CN108977666B - Method for recovering zinc and cobalt in zinc hydrometallurgy purification slag - Google Patents
Method for recovering zinc and cobalt in zinc hydrometallurgy purification slag Download PDFInfo
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- CN108977666B CN108977666B CN201811003366.9A CN201811003366A CN108977666B CN 108977666 B CN108977666 B CN 108977666B CN 201811003366 A CN201811003366 A CN 201811003366A CN 108977666 B CN108977666 B CN 108977666B
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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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 discloses a method for recovering zinc and cobalt in zinc hydrometallurgy purification slag. The process comprises the steps of firstly, placing a cadmium-poor cobalt solution obtained after removing copper and cadmium in copper and cadmium slag generated in a first stage of zinc hydrometallurgy and purification in a cadmium-poor cobalt precipitation tank, then slurrying cobalt and nickel slag generated in a second stage of purification, mixing the slurried solution with the cadmium-poor cobalt solution in the cadmium-poor cobalt precipitation tank, and precipitating cobalt in the cadmium-poor cobalt precipitation solution through zinc powder contained in the cobalt and nickel slag in the presence of an active agent for a certain reaction time and at a certain reaction temperature; the method recycles the zinc powder of the cobalt-nickel slag, simultaneously realizes full sedimentation of cobalt in the cobalt-precipitation liquid poor in cadmium, greatly reduces the consumption of the zinc powder, and reduces the production cost. The process is simple and reasonable, is easy to operate, well realizes the recycling of waste residues, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of metal smelting slag recovery treatment, and particularly relates to a recycling method of zinc hydrometallurgy purification slag, in particular to a recovery method of zinc and cobalt in the zinc hydrometallurgy purification slag. The purification slag is used for replacing zinc powder to carry out cobalt precipitation recovery on the cobalt in the poor cadmium cobalt solution, so that the reutilization of the purification slag is realized, and the recovery of the zinc and the cobalt in the purification slag is also realized.
Technical Field
The hydrometallurgy technology is a metal smelting method with low energy consumption, less pollution, low raw material grade and high valuable metal recovery rate, and plays an important role in the smelting field of copper, lead, zinc and other metals. Wherein, the zinc yield of the zinc hydrometallurgy all over the world accounts for more than 70 percent of the total zinc yield, and the domestic zinc hydrometallurgy yield is more than 2 times of the zinc hydrometallurgy yield in the country.
In the hydrometallurgical process, the adopted hydrometallurgical raw materials usually contain a plurality of associated elements, which affect the grade of the smelting metal. Therefore, in order to smelt a high-quality product with a low impurity content, the metallurgical raw materials need to be purified. Impurities contained in the raw materials are usually removed by adding an excess of singlet metal powder during the purification and deslagging process.
In the process of zinc hydrometallurgy, impurities contained in smelting raw materials are removed through the addition of single-state metal zinc powder and replacement, the replacement is generally divided into two sections, the first section of replacement mainly removes copper and cadmium, the generated waste residue is copper and cadmium slag, the second section of replacement aims at removing trace nickel and cobalt, and the generated waste residue is cobalt and nickel slag. Therefore, the slag generated by replacement contains a large amount of metal zinc and metal elements such as copper, cadmium, cobalt, nickel and the like, and the purified slag has high application value. The cobalt is an important strategic metal and can be used for manufacturing heat-resistant alloy, corrosion-resistant alloy, hard alloy, magnetic material and the like, but the cobalt-containing ore type distributed in China has lower general grade and lower mining value. Therefore, the development of domestic cobalt-containing ores can not meet the domestic demand for cobalt resources, so that the secondary recycling of the cobalt resources has a good application prospect.
In the process of zinc hydrometallurgy, copper and cadmium can be removed by adding zinc powder for replacement, but a large amount of zinc powder is consumed when cobalt and nickel are replaced by the zinc powder, so that the production cost is obviously increased; and in the process, factors such as the granularity of the zinc powder have great influence on the sedimentation of cobalt, so that the industrial application of cobalt removal in the process is not facilitated, and the sediments after the cobalt and nickel removal by replacement contain a large amount of excessive zinc powder, so that the sediments cannot be well recycled.
In addition, in the prior art, purified cobalt nickel slag is crushed by a pulping tank stirrer, waste liquid is pulped and then conveyed to a cobalt slag pickling tank in a cadmium recovery process, the waste liquid is added to leach valuable metals such as zinc, cadmium and the like in dissolved slag, after reaction is finished, a filter press is used for filter pressing and liquid-solid separation, the cobalt slag is used as a raw material in the cobalt process, and liquid is conveyed to a leaching process to recover the valuable metals in the liquid. Meanwhile, in the cadmium working procedure, cobalt metal in the poor cadmium cobalt solution needs to be removed, a zinc powder and antimonate method high-temperature cobalt removal process is adopted, 92% of zinc powder is used in the process, the adding amount of a single groove is 500kg-1000kg of zinc powder, and the production cost is high. Meanwhile, the purified cobalt-nickel slag contains 50-60% of zinc, and contains part of unreacted zinc powder (the main component is simple substance zinc, and the substitution reaction can occur), so that the method has high utilization value. This procedure results in a significant waste of raw materials.
Disclosure of Invention
Aiming at the problems, the invention provides a method for recovering zinc and cobalt in zinc hydrometallurgy purification slag, namely a method for recycling zinc hydrometallurgy purification slag. The method comprises the steps of slurrying cobalt-nickel slag generated in the second stage in the wet zinc smelting process by waste liquid, conveying the slurried cobalt-nickel slag to a cadmium cobalt precipitation tank, adding a certain amount of cobalt liquid poor in cadmium into the cobalt precipitation tank, and removing cobalt metal in the cobalt liquid poor in cadmium by adding antimony salt serving as an activator to ensure sufficient reaction temperature and reaction time so as to reduce the content of liquid cobalt to be below 0.03 g/l.
The invention is realized by the following technical scheme
A method for recovering zinc and cobalt in zinc hydrometallurgy purification slag comprises the following steps:
s1: performing neutral leaching, primary replacement and secondary replacement on the first-stage purified copper-cadmium slag obtained by zinc hydrometallurgy, and placing the produced poor cadmium-cobalt solution in a poor cadmium cobalt precipitation tank for treatment;
s2: recovering cobalt-nickel slag generated in the second stage of zinc hydrometallurgy, slurrying the cobalt-nickel slag, and conveying slurried ore pulp of the cobalt-nickel slag obtained after slurrying to the cobalt precipitation tank with poor cadmium in the step S1 to be mixed with liquid in the cobalt precipitation tank with poor cadmium to obtain mixed liquid;
in the process, the acidity of the liquid used for slurrying the cobalt-nickel slag is 150-200g/l, and the pH value of slurried ore pulp of the cobalt-nickel slag obtained after slurrying is not less than 2; the time of the pulping reaction is 2-6 hours, and the specific gravity of cobalt-nickel slag in the pulp obtained after the pulping reaction is 1.2-1.8 g/cm3。
The acid in the liquid with the acidity of 150-200g/l is sulfuric acid.
S3: antimony trioxide is added into the mixed solution of the poor cadmium cobalt precipitation tank in the step S2, the mixed solution is uniformly stirred, and the reaction is carried out for 2 to 6 hours at the temperature of 70 to 120 ℃; after the reaction is finished, conveying the reaction liquid in the poor cadmium cobalt precipitation tank to a filter press for solid-liquid separation; obtaining filtrate and filter residue;
in the process, determining the using amount of antimony trioxide for cobalt precipitation according to the cobalt content in the cadmium-poor cobalt solution, and according to the cobalt element content in the cadmium-poor cobalt solution, determining the ratio of antimony trioxide to cobalt by mass of 0.2-1: 1 antimony trioxide was added.
The method for recovering zinc and cobalt in the zinc hydrometallurgy purification slag further comprises a step S4 after the step S3, wherein the step S4 is operated as follows: and (5) returning the filtrate obtained in the step (S3) to a main system for recycling (a main system for zinc hydrometallurgy), recovering the obtained filter residue, and separating and recovering zinc and cobalt in the filter residue.
Namely: the recovery method can recover the excessive zinc in the purification slag in the form of simple substance to obtain high-grade simple substance zinc (utilization), and has high utilization value. The zinc powder plays a role in earlier-stage recovery of cobalt and nickel, is well recovered, realizes full recycling, and realizes recovery of elemental cobalt while recovering elemental zinc. The zinc and the cobalt in the first-stage slag and the second-stage slag are simultaneously recovered with high value in the presence of the activating agent, and the method has the advantages of simple process, easy operation and low recovery cost.
The recovery principle of the invention is as follows: the purified copper-cadmium slag generated in the first stage of zinc hydrometallurgy is subjected to neutral leaching, primary replacement and secondary replacement, and the generated poor cadmium-cobalt solution is placed in a poor cadmium cobalt precipitation tank; and then, purified cobalt-nickel slag generated in the second stage of zinc hydrometallurgy purification is placed in a poor-cadmium cobalt precipitation tank to be mixed with the solution in the poor-cadmium cobalt precipitation tank, an activator antimony trioxide is added after mixing, the antimony trioxide can further increase the activity of elemental zinc in the cobalt-nickel slag, the elemental zinc with increased activity further promotes the cobalt in the mixed solution to precipitate and simultaneously precipitate with the elemental zinc to form slag under certain conditions, most of the cobalt element and the elemental zinc in the liquid precipitate to form slag after certain reaction, and a very small amount of elements such as zinc, cobalt and the like are remained in the liquid and are recycled.
Compared with the prior art, the invention has the following positive beneficial effects
The cobalt in the first-stage zinc hydrometallurgy purified copper-cadmium slag is directly replaced by the elemental zinc powder, so that a large amount of zinc powder is consumed, the treatment cost is increased, and the excessive zinc powder cannot be recycled well, so that the resource is seriously wasted. The invention makes the copper-cadmium slag interact with the second-stage purified cobalt-nickel slag after neutral leaching, first-stage replacement and second-stage replacement, in the process, the zinc in the second-stage purified cobalt-nickel slag fully settles the cobalt in the first-stage liquid in the presence of an activator, and simultaneously the zinc in the second-stage purified cobalt-nickel slag fully settles, namely the cobalt in the first-stage purified cobalt-nickel slag from which the copper and the cadmium are removed and the zinc and the cobalt in the second-stage purified cobalt-nickel slag simultaneously settle to form slag, the cobalt is fully settled, and meanwhile, the zinc simple substance is fully recovered. Therefore, in the process, the interaction of the first-stage purification residual liquid and the second-stage purification slag enables the zinc and the cobalt in the first-stage purification residual liquid to be fully settled in the presence of the activating agent, so that the zinc element and the cobalt element in the purification slag are fully recovered, the grade is high, and the reutilization value is high;
therefore, the invention adopts the zinc powder in the cobalt-nickel slag to carry out cobalt precipitation, the purified slag is used for replacing the zinc powder, the cobalt precipitation realizes the zero addition of the zinc powder, and the usage amount of the zinc powder is directly reduced (excessive zinc powder needs to be added in the process of precipitation of copper, cadmium and cobalt); meanwhile, zinc in the purification slag and excessive zinc powder added for removing copper and cadmium in the purification slag are recovered to the maximum extent, and the zinc powder is fully recovered in high grade;
the method has the advantages of reasonable and concise process design, simple operation, no addition of a large amount of extra reagents or complicated operation, high resource utilization rate, capability of recycling the filtrate and the filter residue of the system and no pollution; the whole recovery process saves cost, has high efficiency and low cost, and has good industrial application prospect in the field.
Drawings
FIG. 1 is a process flow diagram of the zinc cobalt recovery method of the present invention.
Detailed Description
The present invention is described in more detail below with reference to specific examples, but the present invention is not limited to the following examples. In the following examples, the acid contained in the acid-containing waste liquid with acidity of 150-200g/l is sulfuric acid.
Example 1
A method for recovering zinc and cobalt in zinc hydrometallurgy purification slag comprises the following steps:
s1: after neutral leaching, primary replacement and secondary replacement are carried out on the first-stage purified copper-cadmium slag obtained by zinc hydrometallurgy, the produced poor cadmium-cobalt solution is placed in a poor cadmium-cobalt precipitation tank for treatment;
wherein, the amount of the cadmium-poor cobalt solution in the cadmium-poor cobalt precipitation tank is 40m3Wherein the cobalt content is 0.089g/l, and the zinc content is 45.5 g/l; s2: recovering cobalt-nickel slag generated in the zinc hydrometallurgy second stage, slurrying (mixing and stirring) the cobalt-nickel slag by adopting 200g/l of waste liquid containing 150-fold acid generated in the electrolysis process, and performing slurrying reaction for 4 hours to obtain slurried ore pulp;
delivering the slurried cobalt nickel slag ore slurry into the low-cadmium cobalt precipitation tank in the step S1 through a delivery pump, mixing the slurried cobalt nickel slag ore slurry with the low-cadmium cobalt solution in the low-cadmium cobalt precipitation tank, and delivering the slurried cobalt nickel slag ore slurry into the low-cadmium cobalt precipitation tank with the amount of 8m3；
Wherein the mass fraction of the singlet metal zinc powder in the two-stage cobalt-nickel slag is 48%; the content of cobalt element is 0.31 percent, and the specific gravity of the cobalt-nickel slag in the slurried ore pulp of the cobalt-nickel slag is 1.4g/cm3；
S3: adding 2kg of antimony trioxide into the mixed solution of the poor cadmium cobalt precipitation tank in the step S2, uniformly stirring, and reacting for 4 hours at the temperature of 70-90 ℃; after the reaction is finished, conveying the reaction liquid in the poor cadmium cobalt precipitation tank to a filter press for solid-liquid separation; obtaining filtrate and filter residue;
s4: returning the filtrate obtained in the step S3 to the zinc hydrometallurgy main system for recycling; and recovering filter residues, and separating and recovering zinc and cobalt in the filter residues.
Detecting the cobalt content in the filtrate obtained in the step S4 by adopting a spectrophotometry, and detecting the content of metal zinc in the filter residue, wherein the result shows that: the cobalt content in the obtained filtrate was 0.012g/l, and the zinc content in the obtained residue was 41.5% by mass. Namely, cobalt and zinc are fully recovered at the same time, so that cobalt in the purification slag is fully recovered, and zinc in the purification slag is fully recovered.
Example 2
A method for recovering zinc and cobalt in zinc hydrometallurgy purification slag comprises the following steps:
s1: after neutral leaching, primary replacement and secondary replacement are carried out on the first-stage purified copper-cadmium slag obtained by zinc hydrometallurgy, the produced poor cadmium-cobalt solution is placed in a poor cadmium-cobalt precipitation tank for treatment;
wherein the solution in the poor cadmium cobalt precipitation tank is 35m3(ii) a The cobalt content in the cobalt liquid poor in cadmium is 0.15g/l, and the zinc content in the waste liquid is 53.8 g/l;
s2: recovering cobalt-nickel slag generated in the zinc hydrometallurgy second-stage, slurrying (mixing and stirring) the cobalt-nickel slag by using acid-containing waste liquid with acidity of 150-;
delivering the slurried cobalt nickel slag slurry into the cadmium-poor cobalt precipitation tank in the step S1 through a delivery pump, mixing the slurried cobalt nickel slag slurry with the cadmium-poor cobalt solution in the cadmium-poor cobalt precipitation tank, and delivering the slurried ore slurry into the cadmium-poor cobalt precipitation tank with the amount of 10m3；
Wherein the mass fraction of the singlet metal zinc powder in the two-stage cobalt-nickel slag is 53%; the content of cobalt element is 0.22 percent; the specific gravity of the cobalt-nickel slag in the obtained cobalt-nickel slag slurried ore pulp is 1.45g/cm3；
S3: adding 3kg of antimony trioxide into the mixed solution of the poor cadmium cobalt precipitation tank in the step S2, uniformly stirring, and reacting for 2 hours at the temperature of 80-100 ℃; after the reaction is finished, conveying the reaction liquid in the poor cadmium cobalt precipitation tank to a filter press for solid-liquid separation; obtaining filtrate and filter residue;
s4: returning the filtrate obtained in the step S3 to the zinc hydrometallurgy main system for recycling; and recovering filter residues, and separating and recovering zinc and cobalt in the filter residues.
Detecting the cobalt content in the filtrate obtained in the step S4 by adopting a spectrophotometry, and detecting the content of metal zinc in the filter residue, wherein the result shows that: the cobalt content in the obtained filtrate is 0.0084g/l, and the zinc content in the obtained filter residue is 45.7% by mass. Namely, cobalt and zinc are fully recovered at the same time, so that cobalt in the purification slag is fully recovered, and zinc in the purification slag is fully recovered.
Example 3
A method for recovering zinc and cobalt in zinc hydrometallurgy purification slag comprises the following steps:
s1: after neutral leaching, primary replacement and secondary replacement are carried out on the first-stage purified copper-cadmium slag obtained by zinc hydrometallurgy, the produced poor cadmium-cobalt solution is placed in a poor cadmium-cobalt precipitation tank for treatment;
wherein the amount of the cadmium-poor cobalt solution in the cadmium-poor cobalt precipitation tank is 30m3The cobalt content in the cobalt liquid poor in cadmium is 0.26g/l, and the zinc content in the waste liquid is 55.6 g/l;
s2: recovering cobalt-nickel slag generated in the zinc hydrometallurgy second stage, slurrying (mixing and stirring) the cobalt-nickel slag by adopting acid-containing waste liquid with acidity of 150-200g/l generated in the electrolysis process, and performing slurrying reaction for 3h to obtain slurried ore pulp;
the slurried cobalt nickel slag slurried ore pulp is conveyed into the cadmium-poor cobalt precipitation tank in the step S1 through a conveying pump, the slurried ore pulp is mixed with the waste liquid in the cadmium-poor cobalt precipitation tank, and the amount of the slurried ore pulp conveyed into the cadmium-poor cobalt precipitation tank is 12m3；
Wherein the mass fraction of the singlet metal zinc powder in the two-stage cobalt-nickel slag is 55%; the content of cobalt element is 0.27%; the specific gravity of the cobalt-nickel slag in the obtained cobalt-nickel slag slurried ore pulp is 1.5g/cm3；
S3: adding 4kg of antimony trioxide into the mixed solution of the poor cadmium cobalt precipitation tank in the step S2, uniformly stirring, and reacting for 4 hours at the temperature of 80-100 ℃; after the reaction is finished, conveying the reaction liquid in the poor cadmium cobalt precipitation tank to a filter press for solid-liquid separation; obtaining filtrate and filter residue;
s4: returning the filtrate obtained in the step S3 to the zinc hydrometallurgy main system for recycling; and recovering filter residues, and separating and recovering zinc and cobalt in the filter residues.
Detecting the cobalt content in the filtrate obtained in the step S4 by adopting a spectrophotometry, and detecting the content of metal zinc in the filter residue, wherein the result shows that: the cobalt content in the obtained filtrate was 0.018g/l, and the zinc content in the obtained residue was 43.9% by mass. Namely, cobalt and zinc are fully recovered at the same time, so that cobalt in the purification slag is fully recovered, and zinc in the purification slag is fully recovered.
Example 4
A method for recovering zinc and cobalt in zinc hydrometallurgy purification slag comprises the following steps:
s1: after neutral leaching, primary replacement and secondary replacement are carried out on the first-stage purified copper-cadmium slag obtained by zinc hydrometallurgy, the produced poor cadmium-cobalt solution is placed in a poor cadmium-cobalt precipitation tank for treatment;
wherein the amount of the cadmium-poor cobalt solution in the cadmium-poor cobalt precipitation tank is 45m3The cobalt content in the cobalt liquid with low cadmium content is 0.088g/l, and the zinc content in the waste liquid is 59.5 g/l;
s2: recovering cobalt-nickel slag generated in the zinc hydrometallurgy second-stage, slurrying (mixing and stirring) the cobalt-nickel slag by adopting acid-containing waste liquid with acidity of 150-;
the slurried cobalt nickel slag slurrying ore pulp is conveyed into the cadmium-poor cobalt precipitation tank in the step S1 through a conveying pump, the slurried cobalt nickel slag slurrying ore pulp is mixed with the cadmium-poor cobalt solution in the cadmium-poor cobalt precipitation tank, and the amount of the slurried ore pulp conveyed into the cadmium-poor cobalt precipitation tank is 8m3；
Wherein the mass fraction of the singlet state metallic zinc powder in the two-stage purified cobalt-nickel slag is 56%; the content of cobalt element is 0.36%; the specific gravity of the cobalt-nickel slag in the obtained cobalt-nickel slag slurried ore pulp is 1.5g/cm3；
S3: adding 3kg of antimony trioxide into the mixed solution of the poor cadmium cobalt precipitation tank in the step S2, uniformly stirring, and reacting for 4 hours at the temperature of 70-90 ℃; after the reaction is finished, conveying the reaction liquid in the poor cadmium cobalt precipitation tank to a filter press for solid-liquid separation; obtaining filtrate and filter residue;
s4: returning the filtrate obtained in the step S3 to the zinc hydrometallurgy main system for recycling; and recovering filter residues, and separating and recovering zinc and cobalt in the filter residues.
Detecting the cobalt content in the filtrate obtained in the step S4 by adopting a spectrophotometry, and detecting the content of metal zinc in the filter residue, wherein the result shows that: the cobalt content in the obtained filtrate was 0.0056g/l, and the zinc content in the obtained residue was 44.3% by mass. Namely, cobalt and zinc are fully recovered at the same time, so that cobalt in the purification slag is fully recovered, and zinc in the purification slag is fully recovered.
Therefore, the method provided by the invention has the advantages that the cobalt and the zinc in the first-stage purification slag of the first-stage zinc hydrometallurgy and the cobalt and the zinc in the second-stage purification slag are efficiently recovered through a simple operation process, the purification slag of the zinc hydrometallurgy is fully recovered and reused, the valuable metals in the first-stage purification slag and the second-stage purification slag are recovered through the interaction between the two kinds of slag, the waste of a large amount of original resources is reduced, the economic benefit is very high, and the method has a good industrial application prospect.
Claims (6)
1. A method for recovering zinc and cobalt in zinc hydrometallurgy purification slag is characterized by comprising the following steps:
s1: after neutral leaching, primary replacement and secondary replacement are carried out on the first-stage purified copper-cadmium slag obtained by zinc hydrometallurgy, the produced poor cadmium-cobalt solution is placed in a poor cadmium-cobalt precipitation tank for treatment;
s2: recovering cobalt-nickel slag generated in the second stage of zinc hydrometallurgy, performing slurrying reaction on the cobalt-nickel slag to obtain slurried ore pulp, conveying the cobalt-nickel slag ore pulp subjected to the slurrying reaction to the low-cadmium cobalt precipitation tank in the step S1, and mixing the cobalt-nickel slag ore pulp with the low-cadmium cobalt solution in the low-cadmium cobalt precipitation tank to obtain mixed solution;
s3, adding antimony trioxide into the mixed solution of the cadmium-poor cobalt precipitation tank in the step S2, uniformly stirring, reacting for 2 ~ 6 hours at the temperature of 70 ~ 120 ℃, and after the reaction is finished, conveying the reaction solution in the cadmium-poor cobalt precipitation tank to a filter press for solid-liquid separation to obtain filtrate and filter residue;
the mass ratio of the addition amount of the antimony trioxide to the cobalt content in the cadmium-depleted cobalt solution in the step S1 is (0.2-1): 1.
2. the method for recovering zinc and cobalt from zinc hydrometallurgy purification slag according to claim 1, wherein the acidity of the liquid used in the cobalt nickel slag slurrying reaction in step S2 is 150 ~ 200g/l, and the pH value of the slurry obtained after the cobalt nickel slag is slurried is not less than 2.
3. The method for recovering zinc and cobalt from zinc hydrometallurgy purification slag according to claim 2, wherein the acid in the liquid with acidity of 150 ~ 200g/l is sulfuric acid.
4. The method for recovering zinc and cobalt from the zinc hydrometallurgy purification slag according to any one of claims 1 ~ 3, wherein the time for carrying out the slurrying reaction on the cobalt-nickel slag in the step S2 is 2 ~ 6 hours.
5. The method for recovering Zn and Co from purified wet zinc smelting slag according to claim 1 ~ 3, wherein the specific gravity of Co and Ni slag in the slurry pulp obtained after the reaction in step S2 is 1.2 ~ 1.8g/cm3。
6. The method for recovering zinc and cobalt from zinc hydrometallurgy purification slag according to claim 1, characterized in that step S4 is further included after step S3, and the operation of step S4 is as follows: and (5) returning the filtrate obtained in the step (S3) to the main system for recycling, recovering the obtained filter residue, and separating and recovering zinc and cobalt in the filter residue.
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| CN114472881A (en) * | 2021-12-30 | 2022-05-13 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Zinc powder activated slurry and preparation method thereof, impurity removal method and impurity removal device |
| CN114875242A (en) * | 2022-04-25 | 2022-08-09 | 河南豫光锌业有限公司 | Method for improving copper recovery rate 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 |
| CN114774693A (en) * | 2022-05-06 | 2022-07-22 | 新疆紫金有色金属有限公司 | Comprehensive utilization method of zinc hydrometallurgy two-clean slag |
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| CN101709382A (en) * | 2009-12-17 | 2010-05-19 | 新乡超能电源有限公司 | Recovery and comprehensive treatment process of valuable metals in zinciferous materials |
| CN103194600A (en) * | 2013-04-23 | 2013-07-10 | 吴鋆 | Method for purifying zinc sulfide solution |
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