CN110016567B - Method for recovering copper from zinc hydrometallurgy copper slag - Google Patents
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Abstract
The invention provides a method for recovering copper from zinc hydrometallurgy copper slag, which comprises the following steps: step 1) primary slurrying process, step 2) secondary slurrying and ball milling, step 3) tertiary slurrying, first-stage leaching process, step 4) quaternary slurrying, second-stage leaching process, step 5) dechlorinating process and step 6) electrodeposition process, wherein O is adopted in the invention2+H2O2As an oxidant, Cu, CuS and CuCl are effectively oxidized in one step by adjusting the process sequence and the oxidation leaching steps, and Cl in the CuCl is released at the same time‑Then Cu (powder) is used for removing Cl‑And when the concentration is below 0.3g/l, the cooled and purified pregnant solution is subjected to electrodeposition to produce cathode copper, sectional electrodeposition is carried out according to the electrodeposition density difference under different copper ion concentration conditions, and the leaching rate of copper metal reaches more than 97%.
Description
Technical Field
The invention relates to a resource recycling process technology, in particular to a method for recycling copper from copper slag, and especially relates to a method for recycling copper from zinc hydrometallurgy copper slag.
Background
According to the prior art, the traditional zinc hydrometallurgy copper slag recycling technology mainly has the following problems:
1. the copper slag has high chlorine content and poor alkali washing effect, and leachate Cl-Out of limits (Cl)-> 1.0g/l), the electrowinning density is low, the yield is therefore limited, and the cathode copper product quality is poor.
2. The oxidation method adopts air oxidation, Cu, CuS and CuCl in the copper slag are not effectively leached and are brought into the tailings, so that the recovery rate is reduced, the grades of lead and silver metals in the tailings are reduced, and the additional value is lowered.
Disclosure of Invention
In order to solve the technical problems, the invention mainly aims to provide a method for recovering copper from zinc hydrometallurgy copper slag.
The technical scheme is as follows:
a method for recovering copper from zinc hydrometallurgy copper slag comprises the following steps:
step 1) primary slurrying process: mixing materials according to a liquid-solid ratio of 3.5-4.5: 0.8-1.2, stirring in a first-stage slurrying tank for 20-50 min, conveying to a first pressure filter for solid-liquid separation, and putting a filter cake into a second-stage slurrying tank for secondary slurrying;
step 2), secondary slurrying and ball milling: putting the primary filter cake obtained in the step 1) into a secondary pulping tank according to a liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and pulping for 5-30 min, then feeding the mixture into a ball mill for grinding by a classifier, wherein the grinding particle size is 90-150 meshes, then feeding the mixture into a third filter press for solid-liquid separation, and putting the secondary filter cake into a third pulping tank for pulping for three times;
step 3) pulping for three times, and one-stage leaching process: putting the secondary filter cake obtained in the step 2) into a third-stage slurrying tank according to the liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and slurrying for 5-30 min, and then sending to a first leaching tank;
step 4), pulping for four times, and performing a second-stage leaching process: putting the secondary filter cake obtained in the step 2) into a four-stage slurrying tank according to the liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and slurrying for 5-30 min, and then sending to a second leaching tank;
step 5) dechlorination: taking a first-stage leaching solution of a first leaching tank for 30-50 m3The second-stage leaching solution of the first leaching tank is 15-30 m3To a second dechlorination tank, respectively detecting Cu2+、Cl-And sulfuric acid content according to Cl-Adding zinc powder into a dechlorinating tank, stirring for 0.5-2 h, and adding Cl into the solution-Reducing the concentration to 0.5g/l, standing and settling dechlorination liquid in the first dechlorination tank and the second dechlorination tank for 0.5-2 h, taking supernate and testing Cu2+、Cl-Pumping the supernatant into an electric pregnant solution storage tank, mixing the first-stage leachate with the second-stage leachate, simultaneously replenishing concentrated sulfuric acid, and preparing the sulfuric acid in the electric pregnant solution to be 100-110 g/l;
step 6) electrodeposition: discharging the barren solution in the electrodeposition circulating tank to an electric barren solution storage tank, mixing the electric barren solution in the electric barren solution storage tank with the electric barren solution in the electric barren solution storage tank until the concentration of copper ions is 45-50 g/l, and controlling the current to be 250A and the electric density to be 500A/m2Turbulent electrodeposition is carried out, the concentration of copper ions is reduced from 45-50 g/l to below 15g/l, and cathode copper is produced.
Further, in the step 1), before feeding, the large copper slag is beaten, ground and crushed, impurities are removed,
and the total amount of the salt water in the primary slurrying process is 10-20 m3And recycling.
Furthermore, in the primary slurrying procedure, sampling is carried out to detect Cu in the saline water after the saline water is circulated for 10 times2+、Cl-Content when Cl-At > 3g/l, according to Cu2+And (3) content, treating the brine in a primary slurrying tank, adding caustic soda flakes or calcined soda for copper precipitation, performing solid-liquid separation on the slurry saturated with filter residues through a first filter press, and directly discharging the brine to a brine tank for storage.
Further, in the step 2), the total amount of the salt water in the secondary slurrying process is 10-20 m3Recycling, sampling and detecting Cu in the brine after 20 times of circulation2+、Cl-Content when Cl-When the concentration is more than 2g/l, the brine is discharged to a brine tank for storage.
Further, in the step 3), steam is introduced into the first leaching tank, the temperature is raised to 60-80 ℃, compressed air is introduced for oxidizing leaching for 4 hours, then the first-stage leaching slurry is subjected to solid-liquid separation by using a fourth filter press with a conveying pump, the third-stage filter cake is rinsed with clear water, then the first-stage leaching slurry is put into a fourth-stage slurrying tank, and the filtrate is pumped to a dechlorinating tank through a transfer tank.
Further, in the step 4), steam is introduced into the second leaching tank to raise the temperature to 60-80 ℃, hydrogen peroxide is slowly added according to the speed of 1 ton/hour, after the hydrogen peroxide is added, compressed air is started to carry out oxidation leaching for 2 hours, slurry in the second leaching tank is subjected to solid-liquid separation by using a fifth conveying pump filter press, filter cakes are leached by using clear water until the filtrate is blue and faded, the filter cakes are packaged by tons and conveyed to a lead-silver residue storage, and the filtrate flows to a second-stage leaching solution storage tank automatically.
Further, in step 6), Zn is added in the electrolyte2+When the concentration is more than 50g/l or As is more than 3g/l, the electrobarren solution is discharged to a decoppering circulation tank in batches, the concentration of copper ions is reduced from 15g/l to less than 1g/l, and black copper powder is produced.
Further, the first stage leach slurry contains Cu2+The ion content is 60-75 g/l, and the sulfuric acid content is 15-30 g/l.
Further, Cu in the secondary leaching slurry2+The ion content is 35-45 g/l, and the sulfuric acid content is 70-90 g/l.
The invention extracts copper from the zinc-copper slag smelted by the wet method, firstly slurries the zinc-copper slag smelted by the wet method, then carries out preliminary dechlorination by alkali washing, then screens the zinc-copper slag by a grader, and ball-mills large particles to 120 meshes. And (3) conveying the copper slag subjected to ball milling to a leaching tank, carrying out high-temperature oxidation leaching under an acidic condition, carrying out solid-liquid separation on leaching slurry, enriching metals such as lead, silver and the like in tailings, and conveying the copper-enriched solution to electrodeposition to produce cathode copper.
In the above, O is used2+H2O2As an oxidant, Cu, CuS and CuCl are effectively oxidized in one step by adjusting the process sequence and the oxidation leaching steps, and Cl in the CuCl is released at the same time-Then Cu (powder) is used for removing Cl-When the concentration is lower than 0.3g/l, the cooled and purified pregnant solution is sent to electrodeposition to produce cathode copper, and sectional electrodeposition is carried out according to the electrodeposition density difference under the condition of different copper ion concentrations, and the leaching rate of copper metal reaches more than 97 percent. The problems of appearance quality and chemical quality of the cathode copper are solved, and the method has capacity release conditions.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
Referring to fig. 1, the invention provides a method for recovering copper from zinc hydrometallurgy copper slag, which comprises the following steps:
step 1) primary slurrying process: mixing materials according to a liquid-solid ratio of 3.5-4.5: 0.8-1.2, stirring in a first-stage slurrying tank for 20-50 min, conveying to a first pressure filter for solid-liquid separation, and putting a filter cake into a second-stage slurrying tank for secondary slurrying;
step 2), secondary slurrying and ball milling: putting the primary filter cake obtained in the step 1) into a secondary pulping tank according to a liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and pulping for 5-30 min, then feeding the mixture into a ball mill for grinding by a classifier, wherein the grinding particle size is 90-150 meshes, then feeding the mixture into a third filter press for solid-liquid separation, and putting the secondary filter cake into a third pulping tank for pulping for three times;
step 3) pulping for three times, and one-stage leaching process: putting the secondary filter cake obtained in the step 2) into a third-stage slurrying tank according to the liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and slurrying for 5-30 min, and then sending to a first leaching tank;
step 4), pulping for four times, and performing a second-stage leaching process: putting the secondary filter cake obtained in the step 2) into a four-stage slurrying tank according to the liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and slurrying for 5-30 min, and then sending to a second leaching tank;
step 5) dechlorination: taking a first-stage leaching solution of a first leaching tank for 30-50 m3The second-stage leaching solution of the first leaching tank is 15-30 m3To a second dechlorination tank, respectively detecting Cu2+、Cl-And sulfuric acid content according to Cl-Adding zinc powder into a dechlorinating tank, stirring for 0.5-2 h, and adding Cl into the solution-Reducing the concentration to 0.5g/l, standing and settling dechlorination liquid in the first dechlorination tank and the second dechlorination tank for 0.5-2 h, taking supernate and testing Cu2+、Cl-Pumping the supernatant into an electric pregnant solution storage tank, mixing the first-stage leachate with the second-stage leachate, simultaneously replenishing concentrated sulfuric acid, and preparing the sulfuric acid in the electric pregnant solution to be 100 g/l;
step 6) electrodeposition: discharging the barren solution in the electrodeposition circulating tank to an electric barren solution storage tank, mixing the electric barren solution in the electric barren solution storage tank with the electric barren solution in the electric barren solution storage tank, and controlling the current to be 250A and the electric density to be 500A/m2Turbulent electrodeposition is carried out, the concentration of copper ions is reduced to below 15g/l from 45-50 g/l, and copper is recovered by a cathode.
Further, in the step 1), before feeding, the large copper slag is beaten, ground and crushed, impurities are removed,
and the total amount of the salt water in the primary slurrying process is 10-20 m3And recycling.
Furthermore, in the primary slurrying procedure, sampling is carried out to detect Cu in the saline water after the saline water is circulated for 10 times2+、Cl-Content when Cl-At > 3g/l, according to Cu2+And (3) content, treating the brine in a primary slurrying tank, adding caustic soda flakes or calcined soda for copper precipitation, performing solid-liquid separation on the slurry saturated with filter residues through a first filter press, and directly discharging the brine to a brine tank for storage.
Further, in the step 2), the total amount of the salt water in the secondary slurrying process is 10-20 m3Recycling, sampling and detecting Cu in the brine after 20 times of circulation2+、Cl-And (4) content. When Cl is present-When the concentration is more than 2g/l, the brine is discharged to a brine tank for storage.
Further, in the step 3), steam is introduced into the first leaching tank, the temperature is raised to 60-80 ℃, compressed air is introduced for oxidizing leaching for 4 hours, then the first-stage leaching slurry is subjected to solid-liquid separation by using a fourth filter press with a conveying pump, the third-stage filter cake is rinsed with clear water, then the first-stage leaching slurry is put into a fourth-stage slurrying tank, and the filtrate is pumped to a dechlorinating tank through a transfer tank.
Further, in the step 4), steam is introduced into the second leaching tank to raise the temperature to 60-80 ℃, hydrogen peroxide is slowly added according to the speed of 1 ton/hour, after the hydrogen peroxide is added, compressed air is started to carry out oxidation leaching for 2 hours, slurry in the second leaching tank is subjected to solid-liquid separation by using a fifth conveying pump filter press, filter cakes are leached by using clear water until the filtrate is blue and faded, the filter cakes are packaged by tons and conveyed to a lead-silver residue storage, and the filtrate flows to a second-stage leaching solution storage tank automatically.
Further, in step 6), Zn is added in the electrolyte2+When the concentration is more than 50g/l or As is more than 3g/l, the electrobarren solution is discharged to a decoppering circulation tank in batches, the concentration of copper ions is reduced from 15g/l to less than 1g/l, and black copper powder is produced.
Further, the first stage leach slurry contains Cu2+The ion content is about 60-75 g/l, and the sulfuric acid content is about 15-30 g/l.
Further, Cu in the secondary leaching slurry2+The ion content is about 35-45 g/l, and the sulfuric acid content is about 70-90 g/l.
Example 1
In the embodiment, the resource project of the zinc hydrometallurgy copper slag is designed as an example, 4242 tons of copper slag are treated in year, and 1000 tons of cathode copper are produced in year. The project adopts a wet process to extract copper, firstly slurrying zinc-copper slag smelted by a wet process, then carrying out alkali washing for preliminary dechlorination, then screening by a grader, and carrying out ball milling on large particles to-120 meshes. And (3) conveying the copper slag subjected to ball milling to a leaching tank, carrying out high-temperature oxidation leaching under an acidic condition, carrying out solid-liquid separation on leached slurry, dechlorinating the liquid by using zinc powder to form an electric rich liquid, enriching metals such as lead, silver and the like in tailings, and conveying the electric rich copper liquid to electrodeposition to produce cathode copper.
The zinc hydrometallurgy copper slag recycling project originally designed capacity annual production of 1000 tons of cathode copper, actually the electrodeposition tank heats too fast under the current of more than 250A, meanwhile, the volume of the on-site storage tank is insufficient, the capacity is inverted according to the electrodeposition tank, calculated by annual production of 924 tons of cathode copper and production days of 330 days, and daily production of 2.80 tons of cathode copper is realized. According to the data of the small test and the middle test of the technical concern, the recovery rate of the copper metal in the project is not less than 95 percent, and 2.95 tons of copper metal are needed to be added into the copper slag every day. According to the historical data of purchased copper slag, the average copper content of wet slag is 29.72 percent, 9.91 tons of wet-based copper slag are required to be input daily, and the value is 10 tons.
In addition, in the process, the acid consumption of the wet-based copper slag is 0.69 ton, and the hydrogen peroxide (H) is consumed by the wet-based copper slag2O2)0.46 ton.
The production operation and process control requirements of each procedure are as follows:
1. and a primary slurrying process.
Before feeding, large copper slag is beaten, ground and crushed, and sundries are removed.
Secondly, according to the liquid-solid ratio of 4:1, 6 cubic meters of water is injected into a single slurrying tank, 1.5 tons of copper slag are added, and stirring is carried out for 30 minutes.
And thirdly, solid-liquid separation of the slag slurry is carried out by pumping the first filter press, the filter cake is put into the pulping tank below for secondary pulping, and the filtrate automatically flows to the pulping tank of the second filter press for storage.
The copper slag was slurried for four days for 10 tons, and the slurry tank was 7 batches.
⑸ Total amount of saline water in primary slurrying process is about 15 cubic meters, and can be recycled, when the circulation is 10 times, sampling is carried out to detect Cu in the saline water2+、Cl-And (4) content. When Cl is present-At > 3g/l, according to Cu2+Treating the salt water in a slurrying tank (without feeding), adding caustic soda flakes or soda ash to precipitate copper, and performing first pressure filtrationSolid-liquid separation is carried out on the machine (full of filter residues), and the brine is directly discharged to a brine tank for storage.
2. And repulping and ball milling.
According to the liquid-solid ratio of 3:1, 9 cubic meters of water is injected into a slurrying tank, 1 plate of filter residues and about 3 tons of wet-base copper residues are added, and stirring and slurrying are carried out for 10 minutes.
And the slurry is ground by a slag slurry pumping classifier and a ball mill, and the granularity is 120 meshes.
And thirdly, performing solid-liquid separation on the slag slurry by pumping through a third filter press, putting the filter cake into a lower slurrying tank for three times of slurrying, and automatically flowing the filtrate into a clean water tank for caching.
⑷ Total amount of brine in repulping process is about 15 cubic meters, and can be recycled, and when the brine is recycled for 20 times, sampling is carried out to detect Cu in the brine2+、Cl-And (4) content. When Cl is present-When the concentration is more than 2g/l, the brine is discharged to a brine tank for storage.
3. Three times of slurrying-one-stage leaching process.
The method comprises the steps of injecting 9 cubic meters of electric barren solution into a third filter press pulping tank once according to a liquid-solid ratio of 3:1, adding 2 plate frame filter cakes, stirring and pulping for 10 minutes, and pumping to a first-stage leaching tank.
And pulping 10 tons of wet-based copper slag which is put into the first-stage leaching tank, and supplementing 40 cubic meters of the electric barren solution (containing the electric barren solution prepared by pulping for three times).
And thirdly, introducing steam, raising the temperature to 70 ℃, and introducing compressed air to oxidize and leach for 4 hours.
And fourthly, pumping the first-stage leached slurry into a fourth filter press for solid-liquid separation, leaching a filter cake with clear water, then putting the filter cake into a lower slurrying tank, and pumping the filtrate into a dechlorinating tank through a transfer tank.
⑸ the first leaching solution is about 42 cubic meters Cu2+The ion content was about 66g/l and the sulfuric acid content was about 20 g/l.
4. Four times of slurrying and two-stage leaching.
The method comprises the steps of injecting 9 cubic meters of electric barren solution into a No. four filter press pulping tank once according to a liquid-solid ratio of 3:1, adding 2 plate frame filter cakes, stirring and pulping for 10 minutes, and pumping to a secondary leaching tank.
And completely putting the once leached filter cake (about 5 tons of wet-based copper slag) into a secondary leaching tank, and supplementing 20 cubic meters of the electric barren solution (containing the electric barren solution prepared by four times of slurrying).
⑶ heating to 60 deg.C by introducing steam, and slowly adding H at a rate of 1 ton/hr2O2Co-feeding of H2O2About 4.6 tons (4.2 cubic meters).
Fourthly, after adding hydrogen peroxide, compressed air is started for oxidizing and leaching for 2 hours.
Fifthly, pumping the slurry in the leaching tank II to a filter press for solid-liquid separation, and leaching the filter cake with clear water until the filtrate is blue to fade. And (4) packing the filter cake into a ton bag, delivering the filter cake to a lead silver slag storage, and storing the filter cake, wherein the filter liquor automatically flows to a two-stage leachate storage tank.
Sixthly, extracting the filter cake of the No. five filter press, detecting the content and the water content of copper metal, and marking the production date and the weight of the filter cake on a ton bag.
⑺ about 25 cubic meters Cu of the second-stage leachate2+The ion content was about 38.8g/l and the sulfuric acid content was about 80 g/l.
5. And (3) a dechlorination process.
⑴ A leaching solution (about 42 cubic meters) is taken to detect Cu2+、Cl-Sulfuric acid content according to Cl-Adding zinc powder into a dechlorinating tank, stirring for 1 hour, and adding Cl into the solution-The concentration is reduced to below 0.5 g/l.
⑵ two-stage leaching solution (about 25 cubic meters) is taken for detecting Cu2+、Cl-Sulfuric acid content according to Cl-Adding zinc powder into a dechlorinating tank, stirring for 1 hour, and adding Cl into the solution-The concentration is reduced to below 0.5 g/l.
⑶ standing the dechlorinated solution for 1 hr, collecting supernatant, and assaying Cu2+、Cl-And the sulfuric acid content. Pumping the supernatant into an electric pregnant solution storage tank, mixing the first-stage leachate with the second-stage leachate (Cu)2+≈56g/l，H2SO4Approximately 42g/l) and simultaneously adding concentrated sulfuric acid, and preparing the sulfuric acid in the electric pregnant solution to 100 g/l.
And fourthly, regularly pumping the copper powder at the bottom of the dechlorination tank to a second filter press, transporting the copper powder outwards for natural oxidation, and automatically flowing the filtrate to an electric pregnant solution storage tank.
6. And (5) an electrodeposition process.
⑴ discharging the barren solution in the electrowinning circulation tank to the electrowinning storage tankBarren solution (Cu)2+≈15g/l，H2SO4130g/l) about 6 cubic meters, and 22 cubic meters (Cu) of supplementary electric pregnant solution2+≈56g/l，H2SO4About 100g/l), mixed electric liquid accumulation Cu2+≈47g/l，H2SO4≈106g/l。
⑵ according to current 250A (electric density 500A/m)2) Turbulent electrodeposition was carried out to reduce the copper ion concentration from 46.4g/l to about 15 g/l. The total yield of cathode copper was 896kg, and in total, 6 groups of 120 cathode copper each weighed about 7.47kg, which took 22 hours.
And thirdly, liquid is changed for 3 times in such a circulating way, the electrodeposition time is 66 hours, the copper production time is 6 hours, and 120 pieces of cathode copper with the weight of about 22.4kg are produced in a single series, namely 2.69 tons of cathode copper are produced in average day. The annual yield of cathode copper is about 888 tons and the annual yield of copper powder is about 40 tons.
⑷ Zn in the electrolyte2+When the concentration is more than 50g/l or As is more than 3g/l, the electrobarren solution is discharged to a decoppering circulation tank in batches, the concentration of copper ions is reduced from 15g/l to below 1g/l, and black copper powder is produced.
The technical solutions disclosed in the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained in the present document by using specific embodiments, and the descriptions of the embodiments are only used to help understanding the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, there may be variations in the specific implementation manners and application ranges, and in summary, the content of the present description should not be construed as a limitation to the present invention.
Claims (7)
1. A method for recovering copper from zinc hydrometallurgy copper slag is characterized by comprising the following steps:
step 1) primary slurrying process: mixing materials according to a liquid-solid ratio of 3.5-4.5: 0.8-1.2, stirring in a first-stage slurrying tank for 20-50 min, conveying to a first pressure filter for solid-liquid separation, and putting a filter cake into a second-stage slurrying tank for secondary slurrying;
step 2), secondary slurrying and ball milling: putting the primary filter cake obtained in the step 1) into a secondary pulping tank according to a liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and pulping for 5-30 min, then feeding the mixture into a ball mill for grinding by a classifier, wherein the grinding particle size is 90-150 meshes, then feeding the mixture into a third filter press for solid-liquid separation, and putting the secondary filter cake into a third pulping tank for pulping for three times;
step 3) pulping for three times, and one-stage leaching process: putting the secondary filter cake obtained in the step 2) into a third-stage slurrying tank according to the liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and slurrying for 5-30 min, and then sending to a first leaching tank;
step 4), pulping for four times, and performing a second-stage leaching process: putting the secondary filter cake obtained in the step 2) into a four-stage slurrying tank according to the liquid-solid ratio of 2.5-3.5: 0.8-1.2, stirring and slurrying for 5-30 min, and then sending to a second leaching tank;
cu in the primary leach slurry2+The ion content is 60-75 g/l, and the sulfuric acid content is 15-30 g/l;
cu in the secondary leaching slurry2+The ion content is 35-45 g/l, and the sulfuric acid content is 70-90 g/l;
step 5) dechlorination: taking a first-stage leaching solution of a first leaching tank for 30-50 m3The second-stage leaching solution of the first leaching tank is 15-30 m3To a second dechlorination tank, respectively detecting Cu2+、Cl-And sulfuric acid content according to Cl-Adding zinc powder into a dechlorinating tank, stirring for 0.5-2 h, and adding Cl into the solution-Reducing the concentration to 0.5g/l, standing and settling dechlorination liquid in the first dechlorination tank and the second dechlorination tank for 0.5-2 h, taking supernate and testing Cu2+、Cl-Pumping the supernatant into an electric pregnant solution storage tank, mixing the first-stage leachate with the second-stage leachate, simultaneously replenishing concentrated sulfuric acid, and preparing the sulfuric acid in the electric pregnant solution to be 100-110 g/l;
step 6) electrodeposition: discharging the barren liquor in the electrowinning circulation tank to an electric barren liquor storage tank, and controlling the concentration of copper ions in the electric barren liquor of the electric barren liquor storage tank and the electric barren liquor of the electric barren liquor storage tank to be 45-50 g/l according to the current of 250A and the electric density of 500A/m2Turbulent electrodeposition is carried out, the concentration of copper ions is reduced from 45-50 g/l to below 15g/l, and cathode copper is produced.
2. The method for recovering copper from zinc hydrometallurgy copper slag according to claim 1, wherein in the step 1), before feeding, the bulk copper slag is beaten, ground and crushed, impurities are removed,
and the total amount of the salt water in the primary slurrying process is 10-20 m3And recycling.
3. The method for recovering copper from zinc hydrometallurgy copper slag according to claim 1, wherein sampling is performed to detect Cu in the brine after 10 times of brine circulation in the primary slurrying process2+、Cl-Content when Cl-At > 3g/l, according to Cu2+And (3) content, treating the brine in a primary slurrying tank, adding caustic soda flakes or calcined soda for copper precipitation, performing solid-liquid separation on the slurry saturated with filter residues through a first filter press, and directly discharging the brine to a brine tank for storage.
4. The method for recovering copper from zinc hydrometallurgy copper slag according to claim 1, wherein in the step 2), the total amount of brine in the secondary slurrying process is 10 to 20m3Recycling, sampling and detecting Cu in the brine after 20 times of circulation2+、Cl-Content when Cl-When the concentration is more than 2g/l, the brine is discharged to a brine tank for storage.
5. The method for recovering copper from zinc hydrometallurgy copper slag according to claim 1, wherein in the step 3), steam is introduced into the first leaching tank to raise the temperature to 60-80 ℃, compressed air is introduced to oxidize and leach for 4 hours, then the first-stage leaching slurry is subjected to solid-liquid separation by a fourth filter press with a conveying pump, a third-stage filter cake is rinsed with clear water, and then the first-stage leaching slurry is put into a fourth-stage slurrying tank, and filtrate is pumped to a dechlorinating tank through a transfer tank.
6. The method for recovering copper from zinc hydrometallurgy copper slag according to claim 1, wherein in the step 4), steam is introduced into the second leaching tank to raise the temperature to 60-80 ℃, hydrogen peroxide is slowly added according to the speed of 1 ton/hour, after the hydrogen peroxide is added, compressed air is started to oxidize and leach for 2 hours, slurry in the second leaching tank is subjected to solid-liquid separation by a conveying pump and a fifth filter press, filter cakes are rinsed by clear water until the filtrate is blue and faded, the filter cakes are packaged in a ton bag and sent to a lead-silver slag storage, and the filtrate flows to a second-stage leaching liquid storage tank automatically.
7. The method for recovering copper from zinc hydrometallurgy copper slag according to claim 1, wherein in step 6), Zn is contained in the electro-hydraulic fluid2+When the concentration is more than 50g/l or As is more than 3g/l, the electrobarren solution is discharged to a decoppering circulation tank in batches, the concentration of copper ions is reduced from 15g/l to less than 1g/l, and black copper powder is produced.
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