CN103014339B - A kind of method for the purification copper removal cadmium that seethes with excitement - Google Patents
A kind of method for the purification copper removal cadmium that seethes with excitement Download PDFInfo
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- CN103014339B CN103014339B CN201210588871.0A CN201210588871A CN103014339B CN 103014339 B CN103014339 B CN 103014339B CN 201210588871 A CN201210588871 A CN 201210588871A CN 103014339 B CN103014339 B CN 103014339B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a kind of method for the purification copper removal cadmium that seethes with excitement, its step includes：A, copper-cadmium slag drop zinc boiling groove in, using add activation after copper-cadmium slag ore pulp, using neutral supernatant copper reduce copper-cadmium slag in zinc, overflow enter copper removal cadmium seethe with excitement groove, the every slagging in 4 hours of bottom ash once, each slagging 5m3~10 m3, send subsequent processing to reclaim copper cadmium；B, in copper removal cadmium boiling groove, be continuously added to pulp zinc powder, accurately control pulp zinc powder addition using current potential, overflow, which enters, removes residual cadmium tank diameter, once, each slagging time is 5m to the every slagging in 4 hours of bottom ash3~10 m3, it is discharged into except copper-cadmium slag activates tank diameter；C, in except copper-cadmium slag activation tank diameter adding electrolysis waste solution, adjusting pH value 3.5~4.5, carry out overflow press filtration, overflow enters second segment purified cobalt.Production technology of the present invention and operating procedure is simple, cost is relatively low, can more effectively copper removal cadmium, reduce zinc consumption.
Description
Technical field
The invention belongs to the method that zinc hydrometallurgy leaches neutral supernatant boiling purification copper removal cadmium, belong to non-ferrous metal smelting
A kind of refining, and in particular to method for the purification copper removal cadmium that seethes with excitement.
Background technology
Zinc hydrometallurgy leaches neutral supernatant and sent before electrolytic deposition, and some objectionable impurities must be reduced further, in neutrality
Clear liquid impurity removal process is generally divided into three sections：I.e. one section copper removal cadmium, two sections except cobalt, three sections are except redissolving cadmium.One section of copper removal cadmium is in boiling
Rise in groove and mechanical agitating tank and be carried out continuously, boiling groove main agents are that zinc powder is continuously added to from groove top, by stirring and leading
Flow cartridge enters the middle and upper part of boiling groove, and neutral supernatant is continuously added to from trench bottom.The solution of last groove outlet passes through machine
Tool tank diameter is removed after cadmium, then carries out solid-liquor separation, and the solution for completing one section of purification process carries out two sections of purifications, and slag reclaims copper cadmium.
Substantial amounts of zinc powder need to be added in one section of copper removal cadmium, because zinc powder is a kind of auxiliary material costly, zinc consumption, drop is reduced
The tool containing zinc is of great significance in low copper-cadmium slag.
The content of the invention
To solve problem of the prior art there is provided a kind of production technology and operating procedure be simple, cost is relatively low, while can again
Copper cadmium is more effectively removed, the boiling purification copper removal cadmium method containing zinc in zinc consumption, reduction copper-cadmium slag is reduced.
The technical solution adopted in the present invention is as follows：A kind of method for the purification copper removal cadmium that seethes with excitement, it is characterised in that：It includes
Following steps：
A, in copper-cadmium slag drop zinc boiling groove, neutral supernatant is continuous to be added from bottom, and flow is controlled in 100 m3/ h~
150m3/ h, temperature：55 DEG C~75 DEG C, the copper-cadmium slag ore pulp added after activation is reduced in copper-cadmium slag using the copper of neutral supernatant
Zinc, 20 minutes~30 minutes reaction time, overflow enter copper removal cadmium seethe with excitement groove, the every slagging in 4 hours of bottom ash once, each slagging
5 m3~10 m3, send subsequent processing to reclaim copper cadmium；
B, in copper removal cadmium boiling groove, overflow that step A is produced is continuous to be added from bottom, and flow is controlled in 100 m3/h
~150m3/ h, temperature is 55 DEG C~75 DEG C, is continuously added to pulp zinc powder, 20 minutes~30 minutes reaction time, accurate using current potential
Pulp zinc powder addition is really controlled, zinc powder addition is more, and current potential is more negative, and cadmium is lower in solution, conversely, as the same；Overflow enters except residual
Cadmium tank diameter, the every slagging in 4 hours of bottom ash once, each slagging 5m3~10 m3, it is discharged into except copper-cadmium slag activates tank diameter；
C, the bottom ash for producing step B are added except in copper-cadmium slag activation tank diameter, often add a bottom ash, while adding electricity
Liquid waste solution, reaction time：30 minutes~60 minutes, temperature：50~70 DEG C.PH value 3.5~4.5 is adjusted, overflow press filtration is carried out, overflow
Stream enters second segment purified cobalt, when neutral supernatant is not enough, and overflow portion is supplemented with zinc powder pulp and neutral supernatant flow quantity.
Described neutral supernatant is liquid after impure copper, cobalt, cadmium, nickel, arsenic, antimony, the zinc sulfate of germanium are leached, and its impurity contains
Measuring scope is：Zn:130 g/l~170 g/l, Cu:0.3 g/l~0.6 g/l, Cd：The g/l of 0.5 g/l~0.9, purification temperature
Degree control is at 55 DEG C~75 DEG C.
Liquid adds zinc powder and is sized mixing to be formed after described pulp zinc powder purifies zinc sulfate in container of sizing mixing
Zinc slurry.
The chemical composition (%) of described zinc powder：ZnAlways≥95 ZnMetal≥90、Pb≤1.0、Fe≤0.3、Cd≤0.25、Al
≤ 0.05, zinc powder particle size is：Mesh >=80% of -50 mesh~+160 and it is uniformly distributed.
Described utilization current potential accurately controls pulp zinc powder addition to refer to adjust zinc powder according to solution potential online data
Consumption, reaches that liquid reaches the quality requirement containing cadmium≤30mg/l after purification.
The composition and content for the electrolysis waste solution that described copper-cadmium slag activation tank diameter is added be：Sulfuric acid：150~200g/l,
Zinc：40~60 g/l, the amount of addition is the bottom ash pH value added every time is controlled between 3.5~4.5.
The present invention possesses following good effect：
1st, the boiling groove in traditional handicraft is changed to series connection by the present invention by parallel connection, and first groove is copper-cadmium slag drop zinc boiling groove,
The copper-cadmium slag ore pulp added in neutral supernatant soln after activation, the zinc in copper-cadmium slag is reduced using the copper of neutral supernatant, the
Two grooves are copper removal cadmium boiling groove, and using pulp zinc powder copper removal cadmium is continuously added to, zinc consumption is greatly reduced in this change, reduction
Production cost.
2nd, the present invention changes the mode that zinc powder is added in traditional handicraft, and tradition is using the side stirred in zincification powder
Formula, is now changed to slurryization after zinc powder purification and adds, added from boiling groove middle and lower part, be conducive to zinc powder to spread, reduction zinc powder disappears
Consumption.
3rd, present invention improves over the zinc powder consumption in traditional operation mode, traditional handicraft is according to result according to periodically chemical examination
Adjust zinc powder consumption, the present invention is changed to adjust zinc powder consumption according to solution potential online data, this mode not only accurately and reliably,
It can save zinc powder consumption, and the time cycle is short, efficiency high.
4th, except copper-cadmium slag activation tank diameter in add electrolysis waste solution, can activated zinc powder, reduce basic zinc sulfate generation,
More effectively copper removal cadmium, is specifically shown in and data is produced by below：
Table 1：Effect list before and after improving
| Content | Slag (%) containing zinc | Copper in Slag (%) | Slag (%) containing cadmium | Zinc powder consumption (Kg/t) | Remarks |
| Before improvement | 40.2 | 6.2 | 5.8 | 21.5 | Liquid contains Cd≤30mg/l after purification |
| After improvement | 30.4 | 9.3 | 8.7 | 16.4 | Liquid contains Cd≤30mg/l after purification |
Explanation：1st, neutral supernatant composition (g/l)：Zn:130~170 Cu:0.3~0.6 Cd0.5~0.9
2nd, zinc powder chemical composition (%)：ZnAlways≥95 ZnMetal≥90 Pb≤1.0 Fe≤0.3 Cd≤0.25 Al≤0.05
Granularity：Mesh >=80% of -50 mesh~+160 and it is uniformly distributed.
Embodiment
The present invention and its embodiment are described in further detail with reference to embodiment.
Embodiment 1
In copper-cadmium slag drop zinc boiling groove, using the copper-cadmium slag ore pulp added after activation, Zn contents 140 g/l, Cu are utilized
Zinc in the copper reduction copper-cadmium slag of the g/l of 0.5 g/l, Cd content of content 0.7 neutral supernatant, overflow is seethed with excitement into copper removal cadmium
Groove, the every slagging in 4 hours of bottom ash once, each slagging 7m3, send subsequent processing to reclaim copper cadmium.In copper removal cadmium boiling groove, use
Pulp adds zinc powder, and the purification temperature of zinc powder pulp is controlled at 60 DEG C~75 DEG C, and zinc powder addition is accurately controlled using current potential, is overflow
Stream enter remove residual cadmium tank diameter, the every slagging in 4 hours of bottom ash once, each slagging 7m3, it is discharged into except copper-cadmium slag activates tank diameter.
Except electrolysis waste solution is added in copper-cadmium slag activation tank diameter, pH value 4 is adjusted, overflow press filtration is carried out, overflow enters second segment cobalt.
Embodiment 2
Copper-cadmium slag drop zinc boiling groove in, using add activation after copper-cadmium slag ore pulp, using the g/l of Zn contents 160,
Zinc in the copper reduction copper-cadmium slag of the g/l of 0.4 g/l, Cd content of Cu contents 0.5 neutral supernatant, overflow is boiled into copper removal cadmium
Rise groove, the every slagging in 4 hours of bottom ash once, each slagging 5m3, send subsequent processing to reclaim copper cadmium.In copper removal cadmium boiling groove, adopt
Zinc powder is added with pulp, the purification temperature of zinc powder pulp is controlled at 60 DEG C~75 DEG C, and zinc powder addition is accurately controlled using current potential,
Overflow enter remove residual cadmium tank diameter, the every slagging in 4 hours of bottom ash once, each slagging 5m3, it is discharged into except copper-cadmium slag activates tank diameter.
Electrolysis waste solution is added in except copper-cadmium slag activation tank diameter, pH value 3.5 is adjusted, carries out overflow press filtration, overflow enters second segment cobalt.
According to YS/T 276.6-2011《The part of indium chemical analysis method the 6th:Copper, cadmium, the measure NITRATE BY FLAME ATOMIC of zinc amount
Absorption spectrometry》, 12689.1~12-2004 of GB/T zinc and kirsite chemical analysis method difference testing example sample
Copper, cadmium, Zn content, test result are as follows：
| Content | Slag (%) containing zinc | Copper in Slag (%) | Slag (%) containing cadmium | Zinc powder consumption (Kg/t) | Remarks |
| Before improvement | 40.2 | 6.2 | 5.8 | 21.5 | Liquid contains Cd≤30mg/l after purification |
| Embodiment 1 | 30.4 | 9.3 | 8.7 | 16.4 | Liquid contains Cd≤30mg/l after purification |
| Embodiment 2 | 28.8 | 8.6 | 7.9 | 15.2 | Liquid contains Cd≤30mg/l after purification |
Claims (6)
1. a kind of method for the purification copper removal cadmium that seethes with excitement, it is characterised in that comprise the following steps：
A, in copper-cadmium slag drop zinc boiling groove, neutral supernatant is continuous to be added from bottom, and flow is controlled in 100 m3/ h~150m3/
H, temperature：55 DEG C~75 DEG C, the copper-cadmium slag ore pulp added after activation reduces the zinc in copper-cadmium slag using the copper of neutral supernatant,
20 minutes~30 minutes reaction time, overflow enter copper removal cadmium seethe with excitement groove, the every slagging in 4 hours of bottom ash once, each m of slagging 53
~10 m3, send subsequent processing to reclaim copper cadmium；
B, in copper removal cadmium boiling groove, overflow that step A is produced is continuous to be added from bottom, and flow is controlled in 100 m3/ h~
150m3/ h, temperature is 55 DEG C~75 DEG C, is continuously added to pulp zinc powder, 20 minutes~30 minutes reaction time, accurate using current potential
Control pulp zinc powder addition, overflow enter remove residual cadmium tank diameter, the every slagging in 4 hours of bottom ash once, each slagging 5m3~10
m3, it is discharged into except copper-cadmium slag activates tank diameter；
C, the bottom ash for producing step B are added except in copper-cadmium slag activation tank diameter, often add a bottom ash, while it is useless to add electrolysis
Liquid, reaction time：30 minutes~60 minutes, temperature：50 DEG C~70 DEG C, pH value 3.5~4.5 is adjusted, overflow press filtration, overflow is carried out
Into second segment purified cobalt.
2. a kind of method of purification copper removal cadmium that seethes with excitement as claimed in claim 1, it is characterised in that：Described neutral supernatant is
Liquid after impure copper, cobalt, cadmium, nickel, arsenic, antimony, the zinc sulfate of germanium are leached, its impurity level is：Zn:130 g/l~170
g/l、 Cu:0.3 g/l~0.6 g/l, Cd：The g/l of 0.5 g/l~0.9, purification temperature is controlled at 55 DEG C~75 DEG C.
3. a kind of method of purification copper removal cadmium that seethes with excitement as claimed in claim 1, it is characterised in that：Described pulp zinc powder refers to
Liquid adds zinc powder and sized mixing formed zinc slurry after zinc sulfate is purified in container of sizing mixing.
4. a kind of method of purification copper removal cadmium that seethes with excitement as claimed in claim 3, it is characterised in that：Described zinc powder chemistry into
Divide (%)：ZnAlways≥95、 ZnMetal>=90, Pb≤1.0, Fe≤0.3, Cd≤0.25, Al≤0.05, zinc powder particle size is：- 50 mesh~
+ 160 mesh >=80% and it is uniformly distributed.
5. a kind of method of purification copper removal cadmium that seethes with excitement as claimed in claim 1, it is characterised in that：Described utilization current potential is accurate
Control pulp zinc powder addition refers to adjust pulp zinc powder consumption according to solution potential online data, reaches that liquid reaches and contained after purification
Cd≤30mg/l quality requirement.
6. a kind of method of purification copper removal cadmium that seethes with excitement as claimed in claim 1, it is characterised in that：Described copper-cadmium slag activation is stirred
Mix groove addition electrolysis waste solution composition and content be：Sulfuric acid：150~200g/l, zinc：40~60 g/l, the amount of addition is to make
The bottom ash pH value added every time is controlled between 3.5~4.5.
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| CN201210588871.0A CN103014339B (en) | 2012-12-31 | 2012-12-31 | A kind of method for the purification copper removal cadmium that seethes with excitement |
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| CN201210588871.0A CN103014339B (en) | 2012-12-31 | 2012-12-31 | A kind of method for the purification copper removal cadmium that seethes with excitement |
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| CN103014339B true CN103014339B (en) | 2017-07-28 |
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| CN112063855A (en) * | 2020-08-06 | 2020-12-11 | 云南云铜锌业股份有限公司 | Method for selectively purifying and removing copper and cadmium by automatic potential control |
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| GB1028469A (en) * | 1963-04-17 | 1966-05-04 | Ass Elect Ind | Preparation of zinc and cadmium sulphides |
| CN101407862B (en) * | 2008-11-28 | 2011-02-09 | 株洲冶炼集团股份有限公司 | Method for previously removing copper from copper-containing solution |
| CN102011001B (en) * | 2010-12-31 | 2012-11-07 | 株洲冶炼集团股份有限公司 | Feeding device and method for cadmium-removing boiling purification tank system |
| CN102417984B (en) * | 2011-12-09 | 2013-04-24 | 株洲冶炼集团股份有限公司 | Method for purifying zinc sulfate solution |
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