CN112080641B - Method for comprehensively recovering valuable metals from byproduct copper sludge of zinc hydrometallurgy - Google Patents
Method for comprehensively recovering valuable metals from byproduct copper sludge of zinc hydrometallurgy Download PDFInfo
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- 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
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- C22B7/007—Wet processes by acid leaching
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- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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- C22B15/0067—Leaching or slurrying with acids or salts thereof
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- C22B17/00—Obtaining cadmium
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- C22B19/00—Obtaining zinc or zinc oxide
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- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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Abstract
Compared with the prior art, the method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy disclosed by the application comprises the following steps: carrying out ball milling and slurrying treatment on the copper mud to obtain slurry liquid; leaching indium and germanium from the slurry; performing filter pressing treatment; carrying out replacement treatment on the leaching solution containing indium and germanium to obtain indium and germanium concentrate; leaching copper, zinc and cadmium from the indium and germanium leaching slag; carrying out copper extraction treatment on the copper-zinc-cadmium leaching solution to obtain copper extraction raffinate and a copper-enriched organic phase; carrying out electrodeposition treatment on the copper sulfate solution obtained by the back extraction method of the enriched organic phase; carrying out iron removal treatment and filter pressing treatment on the copper extraction residual liquid to obtain cadmium-rich liquid; carrying out replacement on the cadmium-rich liquid to obtain sponge cadmium, and carrying out cadmium refining treatment on the sponge cadmium; and concentrating and crystallizing the solution after cadmium removal to obtain zinc sulfate heptahydrate and crystallization mother liquor. The technical scheme can recover valuable metals such as indium, germanium, silver and the like from the byproduct copper sludge of zinc hydrometallurgy, and the whole production flow has no redundant wastewater to achieve zero emission, thereby saving energy, reducing emission and greatly reducing the environmental risk coefficient.
Description
Technical Field
The application relates to the technical field of valuable metal comprehensive recovery treatment, in particular to a method for comprehensively recovering valuable metals from byproduct copper sludge of zinc hydrometallurgy.
Background
The yield of the zinc hydrometallurgy accounts for more than 70% of the total yield of zinc in the whole country, about 1kt of copper slag generated by processing and purifying copper and cadmium slag every year is produced for a zinc hydrometallurgy enterprise with 10 ten thousand of tons, only about 50% of the copper slag is sold to the copper smelting enterprise and enters the pyrometallurgical blister copper smelting, the zinc in the copper slag cannot be effectively recovered, rare and precious metals such as indium, germanium and the like are dispersed and cannot be recovered, and the residual copper-rich slag is stacked in a slag yard to cause the idle of secondary resources and environmental pollution.
Most of metal elements in the copper sludge exist as metal simple substances, and a single wet acid leaching process has the advantages of low copper and zinc leaching rate, dispersed indium and germanium and less than 50 percent of indium and germanium recovery rate. In addition, the copper mud is roasted for 4-5 hours at 600-800 ℃ by adopting an oxidation roasting method, roasting slag is leached by sulfuric acid, copper and zinc can achieve high leaching effect, a roasting furnace and a dust collection and acid mist purification system are matched in the production process, the production flow is long, and the relative energy consumption is slightly high.
Therefore, how to provide a method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy, which can recover valuable metals such as indium, germanium, silver and the like from the byproduct copper sludge of zinc hydrometallurgy, and the whole production process has no redundant wastewater to achieve zero discharge, saves energy, reduces emission and reduces the environmental protection risk coefficient, has become a technical problem to be solved urgently by technical personnel in the field.
Disclosure of Invention
In order to solve the technical problems, the application provides a method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy, the valuable metals such as indium, germanium, silver and the like can be recovered from the byproduct copper sludge of zinc hydrometallurgy, no redundant wastewater exists in the whole production process, zero emission is achieved, energy is saved, emission is reduced, and the environmental protection risk coefficient is greatly reduced.
The technical scheme provided by the application is as follows:
the application provides a method for comprehensively recovering valuable metals from byproduct copper sludge of zinc hydrometallurgy, which comprises the following steps: carrying out ball milling and slurrying treatment on the copper mud to obtain slurry liquid; leaching indium and germanium from the slurry; performing filter pressing treatment, wherein indium and germanium leaching residues and indium and germanium-containing leachate are obtained through the filter pressing treatment; carrying out replacement treatment on the leaching solution containing indium and germanium to obtain indium and germanium concentrate; leaching the indium and germanium leaching residues to obtain a copper-zinc-cadmium leaching solution and lead-silver enriched residues; carrying out copper extraction treatment on the copper-zinc-cadmium leaching solution to obtain copper extraction raffinate and a rich organic phase; carrying out electrodeposition treatment on a copper-enriched organic phase to obtain a copper sulfate solution by a back extraction method to obtain cathode copper; carrying out iron removal treatment and filter pressing treatment on the copper extraction residual liquid to obtain iron-removed liquid, namely cadmium-rich liquid; carrying out replacement on the cadmium-rich liquid to obtain sponge cadmium, and carrying out cadmium refining treatment on the sponge cadmium; and concentrating and crystallizing the solution after cadmium removal to obtain zinc sulfate heptahydrate and crystallization mother liquor.
Further, in a preferred mode of the present invention, the step of "leaching indium and germanium treatment" is specifically: ozone is generated by an ozone generator, and indium and germanium are selectively leached out under normal pressure by an acidic reagent.
Further, in a preferred mode of the present invention, the step of "leaching indium and germanium treatment" is specifically: pumping the slurry into a leaching tank according to the solid-liquid ratio of 1:4, filling 700-900 mL/min of ozone, adding 10-15% of an acid medicament, and keeping the temperature at 40-50 ℃ to leach the indium and germanium.
Further, in a preferred mode of the present invention, the acidic agent is one or two mixed acids of tannic acid, citraconic acid, oxalic acid, hydrochloric acid, and acetic acid.
Further, in a preferred embodiment of the present invention, the step of "leaching the indium and germanium leaching residue to obtain a copper-zinc-cadmium leaching solution and a lead-silver enrichment residue" specifically includes: treating the indium and germanium leaching residues with 60-80 g/L sulfuric acid, introducing 700-900 mL/min ozone, and keeping the temperature at 75-85 ℃ for leaching treatment to obtain copper-zinc-cadmium leaching solution and lead-silver enriched residues.
Further, in a preferred mode of the present invention, the step of performing copper extraction treatment on the copper zinc cadmium leachate to obtain a copper extraction raffinate and a copper-enriched organic phase specifically is: and controlling the pH value of the copper-zinc-cadmium leaching solution to be 1.5-2 for copper extraction treatment.
Further, in a preferred mode of the present invention, the step of "performing iron removal treatment and filter pressing treatment on the copper raffinate to obtain an iron-removed filtrate, i.e. a cadmium-rich solution", specifically comprises: carrying out oxidation iron removal treatment on the copper extraction residual liquid, controlling the pH value to be 3.8-4.0, carrying out filter pressing on the iron removal filtrate obtained after iron removal, namely a cadmium-rich liquid, carrying out zinc replacement treatment on the cadmium-rich liquid to obtain sponge cadmium, carrying out briquetting treatment on the sponge cadmium, and entering a cadmium refining process.
Further, in a preferred embodiment of the present invention, the step "performing stripping treatment and electrodeposition treatment on the copper-rich organic phase to obtain cathode copper" is specifically: the copper-rich organic phase is back extracted by the electrolyzed solution to obtain copper sulfate solution, the copper sulfate solution is used for producing cathode copper by adopting an insoluble anode method for electrodeposition, and the solution after electrodeposition returns to the copper extraction procedure and the copper-zinc-cadmium leaching procedure
Further, in a preferred embodiment of the present invention, the step "performing ball milling and slurrying on the copper sludge" specifically includes: copper mud is mixed according to a solid-liquid ratio of 1: 1, performing ball milling and slurrying treatment.
Further, in a preferred mode of the present invention, the step "performing a displacement treatment on the leaching solution containing indium and germanium to obtain an indium and germanium concentrate" specifically includes: and (3) performing replacement treatment on the leaching solution containing the indium and the germanium by using zinc, replacing the leaching solution into indium and germanium concentrate, and returning the replaced leaching solution to the indium and germanium leaching treatment step.
Compared with the prior art, the method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy provided by the invention comprises the following steps: carrying out ball milling and slurrying treatment on the copper mud to obtain slurry liquid; leaching indium and germanium from the slurry; performing filter pressing treatment, wherein indium and germanium leaching residues and indium and germanium-containing leachate are obtained through the filter pressing treatment; carrying out replacement treatment on the leaching solution containing indium and germanium to obtain indium and germanium concentrate; leaching the indium and germanium leaching residues to obtain a copper-zinc-cadmium leaching solution and lead-silver enriched residues; carrying out copper extraction treatment on the copper-zinc-cadmium leaching solution to obtain copper extraction raffinate and a copper-enriched organic phase; carrying out back extraction on the copper-enriched organic phase to obtain copper sulfate solution, and carrying out electrodeposition treatment on the copper sulfate solution to obtain cathode copper; carrying out iron removal treatment and filter pressing treatment on the copper extraction residual liquid to obtain iron removal filtrate, namely cadmium-rich liquid; carrying out replacement on the cadmium-rich liquid to obtain sponge cadmium, and carrying out cadmium refining treatment on the sponge cadmium; and concentrating and crystallizing the solution after cadmium removal to obtain zinc sulfate heptahydrate and crystallization mother liquor. Compared with the prior art, the technical scheme can recover valuable metals such as indium, germanium and silver from the byproduct copper sludge of zinc hydrometallurgy, and the whole production process has no redundant wastewater to achieve zero discharge, saves energy, reduces emission, and greatly reduces the environmental protection risk coefficient.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for comprehensively recovering valuable metals from a byproduct copper sludge of zinc hydrometallurgy provided by an embodiment of the invention.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or be indirectly disposed on the other element; when an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
It will be understood that the terms "length," "width," "upper," "lower," "front," "rear," "first," "second," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like, as used herein, refer to an orientation or positional relationship indicated in the drawings that is solely for the purpose of facilitating the description and simplifying the description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be considered as limiting the present application.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "plurality" or "a plurality" means two or more unless specifically limited otherwise.
It should be understood that the structures, ratios, sizes, and the like shown in the drawings are only used for matching the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the practical limit conditions of the present application, so that the modifications of the structures, the changes of the ratio relationships, or the adjustment of the sizes, do not have the technical essence, and the modifications, the changes of the ratio relationships, or the adjustment of the sizes, are all within the scope of the technical contents disclosed in the present application without affecting the efficacy and the achievable purpose of the present application.
As shown in fig. 1, the method for comprehensively recovering valuable metals from byproduct copper sludge of zinc hydrometallurgy provided in the embodiment of the present application includes the following steps: carrying out ball milling and slurrying treatment on the copper mud to obtain slurry liquid; leaching indium and germanium from the slurry; performing filter pressing treatment, wherein indium and germanium leaching residues and indium and germanium-containing leachate are obtained through the filter pressing treatment; carrying out replacement treatment on the leaching solution containing indium and germanium to obtain indium and germanium concentrate; leaching the indium and germanium leaching residues to obtain a copper-zinc-cadmium leaching solution and lead-silver enriched residues; carrying out copper extraction treatment on the copper-zinc-cadmium leaching solution to obtain copper extraction raffinate and a copper-enriched organic phase; carrying out back extraction on the copper-enriched organic phase to obtain copper sulfate solution, and carrying out electrodeposition treatment on the copper sulfate solution to obtain cathode copper; carrying out iron removal treatment and filter pressing treatment on the copper extraction residual liquid to obtain iron removal filtrate, namely cadmium-rich liquid; carrying out replacement on the cadmium-rich liquid to obtain sponge cadmium, and carrying out cadmium refining treatment on the sponge cadmium; and concentrating and crystallizing the solution after cadmium removal to obtain zinc sulfate heptahydrate and crystallization mother liquor.
The embodiment of the invention provides a method for comprehensively recovering valuable metals from a byproduct copper sludge of zinc hydrometallurgy, which comprises the following steps: carrying out ball milling and slurrying treatment on the copper mud to obtain slurry liquid; leaching indium and germanium from the slurry; performing filter pressing treatment, wherein indium and germanium leaching residues and indium and germanium-containing leachate are obtained through the filter pressing treatment; carrying out replacement treatment on the leaching solution containing indium and germanium to obtain indium and germanium concentrate; leaching the indium and germanium leaching residues to obtain a copper-zinc-cadmium leaching solution and lead-silver enriched residues; carrying out copper extraction treatment on the copper-zinc-cadmium leaching solution to obtain copper extraction raffinate and a copper-enriched organic phase; carrying out back extraction on the copper-enriched organic phase to obtain copper sulfate solution, and carrying out electrodeposition treatment on the copper sulfate solution to obtain cathode copper; carrying out iron removal treatment and filter pressing treatment on the copper extraction residual liquid to obtain iron removal filtrate, namely cadmium-rich liquid; carrying out replacement on the cadmium-rich liquid to obtain sponge cadmium, and carrying out cadmium refining treatment on the sponge cadmium; and concentrating and crystallizing the solution after cadmium removal to obtain zinc sulfate heptahydrate and crystallization mother liquor. Compared with the prior art, the technical scheme can recover valuable metals such as indium, germanium and silver from the byproduct copper sludge of zinc hydrometallurgy, and the whole production process has no redundant wastewater to achieve zero discharge, saves energy, reduces emission, and greatly reduces the environmental protection risk coefficient.
The valuable metal in the embodiment of the present application specifically refers to a valuable metal such as indium, germanium, silver and the like.
Specifically, in the embodiment of the present invention, the step "indium and germanium leaching treatment" specifically includes: ozone is generated by an ozone generator, and indium and germanium are selectively leached out under normal pressure by an acidic reagent.
Specifically, in the embodiment of the present invention, the step "indium and germanium leaching treatment" specifically includes: pumping the slurry into a leaching tank according to the solid-liquid ratio of 1:4, filling 700-900 mL/min of ozone, adding 10-15% of an acid medicament, and keeping the temperature at 40-50 ℃ to leach the indium and germanium.
Specifically, in the embodiment of the present invention, the acidic agent is one or two mixed acids of tannic acid, citraconic acid, oxalic acid, hydrochloric acid and acetic acid.
Specifically, in the embodiment of the present invention, the step "leaching the indium and germanium leaching residue to obtain the copper-zinc-cadmium leaching solution and the lead-silver enrichment residue" specifically includes: treating the indium and germanium leaching residues with 60-80 g/L sulfuric acid, introducing 700-900 mL/min ozone, and keeping the temperature at 75-85 ℃ for leaching treatment to obtain copper-zinc-cadmium leaching solution and lead-silver enriched residues.
Specifically, in the embodiment of the present invention, the step "performing copper extraction treatment on the copper zinc cadmium leaching solution to obtain a copper extraction raffinate and a copper-enriched organic phase" specifically includes: and controlling the pH value of the copper-zinc-cadmium leaching solution to be 1.5-2 for copper extraction treatment.
Specifically, in the embodiment of the present invention, the steps of "performing iron removal treatment and filter pressing treatment on the copper extraction raffinate to obtain cadmium-removed liquid and cadmium-rich liquid" specifically include: carrying out oxidation iron removal treatment on the copper extraction residual liquid, controlling the pH value to be 3.8-4.0, carrying out filter pressing on the iron removal filtrate obtained after iron removal, namely a cadmium-rich liquid, carrying out zinc replacement treatment on the cadmium-rich liquid to obtain sponge cadmium, carrying out briquetting treatment on the sponge cadmium, and entering a cadmium refining process.
Specifically, in the embodiment of the present invention, the steps of "obtaining copper sulfate solution by a back extraction method for a copper-rich organic phase, and obtaining cathode copper by electrodeposition treatment of the copper sulfate solution" specifically include: the electrolyzed solution is used for back extraction of the rich organic phase to obtain a copper sulfate solution, the copper sulfate solution is used for producing cathode copper by adopting an insoluble anode method for electrodeposition, and the solution after electrodeposition of copper returns to the copper extraction procedure and the copper zinc cadmium leaching procedure
Specifically, in the embodiment of the present invention, the step "performing ball milling and slurrying on the copper sludge" specifically includes: copper mud is mixed according to a solid-liquid ratio of 1: 1, performing ball milling and slurrying treatment.
Specifically, in the embodiment of the present invention, the step "performing a displacement treatment on the leaching solution containing indium and germanium to obtain an indium and germanium concentrate" specifically includes: and (3) performing replacement treatment on the leaching solution containing the indium and the germanium by using zinc, replacing the leaching solution into indium and germanium concentrate, and returning the replaced leaching solution to the indium and germanium leaching treatment step.
More specifically, copper sludge generated by treating copper-cadmium slag in a purification system in a zinc hydrometallurgy process is described, and the copper is specifically 18-20%; 4-6% of lead; 7-9% of zinc, 3-5% of cadmium, 10% of iron, 100-300 g/t of indium, 400-600 g/t of germanium and 500-800 g/t of silver.
The yield of the zinc hydrometallurgy accounts for more than 70% of the total yield of zinc in the whole country, about 1kt of copper slag generated by processing and purifying copper and cadmium slag every year is produced for a zinc hydrometallurgy enterprise with 10 ten thousand of years, only about 50% of the copper slag is sold to the copper smelting enterprise and enters the pyrometallurgical blister copper smelting, the zinc in the copper slag cannot be effectively recovered, rare and precious metals such as indium, germanium and the like are dispersed and cannot be recovered, and the residual copper-rich slag is stacked in a slag yard, so that the secondary resources are left unused and the environment is polluted.
Most of metal elements in the copper sludge exist as metal simple substances, and a single wet acid leaching process has the advantages of low copper and zinc leaching rate, dispersed indium and germanium and less than 50 percent of indium and germanium recovery rate.
The copper mud is roasted for 4-5 hours at 600-800 ℃ by adopting an oxidation roasting method, roasting slag is leached by sulfuric acid, copper and zinc can achieve high leaching effect, a roasting furnace and a dust collection and acid mist purification system are matched in the production process, the production flow is long, and the relative energy consumption is slightly high.
The indium and germanium are selectively leached by adopting normal-pressure ozone and an acidic medicament (the acidic medicament is one or two mixed acids of tannic acid, citraconic acid, oxalic acid, hydrochloric acid and acetic acid), so that the dispersion of the indium and germanium in the hydrometallurgy process is avoided, and the direct yield of the indium and germanium is high;
the low-acid ozone is adopted for leaching under normal pressure, the leaching rate of copper, zinc and cadmium is up to 99 percent, and the lead and silver products entering the slag have few impurities and high grade;
the whole production flow has no redundant wastewater to achieve zero emission;
and the ozone oxidation is adopted to replace roasting oxidation, so that energy is saved, emission is reduced, and the environmental protection risk coefficient is greatly reduced.
Specifically, the technical scheme of the technology is as follows: the copper sludge sampling analysis result is as follows: 20.4% of copper, 5.8% of zinc, 2.7% of cadmium, 310g/t of indium, 608g/t of germanium, 780g/t of silver and 14% of iron;
1200Kg of copper mud is mixed according to the solid-liquid ratio of 1: 1, ball milling and slurrying, pumping slurrying liquid into a leaching tank, filling 700-900 mL/min of ozone, adding 10-15% of an A medicament (the A medicament is one or two mixed acids of tannic acid, citradim acid, oxalic acid, hydrochloric acid and acetic acid), keeping the temperature at 40-50 ℃, selectively leaching indium and germanium at normal pressure, replacing the indium and germanium-containing solution subjected to filter pressing with zinc to obtain indium and germanium concentrate, and returning the solution after replacement to the process of selectively leaching indium and germanium;
and (3) introducing 700-900 mL/min ozone into the leaching residues by using 60-80 g/L sulfuric acid, keeping the temperature at about 80 ℃, and leaching at normal pressure, wherein the leaching solution is a copper-zinc-cadmium mixed solution, and the leaching residues are lead-silver enriched residues.
Selectively extracting copper by using a high-efficiency copper extractant with the pH value of the mixed solution controlled to be 1.5-2, performing back extraction on a copper-enriched organic phase by using an electrolyzed solution to obtain a copper sulfate solution, performing electrodeposition on the copper sulfate solution by using an insoluble anode method to produce cathode copper, returning part of the copper-electrodeposited solution to a copper extraction system, and returning the rest of the copper-zinc-cadmium leaching solution to the copper zinc-cadmium leaching process, wherein the copper-extracted solution is a zinc-cadmium mixed solution;
pumping the raffinate into an iron removal tank for oxidation iron removal to control the pH value to be 3.8-4.0, pumping the press filtrate into a cadmium-rich solution, pumping the cadmium-rich solution into a replacement tank for adding zinc powder to replace sponge cadmium, and feeding the sponge cadmium briquette into a cadmium refining process;
after cadmium is removed, the solution is pumped into a triple-effect evaporator for concentration and crystallization to obtain a zinc sulfide product, and crystallization mother liquor is returned to a zinc system for impurity removal to be used for crystallizing zinc sulfate.
The final product is: firstly, lead-silver slag; 0.65% of copper, 0.05% of zinc, 0.02% of cadmium, 22g/t of indium, 35g/t of germanium, 16.5% of lead and 2500g/t of silver; more than or equal to 99.95 percent of copper, indium-germanium concentrate, 12 percent of germanium, 8 percent of indium, zinc sulfate heptahydrate, more than or equal to 35.34 percent of zinc, class I first-class products.
As described above, compared with the prior art, the technical solution according to the embodiment of the present invention mainly improves the following:
ozone is generated by an ozone generator, and indium and germanium are selectively leached out at normal pressure by using an acidic medicament (one or two mixed acids of tannic acid, citraconic acid, oxalic acid, hydrochloric acid and acetic acid), wherein the leaching rate of indium and germanium at one time is more than 95%, and the direct yield is 92%.
The slag after indium and germanium leaching is leached by low-concentration sulfuric acid and ozone under normal pressure.
The copper, zinc and cadmium mixed liquor adopts high-efficiency extractant to selectively extract copper, and the copper is electrodeposited into metal copper with the concentration of more than 99.9 percent.
The water is recycled in the production process, no waste water is generated, and zero emission is achieved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A method for comprehensively recovering valuable metals from byproduct copper sludge of zinc hydrometallurgy is characterized by comprising the following steps:
carrying out ball milling and slurrying treatment on the copper mud to obtain slurry liquid;
leaching indium and germanium from the slurry;
performing filter pressing treatment, wherein indium and germanium leaching residues and indium and germanium-containing leachate are obtained through the filter pressing treatment;
carrying out replacement treatment on the leaching solution containing indium and germanium to obtain indium and germanium concentrate;
leaching the indium and germanium leaching residues to obtain a copper-zinc-cadmium leaching solution and lead-silver enriched residues;
carrying out copper extraction treatment on the copper-zinc-cadmium leaching solution to obtain copper extraction raffinate and a copper-enriched organic phase;
carrying out back extraction treatment and electrodeposition treatment on the copper-enriched organic phase to obtain cathode copper;
carrying out iron removal treatment and filter pressing treatment on the copper extraction residual liquid to obtain iron removal filtrate, namely cadmium-rich liquid;
carrying out replacement on the cadmium-rich liquid to obtain sponge cadmium, and carrying out cadmium refining treatment on the sponge cadmium; concentrating and crystallizing the solution after cadmium removal to obtain zinc sulfate heptahydrate and crystallization mother liquor; the step of indium and germanium leaching treatment is specifically as follows: ozone is generated by an ozone generator, and indium and germanium are selectively leached out under normal pressure by using an acidic reagent; the step of indium and germanium leaching treatment is specifically as follows: pumping the slurrying solution into a leaching tank according to the solid-to-liquid ratio of 1:4, filling 700-900 mL/min of ozone, adding 10-15% of an acid agent, and leaching indium and germanium at the temperature of 40-50 ℃; the acid medicament is one or two mixed acids of tannic acid, citraconic acid, oxalic acid, hydrochloric acid and acetic acid; the method comprises the following steps of leaching indium and germanium leaching residues to obtain a copper-zinc-cadmium leaching solution and lead-silver enrichment residues: treating the indium and germanium leaching residues with 60-80 g/L sulfuric acid, introducing 700-900 mL/min ozone, and performing leaching treatment at 75-85 ℃ to obtain a copper-zinc-cadmium leaching solution and lead-silver enriched residues.
2. The method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy according to claim 1, wherein the step of performing copper extraction treatment on the copper zinc cadmium leaching solution to obtain a copper extraction raffinate and a copper-enriched organic phase comprises the following specific steps: and controlling the pH value of the copper-zinc-cadmium leaching solution to be 1.5-2 for copper extraction treatment.
3. The method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy according to claim 2, wherein the step of performing iron removal treatment and filter pressing treatment on the copper extraction raffinate to obtain iron removal filtrate, namely cadmium-rich liquid, specifically comprises the following steps: carrying out oxidation iron removal treatment on the copper extraction residual liquid, controlling the pH value to be 3.8-4.0, carrying out filter pressing on the iron removal filtrate obtained after iron removal, namely a cadmium-rich liquid, carrying out zinc replacement treatment on the cadmium-rich liquid to obtain sponge cadmium, carrying out briquetting treatment on the sponge cadmium, and entering a cadmium refining process.
4. The method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy according to the claim 3, wherein the step of obtaining copper sulfate solution by a back extraction method of the enriched organic phase and obtaining cathode copper by electrodeposition comprises the following specific steps: and (3) carrying out back extraction on the copper-enriched machine by using the electrolyzed solution to obtain a copper sulfate solution, producing cathode copper by adopting an insoluble anode method for electrodeposition of the copper sulfate solution, and returning the electrodeposited copper solution to the copper extraction process and the copper-zinc-cadmium leaching process.
5. The method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy according to claim 1, wherein the step of performing ball milling and slurrying treatment on the copper sludge specifically comprises the following steps: copper mud is mixed according to a solid-liquid ratio of 1: 1, performing ball milling and slurrying treatment.
6. The method for comprehensively recovering valuable metals from the byproduct copper sludge of zinc hydrometallurgy according to claim 1, wherein the step of performing replacement treatment on the leaching solution containing indium and germanium to obtain indium and germanium concentrate specifically comprises the following steps: and (3) performing replacement treatment on the leaching solution containing the indium and the germanium by using zinc, replacing the leaching solution into indium and germanium concentrate, and returning the replaced leaching solution to the indium and germanium leaching treatment step.
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