CN103773964A - Method for preparing cadmium metal from copper and cadmium slag leachate - Google Patents

Method for preparing cadmium metal from copper and cadmium slag leachate Download PDF

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Publication number
CN103773964A
CN103773964A CN201410040627.XA CN201410040627A CN103773964A CN 103773964 A CN103773964 A CN 103773964A CN 201410040627 A CN201410040627 A CN 201410040627A CN 103773964 A CN103773964 A CN 103773964A
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cadmium
copper
metal
leaching
pulp slurry
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CN103773964B (en
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杨斌
张昱琛
冶玉花
张鸿烈
金忠
冯伟
段宏志
邵霞
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Baiyin Nonferrous Group Co Ltd
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Baiyin Nonferrous Group Co Ltd
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 aims to provide a method for preparing cadmium metal from a copper and cadmium slag leachate, solving the problems of short process flow of recovering cadmium from the copper and cadmium slag leachate, poor work environment and inconvenience in transportation in the prior art. The cadmium metal is prepared through ball-milling, leaching, deironing, filter-pressing and cooling so that the strip-shaped cadmium metal is obtained. According to the method, the cadmium preparing flow is shortened, and the strip-shaped cadmium metal with high grade of more than 95 percent is produced, so that cadmium ions in the copper slag leachate are separated out in a strip-shaped cadmium metal form, the convenience is brought for transportation and storage; the labor intensity of employees and the environment pollution are reduced, and better economic and social benefits and popularization values are achieved.

Description

A kind of method of preparing cadmium metal from copper-cadmium slag leach liquor
Technical field
The present invention relates to zinc hydrometallurgy field, be specifically related to a kind of method of preparing cadmium metal from copper-cadmium slag leach liquor.
Background technology
Zinc hydrometallurgy industry reclaims cadmium and all adopts zinc dust precipitation method from copper-cadmium slag, at the cadmium of replacement process output all with the continuous form of cadmium, the continuous cadmium that contains of general cadmium is between 60-80%, cadmium silk floss first forms cadmium group through extruding, and cadmium group slightly refines the thick cadmium of output again, the thick further refining output of cadmium pure cadmium.This operation long flow path in suitability for industrialized production, worker's labour intensity is large, work under bad environment.
Summary of the invention
The object of this invention is to provide a kind of method of preparing cadmium metal from copper-cadmium slag leach liquor, in prior art, from copper-cadmium slag, reclaim to solve that cadmium process flow is long, work under bad environment is transported inconvenient problem.
The present invention adopts technical scheme: a kind of method of preparing cadmium metal from copper-cadmium slag leach liquor, comprises the steps:
Step (1) ball milling: the copper-cadmium slag of hydrometallurgy zinc output is entered to wet-type ball mill, add water and carry out ball milling, controlling liquid-solid volume ratio is 2.5-3.5:1;
Step (2) leaches: the ball milling ore pulp that step 1 is obtained pumps into copper-cadmium slag leaching vat and adds water, control liquid-solid ratio is 4-5:1, ball milling ore pulp is heated up simultaneously, and slowly add the vitriol oil, controlling temperature of reaction is 80 ℃-85 ℃, the control reaction times is 6h-8h, react to pH value be 3.0-3.5, obtain leaching ore pulp;
Step (3) deironing: add Manganse Dioxide in the leaching pulp slurry obtaining in step 2, remove the ferrous iron leaching in pulp slurry, reaction times 0.5-1.0h, obtains deironing and leach pulp slurry;
Step (4) press filtration: the deironing leaching pulp slurry that step 3 is obtained pumps into chamber filter press and carries out press filtration, and filter residue is that copper ashes enters copper ashes pickling process, and filtrate is copper-cadmium slag leach liquor;
Step (5) is cooling: the copper-cadmium slag leach liquor that step 4 is obtained pumps into cooling tower circulating cooling, and cooling temperature is 35 ℃-45 ℃;
Step (6) is prepared cadmium metal: cooled step 4 copper-cadmium slag leach liquor is pumped into cadmium metal preparation vessel, slowly add 80-120 object metal zinc, zinc powder add-on is the 35%-40% of cadmium metal total amount in reaction solution, control mixing speed is 35 r/min-45r/min, reaction times is 20min-40min, obtains strip metal cadmium.
Further, when ferrous iron content in leaching pulp slurry in described step 3 is not more than 50mg/L, add ball milling ore pulp to leaching in pulp slurry, regulate PH to 4.5-5, continue reaction 0.5h and be less than 100mg/L to leaching total iron content in pulp slurry, obtain deironing and leach pulp slurry.
Further, the taper cell body of the preparation vessel in described step 6 inner side is provided with stabilier.
Further, described stabilier is at least two.
The main chemical equation of deironing is:
MnO 2+2Fe 2+?+4H 2O=2Fe(OH) 3+Mn 2++2H +
The invention has the beneficial effects as follows: shortened cadmium flow process processed, and the strip metal cadmium of output higher-grade (cadmium content is greater than 95%), cadmium ion in copper ashes leach liquor is separated out with the cadmium metal form of strip, be convenient to transportation and store, reduce worker's labour intensity and environmental pollution simultaneously, and there is better economical, societal benefits and promotional value; Change the simple circumferential motion state of cadmium displacement slot liquid in the past by stabilier is set in preparation vessel, be beneficial to the generation of strip metal cadmium and grow up.
Accompanying drawing explanation
Fig. 1 is cadmium metal preparation vessel schematic diagram of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment 1
Step 1 ball milling: by copper-cadmium slag 7 t(H of hydrometallurgy zinc output 2o:38%, Zn:29%, Cd:4.5%) enter wet-type ball mill, add water and carry out ball milling, controlling liquid-solid volume ratio is 2.5:1;
Step 2 leaches: the ball milling ore pulp that step 1 is obtained pumps into copper-cadmium slag leaching vat and adds water, control liquid-solid ratio is 4:1, ball milling ore pulp is heated up simultaneously, and slowly add the vitriol oil, and controlling temperature of reaction is 80 ℃, the control reaction times is 6h, react to pH value be 3.0, must leach pulp slurry (Zn:76.3g/L, Cd:11.9 g/L, Fe:1.2 g/L);
Step 3 deironing: add Manganse Dioxide 27kg in the leaching pulp slurry obtaining in step 2, remove the ferrous iron leaching in pulp slurry, reaction times 0.5h, the ferrous iron content leaching in pulp slurry is 46mg/L, add ball milling ore pulp to leaching in pulp slurry, regulate PH to 4.5, continue reaction 0.5h to leaching total iron content 77mg/L in pulp slurry, obtain deironing and leach pulp slurry (Zn:77.1g/L, Cd:10.8 g/L);
Step 4 press filtration: the deironing leaching pulp slurry that step 3 is obtained pumps into chamber filter press and carries out press filtration, and filter residue is that copper ashes enters copper ashes pickling process, and filtrate is copper-cadmium slag leach liquor, and zinc ion content is less than 100 g/L, and cadmium ion content is greater than 8 g/L;
Step (5) is cooling: the copper-cadmium slag leach liquor that step 4 is obtained pumps into cooling tower circulating cooling, and cooling temperature is 35 ℃;
Step (6) is prepared strip metal cadmium: cooled step 4 copper-cadmium slag leach liquor is pumped into cadmium metal preparation vessel, slowly add 80 object metal zincs, zinc powder add-on be in reaction solution cadmium metal total amount 37%, controlling mixing speed is 35 r/min, reaction times is 20min, obtain strip metal cadmium 85kg, cadmium content is 95.8%.
Embodiment 2
Step 1 ball milling: by copper-cadmium slag 7.5 t(H of hydrometallurgy zinc output 2o:40%, Zn:31%, Cd:5%) enter wet-type ball mill, add water and carry out ball milling, controlling liquid-solid volume ratio is 3.0:1;
Step 2 leaches: the ball milling ore pulp that step 1 is obtained pumps into copper-cadmium slag leaching vat and adds water, control liquid-solid ratio is 4.5:1, ball milling ore pulp is heated up simultaneously, and slowly add the vitriol oil, and controlling temperature of reaction is 83 ℃, the control reaction times is 7h, react to pH value be 3.2, must leach pulp slurry (Zn:83.7g/L, Cd:13.5 g/L, Fe:1.5 g/L);
Step 3 deironing: add Manganse Dioxide 36kg in the leaching pulp slurry obtaining in step 2, remove the ferrous iron leaching in pulp slurry, reaction times 0.8h, the ferrous iron content leaching in pulp slurry is 40mg/L, add ball milling ore pulp to leaching in pulp slurry, regulate PH to 4.8, continue reaction 0.5h to leaching total iron content 65mg/L in ore pulp, obtain deironing and leach pulp slurry (Zn:84.1g/L, Cd:12.2 g/ L);
Step 4 press filtration: the deironing leaching pulp slurry that step 3 is obtained pumps into chamber filter press and carries out press filtration, and filter residue is that copper ashes enters copper ashes pickling process, and filtrate is copper-cadmium slag leach liquor, and zinc ion content is less than 100 g/L, and cadmium ion content is greater than 8g/L;
Step (5) is cooling: the copper-cadmium slag leach liquor that step 4 is obtained pumps into cooling tower circulating cooling, and cooling temperature is 40 ℃;
Step (6) is prepared strip metal cadmium: cooled step 4 copper-cadmium slag leach liquor is pumped into cadmium metal preparation vessel, slowly add 100 object metal zincs, zinc powder add-on be in reaction solution cadmium metal total amount 38%, controlling mixing speed is 40 r/min, reaction times is 30min, obtain strip metal cadmium 107kg, cadmium content is 96.2%.
Embodiment 3
Step 1 ball milling: by copper-cadmium slag 7.8 t(H of hydrometallurgy zinc output 2o:42%, Zn:30%, Cd:4%) enter wet-type ball mill, add water and carry out ball milling, controlling liquid-solid volume ratio is 3.5:1;
Step 2 leaches: the ball milling ore pulp that step 1 is obtained pumps into copper-cadmium slag leaching vat and adds water, control liquid-solid ratio is 5:1, ball milling ore pulp is heated up simultaneously, and slowly add the vitriol oil, and controlling temperature of reaction is 85 ℃, the control reaction times is 8h, react to pH value be 3.5, must leach pulp slurry (Zn:73.2g/L, Cd:9.9g/l, Fe:1.6 g/L);
Step 3 deironing: add Manganse Dioxide 39kg in the leaching pulp slurry obtaining in step 2, remove the ferrous iron leaching in pulp slurry, reaction times 1.0h, the ferrous iron content leaching in pulp slurry is 38mg/L, add ball milling ore pulp to leaching in pulp slurry, regulate PH to 5.0, continue reaction 0.5h to leaching total iron content 54mg/L in ore pulp, obtain deironing and leach pulp slurry (Zn:72.8 g/L, Cd:9.5g/ L);
Step 4 press filtration: the deironing leaching pulp slurry that step 3 is obtained pumps into chamber filter press and carries out press filtration, and filter residue is that copper ashes enters copper ashes pickling process, and filtrate is copper-cadmium slag leach liquor, and zinc ion concentration is less than 100 g/L, and concentration of cadmium ions is greater than 8g/L;
Step (5) is cooling: the copper-cadmium slag leach liquor that step 4 is obtained pumps into cooling tower circulating cooling, and cooling temperature is 45 ℃;
Step (6) is prepared strip metal cadmium: cooled step 4 copper-cadmium slag leach liquor is pumped into cadmium metal preparation vessel, slowly add 120 object metal zincs, zinc powder add-on be in reaction solution cadmium metal total amount 40%, controlling mixing speed is 45 r/min, reaction times is 40min, obtain strip metal cadmium 88kg, cadmium content is 96.5%.
The present invention has changed the simple circumferential motion state of cadmium displacement slot liquid in the past by least two stabiliers 2 are set in the taper cell body 1 in preparation vessel as shown in Figure 1, is beneficial to the generation of strip metal cadmium and grows up.

Claims (4)

1. a method of preparing cadmium metal from copper-cadmium slag leach liquor, is characterized in that, comprises the steps:
Step (1) ball milling: the copper-cadmium slag of hydrometallurgy zinc output is entered to wet-type ball mill, add water and carry out ball milling, controlling liquid-solid volume ratio is 2.5-3.5:1;
Step (2) leaches: the ball milling ore pulp that step 1 is obtained pumps into copper-cadmium slag leaching vat and adds water, control liquid-solid ratio is 4-5:1, ball milling ore pulp is heated up simultaneously, and slowly add the vitriol oil, controlling temperature of reaction is 80 ℃-85 ℃, the control reaction times is 6h-8h, react to pH value be 3.0-3.5, obtain leaching ore pulp;
Step (3) deironing: add Manganse Dioxide in the leaching pulp slurry obtaining in step 2, remove the ferrous iron leaching in pulp slurry, reaction times 0.5-1.0h, obtains deironing and leach pulp slurry;
Step (4) press filtration: the deironing leaching pulp slurry that step 3 is obtained pumps into chamber filter press and carries out press filtration, and filter residue is that copper ashes enters copper ashes pickling process, and filtrate is copper-cadmium slag leach liquor;
Step (5) is cooling: the copper-cadmium slag leach liquor that step 4 is obtained pumps into cooling tower circulating cooling, and cooling temperature is 35 ℃-45 ℃;
Step (6) is prepared cadmium metal: cooled step 4 copper-cadmium slag leach liquor is pumped into cadmium metal preparation vessel, slowly add 80-120 object metal zinc, zinc powder add-on is the 35%-40% of cadmium metal total amount in reaction solution, control mixing speed is 35 r/min-45r/min, reaction times is 20min-40min, obtains strip metal cadmium.
2. a kind of method of preparing strip metal cadmium from copper-cadmium slag leach liquor according to claim 1, it is characterized in that: when the ferrous iron content in the leaching pulp slurry in described step (3) is not more than 50mg/L, add ball milling ore pulp to leaching in pulp slurry, regulate PH to 4.5-5, continue reaction 0.5h and be less than 100mg/L to leaching total iron content in pulp slurry, obtain deironing and leach pulp slurry.
3. a kind of method of preparing cadmium metal from copper-cadmium slag leach liquor according to claim 1, is characterized in that: taper cell body (1) inner side of the preparation vessel in described step (6) is provided with stabilier (2).
4. a kind of method of preparing cadmium metal from copper-cadmium slag leach liquor according to claim 3, is characterized in that: described stabilier (2) is at least two.
CN201410040627.XA 2014-01-28 2014-01-28 A kind of method preparing cadmium metal from copper-cadmium slag Active CN103773964B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106282569A (en) * 2015-06-12 2017-01-04 陕西瑞凯环保科技有限公司 A kind of copper-cadmium slag puies forward the method for cadmium residue resource reclaim
CN107673400A (en) * 2017-08-18 2018-02-09 西北矿冶研究院 Method for producing zinc sulfate heptahydrate from copper-cadmium slag
CN109161688A (en) * 2018-09-13 2019-01-08 白银有色集团股份有限公司 A method of recycling copper, cadmium from copper-cadmium slag
CN111235406A (en) * 2020-02-13 2020-06-05 潘国祥 Improved sponge cadmium replacement process
CN112095014A (en) * 2020-09-27 2020-12-18 衡阳市大宇锌业有限公司 Method for efficiently recycling copper and cadmium from copper-cadmium slag
CN114774692A (en) * 2022-04-29 2022-07-22 新疆紫金有色金属有限公司 Method for removing cadmium and cobalt from poor cadmium solution of zinc hydrometallurgy system

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CN102517455A (en) * 2011-12-29 2012-06-27 株洲冶炼集团股份有限公司 Method for recovering cadmium from copper cadmium residues

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CN102517455A (en) * 2011-12-29 2012-06-27 株洲冶炼集团股份有限公司 Method for recovering cadmium from copper cadmium residues

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106282569A (en) * 2015-06-12 2017-01-04 陕西瑞凯环保科技有限公司 A kind of copper-cadmium slag puies forward the method for cadmium residue resource reclaim
CN107673400A (en) * 2017-08-18 2018-02-09 西北矿冶研究院 Method for producing zinc sulfate heptahydrate from copper-cadmium slag
CN109161688A (en) * 2018-09-13 2019-01-08 白银有色集团股份有限公司 A method of recycling copper, cadmium from copper-cadmium slag
CN111235406A (en) * 2020-02-13 2020-06-05 潘国祥 Improved sponge cadmium replacement process
CN112095014A (en) * 2020-09-27 2020-12-18 衡阳市大宇锌业有限公司 Method for efficiently recycling copper and cadmium from copper-cadmium slag
CN114774692A (en) * 2022-04-29 2022-07-22 新疆紫金有色金属有限公司 Method for removing cadmium and cobalt from poor cadmium solution of zinc hydrometallurgy system

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