zn in zinc electrolyte2+A concentration of 51.86g/l, Mn7+A concentration of 0.09g/l, Cl-A concentration of 0.5g/l, suspended matter it is a concentration of
0.05g/l, other is impurity or water.The copper ashes that granularity is 180 ~ 325 mesh is chosen, wherein granularity accounts for 80% for the copper ashes of 325 mesh,
The content of copper is 62.56% in copper ashes, and the content of copper oxide is 2.5% in copper ashes, is uniformly added after the fresh copper ashes of 12.5kg is sized mixing
Enter in reactive tank, add in and finish in 10min, the control of reactive tank temperature is 2.5h in 45 DEG C of auto purification dechlorination reaction times；Self-cleaning
To change after dechlorination reaction starts 0.3h and start press filtration, reaction terminates press filtration and also terminates, and chloride ion content is 74.49mg/L in filtrate,
The removal rate of chlorion is 85.95%.
Example IV
A kind of method of solution of zinc sulfate auto purification dechlorination, includes the following steps：By 1m3Zinc electrolyte is added in reactive tank,
Zn in zinc electrolyte2+A concentration of 51.86g/l, Mn7+A concentration of 0.09g/l, Cl-A concentration of 0.53g/l, suspended matter it is a concentration of
0.05g/l, other is impurity or water.Choose granularity be 180 ~ 325 mesh copper ashes, wherein granularity for 325 mesh copper ashes account for 60% with
On, the content of copper is 62.56% in copper ashes, and the content of copper oxide is 2.5% in copper ashes, and the fresh copper ashes of 15.5kg is not sized mixing uniformly
It adds in reactive tank, adds in and finish in 10min, for the control of reactive tank temperature at 15 DEG C, the auto purification dechlorination reaction time is 2.5h；From
Purification dechlorination reaction starts press filtration after starting 0.3h, and reaction terminates press filtration and also terminates, and chloride ion content is 94.03mg/ in filtrate
L, the removal rate of chlorion is 82.26%.
Embodiment five
A kind of method of solution of zinc sulfate auto purification dechlorination, includes the following steps：By 1m3Zinc electrolyte is added in reactive tank,
Zn in zinc electrolyte2+A concentration of 51.86g/l, Mn7+A concentration of 0.09g/l, Cl-A concentration of 0.53g/l, suspended matter it is a concentration of
0.05g/l, other is impurity or water.Choose granularity be 180 ~ 325 mesh copper ashes, wherein granularity for 325 mesh copper ashes account for 60% with
On, the content of copper is 62.56% in copper ashes, and the content of copper oxide is 2.5% in copper ashes, and the fresh copper ashes of 3.2kg is not sized mixing uniformly
It adds in reactive tank, adds in and finish in 10min, for the control of reactive tank temperature at 80 DEG C, the auto purification dechlorination reaction time is 2.5h；From
Purification dechlorination reaction starts press filtration after starting 0.3h, and reaction terminates press filtration and also terminates, and chloride ion content is 69.36mg/ in filtrate
L, the removal rate of chlorion is 86.91%.
The embodiment of the above, only presently preferred embodiments of the present invention, is only used to explain the present invention, not limit
The scope of the present invention processed, to those of ordinary skill in the art, certainly can be according to skill disclosed in this specification
Art content, makes other embodiments easily by way of replacing or changing, therefore all in the principle of the present invention and technique item
Changes and improvements that part is done etc. should all be included in scope of the present invention patent.
Claims (5)
- A kind of 1. method of solution of zinc sulfate auto purification dechlorination, which is characterized in that include the following steps：Zinc electrolyte is added to In reactive tank, copper ashes is added in into reactive tank, auto purification dechlorination reaction, reaction time 2.5h are carried out at 15 DEG C ~ 80 DEG C；It is described Mn in zinc electrolyte7+Content be 0.4 ~ 0.5g/l；The molar ratio of chlorion and copper in copper ashes is 1 in the zinc electrolyte：（2~ 10）, the feed postition of copper ashes is to size mixing to be uniformly added into or do not size mixing to be uniformly added into, and add in and finish in 10min.
- A kind of 2. method of solution of zinc sulfate auto purification dechlorination according to claim 1, which is characterized in that the grain of the copper ashes It spends for 180 ~ 325 mesh, wherein granularity accounts for more than 60% for the copper ashes of 325 mesh.
- A kind of 3. method of solution of zinc sulfate auto purification dechlorination according to claim 2, which is characterized in that copper in the copper ashes Content for 45 ~ 65%, the content of copper oxide is no more than 5% in copper ashes.
- A kind of 4. method of solution of zinc sulfate auto purification dechlorination according to claim 1, which is characterized in that the zinc electrolyte The content of middle suspended matter is less than 50mg/l.
- 5. a kind of method of solution of zinc sulfate auto purification dechlorination according to claim 1, which is characterized in that the auto purification takes off Chlorine reaction carries out the zinc electrolyte after reaction press filtration after starting 0.3h, and reaction terminates press filtration and also terminates.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111549234A (en) * | 2020-05-07 | 2020-08-18 | 云南云铜锌业股份有限公司 | Method and system for dechlorinating zinc hydrometallurgy copper slag |
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| CN111549234A (en) * | 2020-05-07 | 2020-08-18 | 云南云铜锌业股份有限公司 | Method and system for dechlorinating zinc hydrometallurgy copper slag |
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Application publication date: 20180629 |