CN114657387A - Method for recovering copper by synergistic treatment of acidic etching waste liquid and zinc-containing copper dust - Google Patents
Method for recovering copper by synergistic treatment of acidic etching waste liquid and zinc-containing copper dust Download PDFInfo
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- CN114657387A CN114657387A CN202210338158.4A CN202210338158A CN114657387A CN 114657387 A CN114657387 A CN 114657387A CN 202210338158 A CN202210338158 A CN 202210338158A CN 114657387 A CN114657387 A CN 114657387A
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- 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
- C22B7/02—Working-up flue dust
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
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- 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
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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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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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- 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
The invention discloses a method for recovering copper by synergistic treatment of acidic etching waste liquid and zinc-containing copper dust, which comprises the following steps: 1) leaching treatment, namely mixing and leaching smoke dust containing zinc and copper and acidic etching waste liquid, standing and filtering to obtain a copper solvent containing zinc and copper; 2) extracting a copper solvent, namely adding a copper extractant into the copper solvent obtained in the step 1) to obtain a copper-containing extraction liquid and a zinc-containing raffinate; 3) back extraction, namely back extraction is carried out on the copper-containing extract liquid obtained in the step 2) to obtain a back extraction liquid and a secondary copper extractant; 4) electro-depositing copper powder to carry out an electro-deposition process on the stripping solution in the step 3) to obtain copper powder and electro-deposition barren solution; wherein the secondary copper extractant in the step 3) can replace or mix with the copper extractant in the step 2); the electro-winning barren solution in step 4) may be used in the stripping process in step 3). The process obtains high-purity copper sulfate strip liquor through back extraction, and the strip liquor is used for producing an electro-deposited copper powder product by an electro-deposition method; and (3) conveying the zinc-containing raffinate of the copper solvent extraction process to a zinc recovery production line to recover zinc. The product electro-deposited copper powder obtained by the process has lower production cost than the traditional electrolytic copper powder.
Description
Technical Field
The invention relates to the fields of waste liquid and smoke dust collaborative leaching of hydrometallurgy, copper solvent extraction, back extraction, copper powder production by an electrodeposition method, zinc-copper-containing smoke dust hazardous waste comprehensive treatment of acidic etching waste liquid and the like.
Background
The zinc-containing copper smelting dust is solid waste generated in the copper pyrometallurgical process, and is rich in heavy metals such as zinc, copper, lead and tin, a large amount of silicon, aluminum, chlorine, antimony, manganese and the like, and a small amount of arsenic, fluorine, nickel, cobalt and the like. The conventional zinc hydrometallurgy process for treating and smelting smoke dust needs industrial concentrated sulfuric acid and a large amount of industrial water, and the production cost is high.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for recovering copper by synergistic treatment of acidic etching waste liquid and zinc-containing copper dust. The method comprises the following steps:
1) leaching treatment
Mixing and leaching smoke dust containing zinc and copper and acidic etching waste liquid, standing and filtering to obtain a copper solvent containing zinc and copper;
2) solvent extraction of copper
Adding a copper extractant into the copper solvent obtained in the step 1) to obtain a copper-containing extraction liquid and a zinc-containing raffinate;
3) back extraction
Carrying out back extraction on the copper-containing extraction liquid obtained in the step 2) to obtain a back extraction liquid and a secondary copper extractant;
4) electrodeposition copper powder
Carrying out an electrodeposition process on the stripping solution in the step 3) to obtain copper powder and an electrodeposition barren solution;
wherein the secondary copper extractant in the step 3) can replace or mix with the copper extractant in the step 2); the electrodeposition lean solution in step 4) can be used in the back-extraction process in step 3).
Wherein, concentrated sulfuric acid or pure water is not required for leaching treatment in the step 1).
Wherein, before the step 2) is started, the copper solution in the step 1) is subjected to evaporation treatment in advance; the zinc-containing raffinate in the step 2) can replace or mix the acidic etching waste liquid in the step 1) as a leaching solvent, and is used for enriching the zinc content in the zinc-containing raffinate.
Placing the copper solvent and the copper extractant in a rotary cavity with a spiral column by adopting a high-speed countercurrent extraction method in the step 2), continuously inputting the copper extractant into the rotary cavity through a constant flow pump, and continuously separating the copper-containing extract at the other end of the rotary cavity; wherein the flow rate of the copper extractant input into the rotary cavity by the constant-flow pump is 1.5-2.0ml/min, and the temperature of the solution in the rotary cavity is maintained at 30-40 ℃; placing the copper-containing extract liquor and the electrodeposition barren solution into a rotary cavity with a spiral column by adopting a high-speed countercurrent extraction method, continuously inputting the electrodeposition barren solution into the rotary cavity through a constant flow pump, and continuously separating the strip liquor at the other end of the rotary cavity; wherein the flow rate of the electrodeposition barren solution input into the rotary cavity by the constant flow pump is 2-2.5ml/min, and the temperature of the solution in the rotary cavity is maintained at 50-60 ℃; for the selection of the extraction temperature, the extraction rate of copper tends to increase and then decrease along with the increase of the extraction temperature, wherein the extraction rate of copper is the highest at 30 ℃; on the contrary, the back extraction rate of copper tends to decrease and increase after the temperature is higher than the temperature, the extraction rate of copper obviously increases after the temperature is 50-60 ℃, and the stability of the extractant is influenced by the temperature after the temperature exceeds 60 ℃.
Adding a dilute sulfuric acid solution into the copper-containing extraction liquid obtained in the step 2) for washing, and performing back extraction on the washed solution in the step 3). In actual production, due to factors such as mechanical entrainment and the like, a small amount of metal impurities such as iron, arsenic and the like enter a copper stripping solution along with an organic phase to influence the dissolution treatment of copper sulfate, and in order to prevent the entrained impurities from entering the copper stripping solution, a dilute sulfuric acid solution is adopted for washing in an experiment, wherein the pH range of the dilute sulfuric acid solution is 3-4.
Wherein, sodium hydroxide is added into the zinc-containing raffinate in the step 2), and copper hydroxide precipitate obtained after filtration is added into the strip liquor obtained in the step 3), so as to further improve the recovery rate of copper, reduce the amount of impurity copper in the zinc raffinate and improve the recovery rate of zinc.
Wherein the copper extractant comprises Lix 973;
wherein, the acidic etching waste liquid in the step 1) contains 7 percent of Cu and 2mol/L of acid [ H + ]; and adding zinc-copper containing metallurgical dust into the acidic etching waste liquid as bottom water to perform mixed leaching reaction, supplementing part of industrial circulating water until the liquid-solid ratio is 5:1, controlling the free acid content of the leachate to be about 5g/L, reacting for 6 hours at normal temperature, controlling the pH value of the endpoint of the leachate to be about 1-1.5, and performing solid-liquid separation to obtain the copper solvent containing about 40g/L copper.
Wherein, the electrowinning barren solution generated in the electrowinning process is used for carrying out back extraction on the Lix973 loaded with copper in the step 3) to obtain a back extraction solution with the acidity of 140g/l of Cu12g/l and regenerated Lix973, and the regenerated Lix973 is returned to the solvent for extraction and recycling; the back extraction process can directly obtain the copper concentration and the acid concentration of a copper sulfate solution required by copper powder production by an electrodeposition method by controlling the volume ratio of the organic phase Lix973 loaded with copper to an electrodeposition barren solution, and does not need to add dilute sulfuric acid or an aqueous solution for blending.
Pumping the high-purity copper sulfate solution obtained in the back extraction step of the step 3) to an electrodeposition tank to produce electrodeposited copper powder; the anode of the electrodeposition uses a Pb alloy insoluble anode, the cathode uses an electrolytic pure copper plate, the current density is controlled to be 1200-1300A/m2, the temperature of the electrodeposition liquid is 50 ℃, powder is scraped for one time in 30min, and electrolytic copper powder with the mass percentage of over 99 percent is obtained.
Compared with the prior art, the method disclosed by the invention has the following characteristics:
the copper-containing acidic etching waste liquid belongs to hazardous waste and is acidic etching waste liquid from PCB enterprises, and the main components of the acidic etching waste liquid are hydrochloric acid, copper chloride and the like. The leaching process of the patent treats waste by waste, copper-containing acidic etching waste liquid and zinc-containing copper metallurgy smoke dust are mixed and leached, the acid in the acidic etching waste liquid is used for replacing industrial concentrated sulfuric acid to leach metals with recovery value such as zinc, copper and the like in the zinc-containing copper metallurgy smoke dust, meanwhile, the etching waste liquid is used for replacing part of water required by leaching reaction, the using amount of the industrial concentrated sulfuric acid is saved, part of industrial water consumption is saved, comprehensive treatment of dangerous waste such as the acidic etching waste liquid and the metallurgy smoke dust is realized, and meanwhile, the production cost is reduced; the product electro-deposited copper powder obtained by the process has lower production cost than the traditional electrolytic copper powder. The copper powder is produced by solvent extraction, back extraction and electrodeposition, the recovery rate is high, and the added value of the copper powder product is high.
The Lix973 copper extractant can extract copper from leaching reaction leachate containing zinc, copper and various impurities and obtain high-purity copper sulfate strip liquor through back extraction, and can directly obtain the copper sulfate solution copper concentration and acid concentration required by the copper powder production by an electrodeposition method by controlling the extraction and back extraction in the solvent extraction and back extraction processes, and does not need to supplement sulfuric acid to the high-purity copper sulfate solution to improve the acid concentration and supplement water to dilute the copper concentration.
And thirdly, copper-containing acidic etching waste liquid and zinc-containing copper metallurgy dust are mixed and leached, the two dangerous waste raw materials are coordinately treated, the leaching liquid is subjected to copper solvent extraction, the copper and zinc separation process in the system is simple, and the copper and zinc recovery rate is high.
Description of the drawings:
in order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings used in the description of the embodiments will be briefly introduced below.
FIG. 1 is a schematic diagram of the principal process provided herein.
Detailed Description
The following will clearly and completely describe the technical solutions 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.
Additionally, amounts, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity, and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
As used herein, the terms "substantially," "generally," "substantially," "essentially," and "about" are used to describe and illustrate small variations. When used in conjunction with an event or circumstance, the terms can refer to instances where the event or circumstance occurs precisely as well as instances where the event or circumstance occurs in close proximity. For example, when used in conjunction with numerical values, the terms can refer to a range of variation of less than or equal to ± 10% of the stated numerical value, such as less than or equal to ± 5%, less than or equal to ± 4%, less than or equal to ± 3%, less than or equal to ± 2%, less than or equal to ± 1%, less than or equal to ± 0.5%, less than or equal to ± 0.1%, or less than or equal to ± 0.05%. For example, two numerical values are considered to be "substantially" identical if the difference between the two numerical values is less than or equal to ± 10% (e.g., less than or equal to ± 5%, less than or equal to ± 4%, less than or equal to ± 3%, less than or equal to ± 2%, less than or equal to ± 1%, less than or equal to ± 0.5%, less than or equal to ± 0.1%, or less than or equal to ± 0.05%) of the mean of the values.
In the detailed description and claims, a list of items connected by the terms "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means a only; only B; or A and B. In another example, if items A, B and C are listed, the phrase "at least one of A, B and C" means a only; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
The present invention will be described in further detail with reference to the following embodiments, wherein the meaning of the low-leaching or the second low-leaching is the same, and the meaning of the microfiltration dissolution liquid or the microfiltration dissolution liquid is the same, and the ratios of the respective components are mass ratios in the following embodiments unless otherwise specified.
The following steps are disclosed:
1) leaching treatment
Mixing and leaching smoke dust containing zinc and copper and acidic etching waste liquid, standing and filtering to obtain a copper solvent containing zinc and copper; wherein concentrated sulfuric acid or pure water is not required for the leaching treatment. The specific implementation mode is that the acidic etching waste liquid in the step 1) contains 7% of Cu and 2mol/L of acid [ H + ]; and adding zinc-copper containing metallurgical dust into the acidic etching waste liquid as bottom water to perform mixed leaching reaction, supplementing part of industrial circulating water until the liquid-solid ratio is 5:1, controlling the free acid content of the leachate to be about 5g/L, reacting for 6 hours at normal temperature, controlling the pH value of the endpoint of the leachate to be about 1-1.5, and performing solid-liquid separation to obtain the copper solvent containing about 40g/L copper.
2) Solvent extraction of copper
Adding a copper extractant into the copper solvent obtained in the step 1) to obtain a copper-containing extraction liquid and a zinc-containing raffinate; the copper extractant comprises Lix 973; and (3) extracting the leachate obtained in the step (1) by using a copper extractant Lix973 to obtain copper-loaded Lix973 and raffinate, sending the raffinate to a zinc recovery production line to recover valuable metals such as zinc and the like, and carrying out back extraction on the copper-loaded Lix 973.
Wherein, before the step 2) is started, the copper solution in the step 1) is subjected to evaporation treatment in advance; the copper solution is evaporated in advance, so that the concentration of the copper solution is improved after evaporation, the dosage of an extracting agent in the subsequent extraction process can be reduced, and the extraction efficiency of the subsequent process is improved; the zinc-containing raffinate in the step 2) can replace or mix the acidic etching waste liquid in the step 1) as a leaching solvent, and is used for enriching the content of zinc in the zinc-containing raffinate, so that the subsequent process of zinc extraction is facilitated.
The copper solvent and the copper extractant Lix973 are placed in a rotary cavity with a spiral column by adopting a high-speed countercurrent extraction method in the step 2), the copper extractant Lix973 is continuously input into the rotary cavity through a constant flow pump, and when the liquid flow input into the copper extractant Lix973 contacts the solution in the rotary cavity, the liquid flow input direction of the copper extractant Lix973 is opposite to the liquid direction in the rotary cavity, so that the liquid mixing capacity in the rotary cavity is improved; continuously separating the copper-containing extraction liquid from the other end of the rotary cavity; wherein the flow rate of the copper extractant input into the rotary cavity by the constant-flow pump is 1.5-2.0ml/min, and the temperature of the solution in the rotary cavity is maintained at 30-40 ℃; the flow rate of 1.5-2.0ml/min is adopted, so that the tested viscosity of the copper extractant Lix973 at the use temperature of 30-40 ℃ in the step is 30-33cSt, if the flow rate of the copper extractant Lix973 which is pumped into the rotary cavity by the constant flow pump is lower than 1.5ml/min, the flow rate is influenced by the viscosity, and the flow of the copper extractant Lix973 which is pumped into the rotary cavity by the constant flow pump is unstable, so that the subsequent recovery of the copper-containing extract is not facilitated, and the efficiency of other steps is further influenced; if the flow rate of inputting the copper extractant Lix973 into the rotary cavity by the constant-flow pump is higher than 2ml/min, the copper content in the copper-containing extract liquid after subsequent separation is lower than 90%, and the analysis reason is that when the flow rate of the copper extractant Lix973 is high, the copper extractant Lix973 is mixed with a copper solution for a short time and cannot fully complete extraction reaction, which means that the using capacity of the copper extractant Lix973 is not reached; and in the flow rate range, the flow rate is 1.5-2.0ml/min, and the high-speed countercurrent extraction in the step can stably form a copper extraction liquid with the copper content of more than 95%.
In the step 3), a high-speed countercurrent extraction method is adopted, the copper-containing extraction liquid and the electrodeposition barren solution are placed in a rotary cavity with a spiral column, the electrodeposition barren solution is continuously input into the rotary cavity through a constant flow pump, and when the flow of the input electrodeposition barren solution contacts the solution in the rotary cavity, the flow input direction of the electrodeposition barren solution is opposite to the flow direction in the rotary cavity, so that the liquid mixing capacity in the rotary cavity is improved; and continuously separating the strip liquor at the other end of the rotary cavity; wherein the flow rate of the electrodeposition barren solution input into the rotary cavity by the constant flow pump is 2-2.5ml/min, and the temperature of the solution in the rotary cavity is maintained at 50-60 ℃; the flow rate of 2-2.5ml/min has the advantages that the working temperature in the rotary cavity is 50-60 ℃, the viscosity of the copper-containing extraction liquid is 23-27cSt at the temperature through tests, and if the flow rate is lower than 2ml/min, the content of copper in the obtained secondary copper extractant is unstable in the back extraction process, which is not beneficial to parameter setting of the subsequent process; if the flow rate is higher than 2.5ml/min, the copper content in the obtained secondary copper extractant is higher than 5%, which means that the extraction reaction cannot be fully completed.
Compared with the existing extraction method of mixing, stirring and standing, the high-speed countercurrent extraction method used in the steps 2) and 3) adopts the methods of high-speed rotation, high-speed pumping and countercurrent extraction, greatly shortens the extraction time, and is more favorable for the matching of the steps between the industrial assembly lines.
Further, in order to improve the overall process efficiency, two sets of constant flow pump systems can be arranged, one set of constant flow pump pumps the copper-containing extract separated in the step 2) into the rotary cavity with the spiral column, the other set of constant flow pump pumps the electrodeposition barren solution into the rotary cavity with the spiral column in the step 4), and when the two sets of constant flow pumps jet the liquid in the rotary cavity, the jetting directions of the two liquids are opposite, so that the two liquids are favorably and fully mixed.
For the selection of the extraction temperature, the extraction rate of copper tends to increase and then decrease along with the increase of the extraction temperature, wherein the extraction rate of copper is the highest at 30 ℃; on the contrary, the back extraction rate of copper tends to decrease and increase after the temperature is higher than the temperature, the extraction rate of copper obviously increases after the temperature is 50-60 ℃, and the stability of the extractant is influenced by the temperature after the temperature exceeds 60 ℃.
Adding a dilute sulfuric acid solution into the copper-containing extraction liquid obtained in the step 2) for washing, and performing back extraction on the washed solution in the step 3). In actual production, due to factors such as mechanical entrainment and the like, a small amount of metal impurities such as iron, arsenic and the like enter a copper stripping solution along with an organic phase to influence the dissolution treatment of copper sulfate, and in order to prevent the entrained impurities from entering the copper stripping solution, a dilute sulfuric acid solution is adopted for washing in an experiment, wherein the pH range of the dilute sulfuric acid solution is 3-4.
Wherein, sodium hydroxide is added into the zinc-containing raffinate in the step 2), and copper hydroxide precipitate obtained after filtration is added into the strip liquor obtained in the step 3), so as to further improve the recovery rate of copper, reduce the amount of impurity copper in the zinc raffinate and improve the recovery rate of zinc.
3) Back extraction
Carrying out back extraction on the copper-containing extraction liquid obtained in the step 2) to obtain a back extraction liquid and a secondary copper extractant; wherein the secondary copper extractant in the step 3) can replace or mix with the copper extractant in the step 2);
wherein, the electrowinning barren solution generated in the electrowinning process is used for carrying out back extraction on the Lix973 loaded with copper in the step 3) to obtain a back extraction solution with the acidity of 140g/l of Cu12g/l and regenerated Lix973, and the regenerated Lix973 is returned to the solvent for extraction and recycling; the back extraction process can directly obtain the copper concentration and the acid concentration of a copper sulfate solution required by copper powder production by an electrodeposition method by controlling the volume ratio of the organic phase Lix973 loaded with copper to an electrodeposition barren solution, and does not need to add dilute sulfuric acid or an aqueous solution for blending.
4) Electrodeposition copper powder
Carrying out an electrodeposition process on the stripping solution in the step 3) to obtain copper powder and an electrodeposition barren solution; wherein the electro-deposition barren solution in the step 4) can be used for the back extraction process in the step 3).
Pumping the high-purity copper sulfate solution obtained in the back extraction step of the step 3) to an electrodeposition tank to produce electrodeposited copper powder; the anode of the electrodeposition is a Pb alloy insoluble anode, the cathode of the electrodeposition is an electrolytic pure copper plate, the current density is controlled to be 1200-1300A/m2, the temperature of the electrodeposition is 50 ℃, powder is scraped for one time within 30min, and the electrolytic copper powder with the mass percentage of over 99 percent is obtained. The mass percentage of each substance in the finally obtained copper powder is as follows (unit%):
while the invention has been described with reference to specific embodiments, the scope of the invention is not limited thereto, and those skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims. While the present application has been described and illustrated with reference to particular embodiments thereof, such description and illustration are not intended to limit the present application. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the application, as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of the application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present application. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (10)
1. A method for recovering copper by the synergistic treatment of acidic etching waste liquid and zinc-containing copper dust is characterized by comprising the following steps:
leaching treatment
Mixing and leaching smoke dust containing zinc and copper and acidic etching waste liquid, standing and filtering to obtain a copper solvent containing zinc and copper;
solvent extraction of copper
Adding a copper extractant into the copper solvent obtained in the step 1) to obtain a copper-containing extraction liquid and a zinc-containing raffinate;
back extraction
Carrying out back extraction on the copper-containing extraction liquid obtained in the step 2) to obtain a back extraction liquid and a secondary copper extractant;
electrodeposition copper powder
Carrying out an electrodeposition process on the stripping solution in the step 3) to obtain copper powder and an electrodeposition barren solution;
wherein the secondary copper extractant in the step 3) can replace or mix the copper extractant in the step 2); the electro-winning barren solution in step 4) may be used in the stripping process in step 3).
2. The method for recovering copper by using the acidic etching waste liquid and the zinc-containing copper dust for the synergistic treatment as claimed in claim 1, wherein concentrated sulfuric acid or pure water is not additionally added in the step 1) for leaching treatment.
3. The method for recovering copper by using the acidic etching waste liquid and the zinc-containing copper dust for the synergistic treatment according to claim 1, wherein before the step 2), the copper solution in the step 1) is subjected to evaporation treatment in advance; the zinc-containing raffinate in the step 2) can replace or mix the acidic etching waste liquid in the step 1) as a leaching solvent.
4. The method for recovering copper by the synergistic treatment of the acidic etching waste liquid and the zinc-containing copper dust according to claim 3, wherein the step 2) adopts a high-speed countercurrent extraction method, the copper solvent and the copper extractant are placed in a rotary cavity with a spiral column, the copper extractant is continuously input into the rotary cavity through a constant flow pump, and the copper-containing extract is continuously separated from the other end of the rotary cavity; wherein the flow rate of the copper extractant input into the rotary cavity by the constant-flow pump is 1.5-2.0ml/min, and the temperature of the solution in the rotary cavity is maintained at 30-40 ℃;
placing the copper-containing extraction liquid and the electrodeposition barren solution into a rotary cavity with a spiral column by adopting a high-speed countercurrent extraction method in step 3), continuously inputting the electrodeposition barren solution into the rotary cavity through a constant flow pump, and continuously separating the strip liquor from the other end of the rotary cavity; wherein the flow rate of the electrodeposition barren solution which is input into the rotary cavity by the constant flow pump is 2-2.5ml/min, and the temperature of the solution in the rotary cavity is maintained at 50-60 ℃.
5. The method for recovering copper by using the synergistic treatment of the acidic etching waste liquid and the zinc-containing copper dust ash according to claim 4, wherein a constant flow pump system is additionally arranged on the basis of the step 3) and is used for continuously inputting the copper-containing extraction liquid into the rotary cavity.
6. The method for recovering copper by the synergistic treatment of acidic etching waste liquid and zinc-containing copper dust according to claim 5,
adding a dilute sulfuric acid solution into the copper-containing extraction liquid obtained in the step 2) for washing, and performing back extraction in the step 3) on the washed solution
Adding sodium hydroxide into the zinc-containing raffinate obtained in the step 2), filtering to obtain copper hydroxide precipitate, and adding the copper hydroxide precipitate into the strip liquor obtained in the step 3).
7. The method for recovering copper by using the acidic etching waste liquid and the zinc-containing copper dust for synergistic treatment as claimed in claim 5, wherein the copper extracting agent comprises Lix 973; the acidic etching waste liquid comprises acidic etching waste liquid from PCB enterprises, and the components of the acidic etching waste liquid comprise hydrochloric acid and copper chloride.
8. The method for recovering copper by the synergistic treatment of the acidic etching waste liquid and the zinc-containing copper dust according to claim 7, wherein in the step 1), the acidic etching waste liquid contains 7% of Cu and contains 2mol/L of acid [ H + ]; and adding zinc-copper containing metallurgical dust into the acidic etching waste liquid as bottom water to perform mixed leaching reaction, supplementing part of industrial circulating water until the liquid-solid ratio is 5:1, controlling the free acid content of the leachate to be about 5g/L, reacting for 6 hours at normal temperature, controlling the pH value of the endpoint of the leachate to be about 1-1.5, and performing solid-liquid separation to obtain the copper solvent containing about 40g/L copper.
9. The method for recovering copper by the synergistic treatment of the acidic etching waste liquid and the zinc-containing copper soot ash according to claim 8, wherein in the step 3), the electrowinning barren solution generated in the electrowinning process is used for back-extracting the copper-loaded Lix973 to obtain a back-extraction solution with the acidity of 140g/l of Cu12g/l and regenerated Lix973, and the regenerated Lix973 is returned to the solvent extraction for recycling; the back extraction process can directly obtain the copper concentration and acid concentration of the copper sulfate solution required by the copper powder production by the electrodeposition method by controlling the volume ratio of the copper-loaded organic phase Lix973 to the electrodeposition barren solution, and does not need to add dilute sulfuric acid or aqueous solution for blending.
10. The method for recovering copper by the synergistic treatment of the acidic etching waste liquid and the zinc-containing copper dust according to claim 9, wherein the high-purity copper sulfate solution obtained in the back-extraction process in the step 3) is pumped to an electrodeposition tank to produce electrodeposited copper powder; the anode of the electrodeposition is a Pb alloy insoluble anode, the cathode of the electrodeposition is an electrolytic pure copper plate, the current density is controlled to be 1200-1300A/m2, the temperature of the electrodeposition is 50 ℃, powder is scraped for one time within 30min, and the electrolytic copper powder with the mass percentage of over 99 percent is obtained.
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| CN113999972A (en) * | 2021-10-11 | 2022-02-01 | 苏州仕净科技股份有限公司 | Resource utilization production process for waste metal composite material |
| CN113999972B (en) * | 2021-10-11 | 2023-09-08 | 苏州仕净科技股份有限公司 | Resource utilization production process of waste metal composite material |
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