CN111733327A

CN111733327A - Recovery method and recovery device for valuable metals in scrap copper electrolysis anode mud

Info

Publication number: CN111733327A
Application number: CN202010648583.4A
Authority: CN
Inventors: 李冲; 王晓丹; 徐小锋; 崔沐; 宋珍珍
Original assignee: China ENFI Engineering Corp
Current assignee: China ENFI Engineering Corp
Priority date: 2020-07-07
Filing date: 2020-07-07
Publication date: 2020-10-02
Anticipated expiration: 2040-07-07
Also published as: CN111733327B

Abstract

The invention provides a method and a device for recovering valuable metals in scrap copper electrolysis anode mud. The recovery method comprises the following steps: carrying out oxidizing roasting and acid leaching treatment on the scrap copper electrolytic anode mud in sequence to obtain copper-containing acid leaching solution and acid leaching residue; carrying out electrodeposition treatment on the copper-containing pickle liquor for multiple times to obtain cathode copper; and carrying out alkaline leaching treatment on the acid leaching residue to obtain lead-tin alkaline leaching solution and precious metal residue. The method has the advantages of short flow, high copper leaching rate and high direct yield, and in the acid leaching treatment step, impurity elements such as nickel, arsenic and the like are removed in advance while copper is recovered by electrodeposition, so that the burden of impurity removal in the subsequent precious metal recovery process of the precious metal slag is effectively reduced. The method has the advantages of low consumption of process reagents, sealed electrodeposition process, no acid mist, good working environment and no pollution.

Description

Recovery method and recovery device for valuable metals in scrap copper electrolysis anode mud

Technical Field

The invention relates to the field of valuable metal recovery, in particular to a method and a device for recovering valuable metals in scrap copper electrolysis anode mud.

Background

The scrap copper is prepared by carrying out pyrogenic process smelting on scrap copper, copper-containing sludge, electroplating sludge, smelting smoke dust, waste circuit boards and other complex raw materials, carrying out electrolytic refining on the scrap copper to obtain high-purity electrolytic copper, and depositing a large amount of scrap copper electrolytic anode mud at the bottom of an electrolytic tank in the electrolytic process. In recent years, with the continuous and rapid development of the regenerated electrolytic refined copper industry, the yield of the scrap copper electrolytic anode mud is continuously improved, the components of the scrap copper electrolytic anode mud are complex and have large fluctuation, and the scrap copper electrolytic anode mud usually contains various heavy metals such as copper, lead, tin, arsenic and the like and precious metals such as gold, silver and the like, and if the scrap copper electrolytic anode mud is not treated in time, the scrap copper electrolytic anode mud threatens the ecological environment and the human health.

At present, the research on the recovery process of the electrolytic anode slime of the ore copper is wide at home and abroad, and methods for recovering valuable metals from the scrap copper anode slime are reported, but the methods mainly aim at recovering lead, tin and precious metals (gold, silver and the like), and the energy consumption of the recovery methods is high.

Disclosure of Invention

The invention mainly aims to provide a method and a device for recovering valuable metals from scrap copper electrolysis anode mud, so as to recover more valuable metals from the scrap copper electrolysis anode mud with low energy consumption and low cost.

In order to achieve the above object, according to one aspect of the present invention, there is provided a method for recovering valuable metals from scrap copper electrolytic anode slime, the method comprising: carrying out oxidizing roasting and acid leaching treatment on the scrap copper electrolytic anode mud in sequence to obtain copper-containing acid leaching solution and acid leaching residue; carrying out electrodeposition treatment on the copper-containing pickle liquor for multiple times to obtain cathode copper; and carrying out alkaline leaching treatment on the acid leaching residue to obtain lead-tin alkaline leaching solution and precious metal residue.

Further, the recovery method further comprises: carrying out electrodeposition treatment on the lead-tin alkaline leaching solution to obtain a solution after tin soldering and tin electrodeposition; preferably, after the tin electrodeposition liquid is obtained, the recovery method further comprises the step of performing precipitation treatment on part of lead and tin remained in the tin electrodeposition liquid to obtain lead and tin slag.

Further, the oxidizing roasting temperature is 400-700 ℃, and the time is 0.5-2.0 h; preferably, the oxidizing roasting temperature is 600-700 ℃, and the time is 0.5-1 h.

Further, sulfuric acid with the concentration of 100-200 g/L, more preferably 150-200 g/L is adopted for acid leaching treatment; preferably, the liquid-solid ratio of the acid leaching treatment is 2-5: 1; preferably, the temperature of the acid leaching treatment is 60-80 ℃; preferably, the acid leaching treatment is carried out for 0.1-5 h under the stirring condition.

Further, the step of carrying out multiple electrodeposition treatment on the copper-containing pickle liquor to obtain cathode copper comprises the following steps: carrying out first electrodeposition treatment on the copper-containing pickle liquor to obtain cathode copper I and copper electrodeposition liquor I; carrying out second electrodeposition treatment on the copper electrodeposition solution I to obtain cathode copper II and copper electrodeposition solution II; carrying out third electrodeposition treatment on the copper electrodeposition solution II to obtain cathode copper III and copper electrodeposition solution III; preferably, the concentration of copper in the copper-containing pickle liquor is 40-50 g/L, and the current density of the first electrodeposition treatment is 400-500A/m²The concentration of copper in the solution I after copper electrodeposition is 30-35 g/L; preferably, the current density of the second electrodeposition treatment is 500-700A/m²The concentration of copper in the solution II after copper electrodeposition is 10-15 g/L; preferably, the current density of the third electrodeposition treatment is 600-800A/m²And the concentration of copper in the solution III after copper electrodeposition is 0.5-1.0 g/L.

Further, NaOH and NaNO are used₃The mixed solution of (2) is subjected to alkaline leaching treatment, preferably, the concentration of NaOH is 150-200 g/L, and NaNO is added₃The concentration of (A) is 15-40 g/L; preferably, the liquid-solid ratio of the alkaline leaching treatment is 5-10: 1; preferably, the temperature of the alkaline leaching treatment is 80-100 ℃; preference is given toAnd (3) carrying out alkaline leaching treatment for 2-6 h under the stirring condition.

Further, when the lead-tin alkaline leaching solution is subjected to electrodeposition treatment, the current density is controlled to be 400-600A/m²Thus, soldering was obtained.

Further, while obtaining cathode copper, copper arsenic slag and copper electrodeposition liquid are also obtained, and the copper arsenic slag is returned to the oxidizing roasting process or sent to a pyrometallurgical system for treatment; preferably, the copper electrodeposition solution is returned to the acid leaching step.

Further, returning part of the solution after tin electrodeposition to the process of alkaline leaching treatment; preferably, the lead-tin slag is returned to the oxidizing roasting process or to the pyrometallurgical system for treatment.

Further, the electrodeposition treatment is rotational flow electrodeposition treatment or flow electrodeposition treatment; preferably, before the acid leaching residue is subjected to alkaline leaching treatment, the recovery method further comprises the following steps: washing the acid leaching residue; more preferably, water is flushed multiple times.

According to the second aspect of the application, there is also provided a recovery device of valuable metals in scrap copper electrolysis anode mud, comprising: the acid leaching unit comprises a copper-containing acid leaching liquid outlet and an acid leaching slag outlet; the copper electrodeposition unit comprises a plurality of electrodeposition tanks which are sequentially communicated, and the outlet of the copper-containing acid immersion liquid is communicated with the inlet of a first electrodeposition tank in the plurality of electrodeposition tanks which are sequentially communicated; and the inlet of the alkaline leaching unit is communicated with the acid leaching residue outlet, and the alkaline leaching unit comprises a lead-tin alkaline leaching solution outlet and a noble metal residue outlet.

Further, the temperature of the oxidizing roasting unit is controlled to be 400-700 ℃, and the leaching unit contains sulfuric acid with the concentration of 100-200 g/L; preferably, the temperature of the acid leaching unit is controlled to be 60-80 ℃; preferably, the solid-to-liquid ratio of the acid leaching unit is controlled to be 2-5: 1; preferably, the pickling unit further comprises a stirring member for stirring the pickling material.

Further, the recovery device further comprises: and the inlet of the tin electrodeposition unit is communicated with the outlet of the lead-tin alkaline leaching solution.

Further, tin electrodeposition unit still includes tin electrodeposition back liquid export, and recovery unit still includes: and the inlet of the lead-tin precipitation unit is communicated with the tin electrodeposition liquid outlet.

Furthermore, the number of the electrodeposition cells is 2 to 5, preferably 2 to 3.

Further, the copper electrodeposition unit further comprises: and the copper arsenic slag outlet is communicated with an inlet of the oxidizing roasting unit or communicated with a pyrometallurgical system.

Further, the copper electrodeposition unit further comprises: and the liquid outlet after copper electrodeposition is communicated with the inlet of the acid leaching unit.

Further, a liquid outlet after tin electrodeposition is communicated with an inlet of the alkaline leaching unit; preferably, the alkaline leaching unit contains NaOH and NaNO₃The mixed solution of (1); preferably, the concentration of NaOH is 150-200 g/L, and NaNO₃The concentration of (A) is 150-400 g/L; preferably, the liquid-solid ratio of the alkaline leaching unit is 5-10: 1; preferably, the temperature of the alkaline leaching unit is 80-100 ℃; preferably, the alkaline leaching unit further comprises a stirring member.

Further, the lead-tin precipitation unit also comprises a lead-tin slag outlet, and the lead-tin slag outlet is communicated with an inlet of the oxidizing roasting unit or communicated with a pyrometallurgical system.

Further, the recovery device also comprises a washing and filtering unit which is arranged between the acid leaching residue outlet and the inlet of the alkaline leaching unit.

Further, the noble metal slag outlet is communicated with a noble metal extraction device.

By applying the technical scheme of the invention, through oxidizing roasting and acid leaching treatment, firstly, copper, arsenic, nickel and other impurity elements are leached into copper-containing acid leaching liquid, and gold, silver, platinum, palladium and other noble metal elements are enriched in acid leaching residue, and then the noble metal residue can be obtained after alkali leaching treatment, so that the separation and extraction of noble metals can be realized after impurity removal. And performing electrodeposition treatment on the leachate obtained after the acid leaching treatment, namely the copper-containing acid leachate, so as to efficiently recover copper in the leachate, obtain high-grade cathode copper, and directly sell the high-grade cathode copper. The method has the advantages of short flow, high copper leaching rate and high direct yield, and in the acid leaching treatment step, impurity elements such as nickel, arsenic and the like are removed in advance while copper is recovered by electrodeposition, so that the burden of impurity removal in the subsequent precious metal recovery process of the precious metal slag is effectively reduced. The method has the advantages of low consumption of process reagents, sealed electrodeposition process, no acid mist, good working environment and no pollution.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:

fig. 1 shows a schematic flow diagram of a method for recovering valuable metals from scrap copper anode slime according to a preferred embodiment of the present invention;

fig. 2 shows a schematic structure diagram of a recovery device of valuable metals in scrap copper electrolysis anode mud in a preferred embodiment according to the invention.

Wherein the figures include the following reference numerals:

10. an oxidizing roasting unit; 20. an acid leaching unit; 30. a copper electrodeposition unit; 40. an alkaline leaching unit;

50. a tin electrodeposition unit; 60. a lead-tin precipitation unit; 70. a washing and filtering unit; 80. noble metal extraction element.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

Scrap copper electrolysis anode mud: the scrap copper is obtained from crude copper obtained by smelting secondary resources such as copper-containing sludge, smoke dust and the like, the crude copper is subjected to electrolytic refining to obtain high-purity electrolytic copper, and a large amount of substances deposited at the bottom of an electrolytic tank in the electrolytic refining process are scrap copper electrolytic anode mud.

The difference between electrodeposition and electrolysis: the electrodeposition anode plate is not dissolved, and the electrolysis anode plate is dissolved; the electrodeposition adopts an insoluble anode to continuously supplement metal ions to be produced, and the metal is separated out at a cathode, and the electrolysis process is that crude metal is dissolved at the cathode through the anode to be separated out. In the application, the metal is produced by adopting rotational flow electrodeposition, turbulent flow electrodeposition or similar equipment by applying an electrochemical principle. The essence of the method is that mass transfer is enhanced by enhancing the flow of the solution, the concentration polarization phenomenon is weakened, and the method is suitable for the treatment of low-concentration solution.

The waste impure copper anode slime contains 5-10% of copper, is a good copper smelting resource, and if the copper can be recovered and separated from lead, tin and precious metals (gold, silver and the like) under the conditions of low energy consumption and low cost, the comprehensive recovery utilization rate of valuable metals in the waste impure copper anode slime can be improved, and the environmental hazard can be reduced. In order to achieve the above purpose, the inventor of the present application has conducted analysis, comparison and research on the existing recovery process, and found that if copper is preferentially separated, not only is raw material provided for copper smelting, but also subsequent separation and extraction of metal elements such as tin and lead are facilitated.

On the basis of the above, the applicant proposes the scheme of the application. In an exemplary embodiment, there is provided a method for recovering valuable metals from scrap copper electrolysis anode slime, the method comprising: carrying out oxidizing roasting and acid leaching treatment on the scrap copper electrolytic anode mud in sequence to obtain copper-containing acid leaching solution and acid leaching residue; carrying out electrodeposition treatment on the copper-containing pickle liquor for multiple times to obtain cathode copper; carrying out alkaline leaching treatment on the acid leaching residue to obtain lead-tin alkaline leaching solution and precious metal residue; carrying out electrodeposition treatment on the lead-tin alkaline leaching solution to obtain a solution after tin soldering and tin electrodeposition; and precipitating the lead and tin remained in the solution after electrodeposition to obtain lead and tin slag.

According to the recovery method, through oxidizing roasting and acid leaching treatment, firstly, impurity elements such as copper, arsenic and nickel are leached into copper-containing acid leaching liquid, precious metal elements such as gold, silver, platinum and palladium are enriched in acid leaching residues, and the precious metal residues can be obtained through alkali leaching treatment, so that the precious metals can be separated and extracted through impurity removal. And performing electrodeposition treatment on the leachate obtained after the acid leaching treatment, namely the copper-containing acid leachate, so as to efficiently recover copper in the leachate, obtain high-grade cathode copper, and directly sell the high-grade cathode copper. The method has the advantages of short flow, high copper leaching rate and high direct yield, and in the acid leaching treatment step, impurity elements such as arsenic, nickel and the like are removed in advance while copper is recovered by electrodeposition, so that the burden of impurity removal in the subsequent precious metal recovery process of the precious metal slag is effectively reduced. The method has the advantages of low consumption of process reagents, sealed electrodeposition process, no acid mist, good working environment and no pollution.

In order to further efficiently recover metals from the leachate after the alkaline leaching treatment, in a preferred embodiment, the recovery method further comprises: carrying out electrodeposition treatment on the lead-tin alkaline leaching solution to obtain a solution after tin soldering and tin electrodeposition; preferably, after the tin electrodeposition liquid is obtained, the recovery method further comprises the step of performing precipitation treatment on part of lead and tin remained in the tin electrodeposition liquid to obtain lead and tin slag.

And performing electrodeposition treatment on the leachate obtained after the alkaline leaching treatment, namely the lead-tin alkaline leaching solution, so that the tin in the leachate is efficiently recovered, and high-grade tin soldering is obtained and can be directly used for selling. And the lead and tin remained in the solution after tin electrodeposition are subjected to precipitation treatment, so that the recovery rate of the lead and tin is further improved.

Before the oxidizing roasting, the anode mud is usually placed naturally and dried (with a water content of 8 wt% -10 wt%), and then placed in oxidizing roasting equipment for oxidizing roasting, for example, the anode mud is placed in a rotary kiln, and air is introduced for drying in a drying section and oxidizing roasting in a roasting section to obtain roasted sand and flue gas. Leaching the calcine with sulfuric acid to obtain a copper-containing acid leaching solution, and introducing the flue gas into a flue gas treatment device for flue gas treatment.

The purpose of the oxidizing roasting is to oxidize the valuable metals in the scrap copper anode slime into respective oxides, and therefore, the temperature and time of the oxidizing roasting may be subject to this, and is not particularly limited in this application. In order to facilitate the leaching of copper more thoroughly in the subsequent acid leaching treatment, in a preferred embodiment, the temperature of oxidizing roasting is controlled to be 400-700 ℃ and the time is 0.5-2.0 h. In the temperature range, the valuable metal is fully oxidized, the unfavorable condition that the metal is not fully oxidized is easy to occur below 400 ℃, and the unfavorable conditions that the energy consumption is excessive and partial components are melted and the like are likely to occur above 700 ℃. The time is too short, the metal is not completely oxidized, the time is too long, and the oxidization has already reached the limit unfavorable condition. More preferably, the temperature of the oxidizing roasting is controlled to be 500-700 ℃, 550-700 ℃, or 600-700 ℃, and can also be 650 ℃ or 680 ℃. Compared with the prior art in which treatment is carried out by a smelting mode and treatment is carried out by adopting a smelting temperature higher than the melting point of copper, the method has the advantages of simple oxidizing roasting equipment, low investment, simple process and low energy consumption.

The acid leaching treatment step is obtained by adjusting the existing acid leaching conditions. In order to further improve the leaching rate of impurity elements such as copper, nickel, arsenic and the like and improve the recovery rate and impurity removal rate of copper, in a preferred embodiment, sulfuric acid with the concentration of 100-200 g/L is used for acid leaching treatment; preferably, the liquid-solid ratio of the acid leaching treatment is 2-5: 1; preferably, the temperature of the acid leaching treatment is 60-80 ℃; preferably, the acid leaching treatment is carried out for 0.1-5 h under the stirring condition.

When the concentration is higher than 200g/L, the leaching rate of target elements such as copper, nickel, arsenic and the like reaches the limit, the leaching rate of the elements is not obviously affected by continuously improving the acidity of the leaching solution, meanwhile, the corrosion of the equipment is also intensified, and when the concentration is lower than 100g/L, the condition of incomplete leaching is easy to occur due to too low acid concentration. The liquid-solid ratio is within the range of 2-5: 1 (volume-mass ratio L: g), so that the solid calcine and the liquid sulfuric acid can be fully contacted and reacted, and the leaching rate of valuable metals is improved. The leaching rate of the valuable metals can be high by leaching for 0.1-5 hours under the stirring condition of 60-80 ℃ in the acid leaching treatment. The concentration of the sulfuric acid is preferably 150 to 200g/L, more preferably 160 to 200g/L, 170 to 200g/L or 180 to 200 g/L. The liquid-solid ratio is more preferably 2-4: 1, and further preferably 2-3: 1, more preferably 2 to 2.5:1 or the liquid-solid ratio is 2:1 or 2.5: 1.

In the prior art, 30-50% (365-697 g/L) of sulfuric acid is reported to be used for leaching, the concentration of the sulfuric acid is far higher than that in the application, and nickel is not easy to leach because copper in anode mud is not oxidized. Theoretically, the copper sulfide and elemental copper in the anode sludge and slag will not react with the sulfuric acid of the concentration. The leaching rate is lower than that of the technology. In addition, lead and tin in the anode slime are not leached by sulfuric acid, because lead is leached by the sulfuric acidPbSO is formed in the process₄Precipitate and do not enter the solution, and tin does not react with sulfuric acid.

The acid leaching treatment is carried out to obtain the acid leaching solution containing impurity metals such as copper, arsenic and the like, 2-4 sections or even 2-5 sections of electrodeposition treatment can be set according to the concentration of copper in the copper-containing acid leaching solution for further efficiently separating copper, and the number of the specific sections of the electrodeposition treatment can be reasonably adjusted.

In a preferred embodiment, the multiple electrodeposition of the copper-containing pickle liquor to obtain cathode copper comprises: carrying out first electrodeposition treatment on the copper-containing pickle liquor to obtain cathode copper I and copper electrodeposition liquor I; carrying out second electrodeposition treatment on the copper electrodeposition solution I to obtain cathode copper II and copper electrodeposition solution II; and carrying out third electrodeposition treatment on the copper electrodeposition post-liquid II to obtain cathode copper III and copper electrodeposition post-liquid III.

In the above electrodeposition treatment step, an inert material such as graphite, titanium-coated ruthenium is used as an anode, titanium or stainless steel is used as a cathode, a copper-containing acid leachate is used, and each of the post-electrodeposition solutions (mainly containing copper sulfate) is used as an electrolyte. Preferably, the current density of the electrodeposition is 400 to 800A/m²The temperature is 40-60 ℃, and under the current density and the temperature, the method has the advantages of high unit device production efficiency, stable cathode copper chemical composition, flat appearance and the like.

In a preferred embodiment, the copper concentration in the copper-containing acid immersion liquid is 40-50 g/L, and the current density of the first electrodeposition treatment is 400-500A/m²The concentration of copper in the solution I after copper electrodeposition is 30-35 g/L; preferably, the current density of the second electrodeposition treatment is 500-700A/m²The concentration of copper in the solution II after copper electrodeposition is 10-15 g/L; preferably, the current density of the third electrodeposition treatment is 600-800A/m²And the concentration of copper in the solution III after copper electrodeposition is 0.5-1.0 g/L.

When the concentration of copper in the copper acid immersion liquid is 40-50 g/L, 400-500A/m is adopted²The current density of the anode is subjected to electrodeposition treatment, and the beneficial effect of low electrodeposition energy consumption can be obtained. When the concentration of copper is 30-35 g/L, 500-700A/m is adopted²Can make the cathode copper chemicallyThe components reach the standard, and the energy consumption level is lower. When the concentration of copper is 10-15 g/L, 600-800A/m is adopted²The electrodeposition treatment is carried out under the current density of the copper solution, and the beneficial effect of deep copper extraction from the low-copper solution can be obtained.

The acid leaching treatment enables impurity elements such as arsenic and the like to enter the acid leaching solution, and precious metals such as gold, silver, tin, lead and the like are reserved in the acid leaching residue, so that the concentrated enrichment of the precious metals is realized. In a preferred embodiment, NaOH and NaNO are used₃The mixed solution of (2) is subjected to alkaline leaching treatment, preferably, the concentration of NaOH is 150-200 g/L, and NaNO is added₃The concentration of (A) is 150-400 g/L; preferably, the liquid-solid ratio of the alkaline leaching treatment is 5-10: 1; preferably, the temperature of the alkaline leaching treatment is 80-100 ℃; preferably, the alkaline leaching treatment is carried out for 2-6 h under the stirring condition.

By using NaOH and NaNO₃Compared with the single alkali leaching treatment by adopting NaOH, the alkali leaching treatment of the mixed solution has the beneficial effect that the leaching rate of the lead and the tin is further improved due to the oxidation and catalysis of the NaNO3, so that the lead and the tin are effectively separated from precious metals such as gold, silver and the like, and the precious metals are convenient to recover respectively. Compare NaOH with Na₂SO₄Or NaCl mixture, using NaOH and NaNO₃The mixed solution is subjected to alkaline leaching treatment, the technology has low corrosivity on equipment, a soldering tin product can be obtained at the same time, Na is added₂SO₄Leaching causes lead to form a precipitate, and the addition of NaCl accelerates the loss of subsequent electrodeposition equipment.

To control NaOH and NaNO₃The concentrations of the lead and the tin are respectively in the ranges, the leaching rate of the lead and the tin in the concentration range is considered to be optimal, and the leaching rate which is too low cannot guarantee that the effect of the lead and the tin which are too high on improving the leaching rate is extremely limited. More preferably, NaNO₃The concentration of (B) is 200 to 400g/L, more preferably 200 to 300g/L, and still more preferably 200 to 250 g/L. Specifically, NaNO₃Can be 150g/L, 160g/L, 180g/L, 200g/L, 240g/L, 280g/L, 320g/L, 360g/L, or 400 g/L. The concentration of NaOH may be 150g/L, 160g/L, 170g/L, 180g/L, 190g/L, or 200 g/L.

The liquid-solid ratio (volume-mass ratio L: g) of alkaline leaching treatment is controlled within 5-10: 1, so that alkaline energy consumption can be controlled, and efficient leaching of lead and tin can be realized. The temperature of the alkaline leaching treatment is controlled to be 80-100 ℃, because the leaching rate of lead and tin is not high at low temperature, the leaching of lead and tin reaches a target value in the temperature range, and the excessive high leaching rate increases energy consumption and does not help to improve the leaching rate. Preferably, the alkaline leaching treatment is carried out for 2-6 hours under the stirring condition, so that the efficient leaching of lead and tin can be realized. More preferably, the liquid-solid ratio of the alkaline leaching treatment is 6-10: 1, 7-10: 1, 8-10: 1, 9-10: 1, or 5-9: 1, 5-8: 1, 5-7: 1, 5-6: 1, or 6-9: 1, 6-8: 1, 6-7: 1, or 7-9: 1 or 7-8: 1.

The lead and tin in the lead-tin alkaline leaching solution can be subjected to precipitation treatment or electrodeposition treatment respectively as required. In a preferred embodiment, the current density is controlled to be 400-600A/m when electrodeposition treatment is carried out on the lead-tin alkaline leaching solution by comprehensively considering the recovery cost and the recovery efficiency²Thus, soldering was obtained. The concentration of tin in the lead-tin alkaline leaching solution is approximately within the range of 10-50 g/L, and therefore 400-600A/m is adopted²The electrodeposition treatment is carried out at the current density of (2) so that most of tin in the alkaline leaching solution can form tin soldering with high quality and can be sold directly.

In order to reduce pollution emission and improve the utilization efficiency of each valuable metal, in a preferred embodiment, the cathode copper is obtained, copper arsenic slag and copper after-electrodeposition liquid are also obtained, and the copper arsenic slag is returned to the process of oxidizing roasting or sent to a pyrometallurgical system for treatment; preferably, the copper electrodeposition solution is returned to the acid leaching step. The copper and arsenic slag is returned to the process of oxidizing roasting or the process of returning the solution after copper electrodeposition to the process of acid leaching treatment, so that the copper recovery forms a closed cycle and can be efficiently recycled. And the copper arsenic slag is sent to a pyrometallurgical system to realize the re-smelting extraction of copper, and the arsenic can be opened.

In a preferred embodiment, part of the solution after tin electrodeposition is returned to the alkaline leaching process to further improve the recovery efficiency of tin; preferably, the lead-tin slag is returned to the oxidizing roasting process or treated in a pyrometallurgical system, and the recovery efficiency of tin can be further improved.

The electrodeposition treatment mainly refers to rotational flow electrodeposition treatment or turbulent flow electrodeposition treatment, which is substantially characterized in that mass transfer is enhanced through flow of an enhanced solution, the phenomenon of concentration polarization is weakened, and the method is suitable for treatment of low-concentration solutions.

In order to further reduce the alkali consumption in the alkali leaching treatment step, in a preferred embodiment, before the alkali leaching treatment is performed on the acid leaching residue, the recovery method further comprises: washing the acid leaching residue; preferably with multiple rinses of water. The residual acid liquor on the acid leaching residues is washed by water, so that the consumption of alkali liquor in the alkali leaching step is reduced.

And performing electrodeposition on the lead-tin leachate to obtain a soldering tin product, returning part of the liquid after electrodeposition to an alkaline leaching treatment process, opening a circuit to precipitate lead and tin, returning the obtained lead-tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment. Partial open circuit is selected to precipitate lead and tin, and the amount of slag in the recovery cycle is reduced on the premise of improving the recovery efficiency of lead and tin.

According to the preferred embodiments, the process takes the scrap copper electrolysis anode slime as a raw material, fully separates and extracts copper, lead and tin in the scrap copper electrolysis anode slime by adopting a short-process oxidizing roasting-leaching-electrodeposition process, and removes impurity elements such as arsenic, nickel and the like in the leachate of the scrap copper electrolysis anode slime. And (3) enriching precious metal elements such as gold, silver, platinum, palladium and the like in the leaching residue, and separating and extracting the precious metals after impurity removal treatment. The method has the advantages that the pretreatment process of the anode mud is short, the copper leaching rate is high, the direct recovery rate is high, the cathode copper grade is high, and the anode mud can be directly sold; the lead and tin are recovered to obtain a soldering tin product which can be directly sold; impurity elements such as part of arsenic, nickel and the like are removed in advance, so that the burden of impurity removal in the subsequent precious metal recovery process is effectively reduced; the consumption of process reagents is low; the electrodeposition process is sealed operation, has no acid mist and has good working environment.

In an exemplary embodiment, there is provided a recycling apparatus for valuable metals in scrap copper electrolysis anode slime, as shown in fig. 2, the recycling apparatus comprising: the copper-tin electrolytic bath comprises an oxidizing roasting unit 10, an acid leaching unit 20, a copper electrodeposition unit 30, an alkali leaching unit 40, a tin electrodeposition unit 50 and a lead-tin precipitation unit 60 which are sequentially communicated, wherein the oxidizing roasting unit 10 and the acid leaching unit 20 are sequentially communicated, and the acid leaching unit 20 comprises a copper-containing acid leaching solution outlet and an acid leaching residue outlet; the copper electrodeposition unit 30, the copper electrodeposition unit 30 includes a plurality of electrodeposition cells that are communicated in sequence, the outlet of the immersion fluid containing copper is communicated with the inlet of the first electrodeposition cell among the plurality of electrodeposition cells that are communicated in sequence; and the alkaline leaching unit 40 is communicated with the acid leaching residue outlet at the inlet of the alkaline leaching unit 40, and the alkaline leaching unit 40 comprises a lead-tin alkaline leaching solution outlet and a precious metal residue outlet.

The recovery device obtains the calcine through the oxidizing roasting of oxidizing roasting unit earlier, sends the calcine into the acid leaching unit and carries out the acid leaching and handle, can leach impurity elements such as copper and arsenic, nickel earlier in the copper-containing acid leaching liquid, and with noble metal element enrichment such as gold, silver, platinum, palladium in the acid leaching sediment, has carried out edulcoration preliminary treatment in other words to the recovery of follow-up noble metal. And the copper-containing acid leaching solution flowing out of the copper-containing acid leaching solution outlet of the acid leaching unit flows into a plurality of sequentially communicated electrodeposition tanks through the inlet of the first electrodeposition tank to be subjected to electrodeposition treatment, so that cathode copper is obtained. The acid leaching residue outlet of the acid leaching unit is communicated with the inlet of the alkali leaching unit, so that lead-tin alkali leaching liquid generated after the acid leaching residue is subjected to alkali leaching treatment flows out of the lead-tin alkali leaching liquid outlet, and flows into the tin electrodeposition unit through the inlet of the tin electrodeposition unit for electrodeposition treatment, and thus tin soldering is obtained. And the noble metal slag generated by the alkaline leaching unit can be discharged from a noble metal slag port for subsequent separation.

The device has simple structure, high copper leaching rate and high direct recovery rate, and in the acid leaching unit, impurity elements such as partial arsenic, antimony, bismuth and the like are removed in advance while copper is recovered by electrodeposition, so that the impurity removal burden of a subsequent noble metal separation device is effectively reduced. The electrodeposition tank in the device is a sealing device, and the electrodeposition process has no acid mist, good working environment and no pollution.

The oxidizing and roasting unit oxidizes the valuable metals in the waste copper anode slime into respective oxides, so the temperature and time of oxidizing and roasting can be controlled, and the oxidizing and roasting unit is not particularly limited in the application. In order to facilitate the copper leaching to be more thorough in the acid leaching process of the subsequent acid leaching unit, in a preferred embodiment, the temperature of the oxidizing roasting unit is controlled to be 400-700 ℃ and the time is controlled to be 0.5-2.0 h. In the temperature range, the valuable metal is fully oxidized, the unfavorable condition that the metal is not fully oxidized is easy to occur below 400 ℃, and the unfavorable conditions that the energy consumption is excessive and partial components are melted and the like are likely to occur above 700 ℃. The time is too short, the metal is not completely oxidized, the time is too long, and the oxidization has already reached the limit unfavorable condition. More preferably, the temperature of the oxidizing roasting is controlled to be 500-700 ℃, 550-700 ℃, or 600-700 ℃, and can also be 650 ℃ or 680 ℃.

The acid leaching unit is obtained by adjusting the existing acid leaching conditions. In order to further improve the leaching rate of copper, nickel, arsenic and other impurity elements and the recovery rate and impurity removal rate of copper, in a preferred embodiment, the acid leaching unit is used for acid leaching treatment by adopting sulfuric acid with the concentration of 100-200 g/L; preferably, the liquid-solid ratio of the acid leaching treatment is 2-5: 1; preferably, the temperature of the acid leaching treatment is 60-80 ℃; preferably, the acid leaching treatment is carried out for 0.1-5 h under the stirring condition.

In the prior art, 30-50% (365-697 g/L) of sulfuric acid is reported to be adopted for leaching, and the concentration of the sulfuric acid is far higher than that in the application because of the anodeCopper in the mud is not oxidized, and nickel is not easy to leach. Theoretically, the copper sulfide and elemental copper in the anode sludge and slag will not react with the sulfuric acid of the concentration. The leaching rate is lower than that of the technology. In addition, lead and tin in the anode slime are not leached by sulfuric acid, because the lead can form PbSO in the sulfuric acid leaching process₄Precipitate and do not enter the solution, and tin does not react with sulfuric acid.

In order to further recover lead and tin with high efficiency, in a preferred embodiment, as shown in fig. 2, the recovery device further comprises a tin electrodeposition unit 50, and an inlet of the tin electrodeposition unit 50 is communicated with an outlet of the lead-tin alkaline leaching solution.

In another preferred embodiment, the tin electrodeposition unit 50 further comprises a tin post-electrodeposition liquid outlet; the recovery device also comprises a lead-tin precipitation unit 60, wherein the inlet of the lead-tin precipitation unit 60 is communicated with the liquid outlet after tin electrodeposition. The tin electrodeposition unit is used for conducting liquid after electrodeposition, and the liquid outlet part is opened and communicated with the inlet of the lead-tin precipitation unit after tin electrodeposition, so that lead-tin precipitation is achieved, and subsequent recycling of lead-tin precipitation is facilitated.

The oxidizing roasting unit can be communicated with upstream drying equipment so as to pre-dry the scrap copper anode mud, for example, the oxidizing roasting unit can also be used in a drying equipment or a natural airing place, so that the water content of the scrap copper anode mud is reduced to 8-10 wt%. Then the mixture is sent into an oxidizing roasting unit for oxidizing roasting. The oxidizing roasting unit is preferably a rotary kiln, the rotary kiln comprises a drying section and a roasting section, air is introduced, drying is carried out in the drying section, and roasting is carried out in the roasting section to obtain roasted sand and flue gas. And conveying the calcine into an acid leaching unit for acid leaching treatment to obtain copper-containing acid leaching solution, and introducing the flue gas into a flue gas treatment device for flue gas treatment.

In the recovery device, in order to further separate copper from the copper-containing acid leaching solution efficiently, 2-5 electrodeposition tanks, preferably 2-3 electrodeposition tanks, and more preferably 3 electrodeposition tanks can be reasonably arranged according to the concentration of copper in the copper-containing acid leaching solution treated by the acid leaching unit. The copper concentration is high, the number of the electrodeposition tanks can be more than appropriate, the concentration is low, and the number is less.

The electrodeposition bath may be made of an inert material such as graphite or titaniumRuthenium is coated as an anode, titanium or stainless steel is used as a cathode, a copper-containing acid leaching solution and each post-electrodeposition solution (mainly containing copper sulfate) are used as electrolyte. Preferably, the current density of the electrodeposition cell is 400 to 800A/m²The temperature is 40-60 ℃, and under the current density and the temperature, the method has the advantages of high unit device production efficiency, stable cathode copper chemical composition, flat appearance and the like.

In a preferred embodiment, there are 3 electrodeposition cells, and the concentration of copper in the copper-containing pickle liquor in the first electrodeposition cell is 40 to 50g/L and the current density is 400 to 500A/m²The concentration of copper in the solution I after copper electrodeposition is 30-35 g/L; preferably, the current density in the second electrodeposition cell is 500 to 700A/m²The concentration of copper in the solution II after copper electrodeposition is 10-15 g/L; preferably, the current density in the third electrodeposition cell is 600 to 800A/m²And the concentration of copper in the solution III after copper electrodeposition is 0.5-1.0 g/L.

When the concentration of copper in the copper acid immersion liquid is 40-50 g/L, 400-500A/m is adopted²The current density of the anode is subjected to electrodeposition treatment, and the beneficial effect of low electrodeposition energy consumption can be obtained. When the concentration of copper is 30-35 g/L, 500-700A/m is adopted²The electrodeposition treatment is carried out under the current density, so that the chemical components of the cathode copper can reach the standard, and the energy consumption level is lower. When the concentration of copper is 10-15 g/L, 600-800A/m is adopted²The electrodeposition treatment is carried out under the current density of the copper solution, and the beneficial effect of deep copper extraction from the low-copper solution can be obtained.

To further improve the copper recovery efficiency, in a preferred embodiment, as shown in fig. 2, the copper electrodeposition unit 30 further comprises: and a copper arsenic slag outlet which is communicated with an inlet of the oxidizing roasting unit 10 or a pyrometallurgical system (not shown). In a preferred embodiment, the copper electrodeposition cell 30 further comprises: and a liquid outlet after copper electrodeposition is communicated with an inlet of the acid leaching unit 20.

In order to further improve the recovery rate of tin, in a preferred embodiment, as shown in fig. 2, the tin post-electrodeposition liquid outlet is communicated with the inlet of the alkaline leaching unit 40.

In a preferred embodiment of the present invention,using NaOH and NaNO₃The mixed solution of (2) is used as an alkaline leaching solution of the alkaline leaching unit, preferably, the concentration of NaOH is 150-200 g/L, and NaNO is₃The concentration of (A) is 150-400 g/L; preferably, the liquid-solid ratio of the alkaline leaching unit in the alkaline leaching treatment process is 5-10: 1; preferably, the temperature of the alkaline leaching unit is 80-100 ℃; preferably, the alkaline leaching unit is used for treating for 2-6 h under the stirring condition.

By using NaOH and NaNO₃Compared with the single NaOH, the mixed solution of the NaNO solution is subjected to alkaline leaching treatment, so that the NaNO solution is obtained due to the fact that the NaNO solution is subjected to alkaline leaching treatment₃Has the advantages of oxidation and catalysis, and further improves the leaching rate of lead and tin, thereby effectively separating lead and tin from noble metals such as gold, silver and the like, and facilitating the respective recovery. Compare NaOH with Na₂SO₄Or NaCl mixture, using NaOH and NaNO₃The mixed solution is subjected to alkaline leaching treatment, the technology has low corrosivity on equipment, a soldering tin product can be obtained at the same time, Na is added₂SO₄Leaching causes lead to form a precipitate, and the addition of NaCl accelerates the loss of subsequent electrodeposition equipment.

In order to further improve the recycling rate of lead and tin, in a preferred embodiment, as shown in fig. 2, the lead and tin precipitation unit 60 further comprises a lead and tin slag outlet, and the lead and tin slag outlet is communicated with the inlet of the oxidizing and roasting unit 10 or communicated with a pyrometallurgical system (not shown).

In order to further reduce the lye consumption of the alkaline leaching unit, in a preferred embodiment, as shown in fig. 2, the recovery apparatus further comprises a washing filter unit 70, the washing filter unit 70 being arranged between the acid sludge outlet and the inlet of the alkaline leaching unit 40. The acid liquor remained on the acid leaching residue at the acid leaching residue outlet is washed clean by water and then enters the alkaline leaching unit, so that the alkaline consumption can be reduced.

In order to further reduce the emission of polluting exhaust gases, in a preferred embodiment, as shown in fig. 2, the oxidizing roasting unit 10 further comprises a flue gas outlet, which is in communication with the flue gas treatment device. On the one hand, the heat in the flue gas is conveniently and reasonably utilized, and on the other hand, the pollution of harmful gas in the flue gas to the air is also reduced.

According to the subsequent utilization condition of the noble metal, the noble metal can be respectively recovered. In a preferred embodiment, as shown in FIG. 2, the precious metal slag outlet communicates with a precious metal extraction device 80 to allow for the rational utilization of different precious metals.

In order to further reduce the environmental pollution caused by the discharge of waste liquid, in a preferred embodiment, the lead-tin precipitation unit 60 further includes a post-lead-tin precipitation liquid outlet, and the post-lead-tin precipitation liquid outlet is communicated with a wastewater treatment device (not shown) and is discharged after harmless treatment.

The different metal slag discharged from the outlets can be sent to a pyrometallurgical smelting system for respectively recovering elements such as tin, lead, noble metals and the like.

And performing electrodeposition on the lead-tin leachate to obtain a soldering tin product, returning part of the liquid after electrodeposition to the alkaline leaching treatment process, opening the other part of the liquid to precipitate lead and tin, returning the obtained lead-tin slag to an oxidizing roasting or pyrogenic system, and delivering the liquid after lead and tin precipitation to wastewater treatment. Partial open circuit is selected to precipitate lead and tin, and the amount of slag in the recovery cycle is reduced on the premise of improving the recovery efficiency of lead and tin.

The advantageous effects of the present application will be further described with reference to specific examples. In the following examples, the apparatus of FIG. 2 was used to recover the product according to the flow shown in FIG. 1.

Example 1

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting at the roasting temperature of 700 ℃ for 1h, and then air cooling. Stirring the obtained calcine for 1h at the sulfuric acid concentration of 150g/L, the liquid-solid ratio of 3:1 and the temperature of 70 ℃, filtering to obtain leachate and leaching residues, analyzing the leachate to obtain the copper concentration of 48g/L and the leaching rate of 98.9 percent; the obtained leachate is treated at a current density of 450A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 35 g/L; the solution I after electrodeposition is carried out at the current density of 550A/m²Performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 15g/L after electrodeposition; the solution II after electrodeposition is carried out at the current density of 700A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 1.0 g/L. Leaching residue is treated at the concentration of 150g/L, NaNO NaOH₃Stirring and leaching for 2h at the temperature of 80 ℃ with the concentration of 20g/L and the liquid-solid ratio of 5:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are 90% and 85% respectively; leaching the lead-tin leaching solution at the current density of 400A/m²And (3) carrying out turbulent electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 2

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 650 ℃ for 1.5h, and then air-cooling the materials. Stirring the obtained calcine for 1h at the sulfuric acid concentration of 180g/L, the liquid-solid ratio of 2.5:1 and the temperature of 70 ℃, filtering to obtain leachate and leaching residues, analyzing the leachate to obtain 45g/L of copper concentration and 95.5% of leaching rate; leaching the obtained solutionThe current density of the effluent is 480A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 33 g/L; the solution I after electrodeposition is carried out at a current density of 600A/m²Performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 12g/L after electrodeposition; the solution II after electrodeposition is carried out at the current density of 750A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.8 g/L. Leaching residue is treated at the concentration of NaOH of 180g/L, NaNO₃Stirring and leaching for 2h at the temperature of 90 ℃ with the concentration of 30g/L and the liquid-solid ratio of 6:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are 93% and 88% respectively; leaching the lead-tin leaching solution at the current density of 500A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 3

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting at the roasting temperature of 600 ℃ for 2.0h, and then air-cooling. Stirring the obtained calcine for 1h at the sulfuric acid concentration of 200g/L, the liquid-solid ratio of 2.5:1 and the temperature of 70 ℃, filtering to obtain leachate and leaching residue, and analyzing the leachate to obtain the copper concentration of 43g/L and the leaching rate of 91.6 percent; the obtained leachate is treated at a current density of 500A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 30 g/L; the solution I after electrodeposition is carried out at a current density of 650A/m²Performing two-stage cyclone electrodeposition to obtain a solution II after electrodeposition, wherein the copper concentration is 10 g/L; the solution II after electrodeposition is carried out at the current density of 780A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching residue is added with NaOH with the concentration of 200g/L, NaNO₃Stirring and leaching for 2.5h at the temperature of 100 ℃ with the concentration of 40g/L and the liquid-solid ratio of 8:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are 95% and 90% respectively; leaching the lead-tin leaching solution at the current density of 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 4

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting at the roasting temperature of 400 ℃ for 2.0h, and then air-cooling. Stirring the obtained calcine for 0.5h at the sulfuric acid concentration of 100g/L, the liquid-solid ratio of 5:1 and the temperature of 80 ℃, filtering to obtain a leaching solution and leaching residues, and analyzing the copper concentration of the leaching solution to be 30g/L and the leaching rate to be 70%; the obtained leachate is treated at a current density of 500A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I with copper concentration of 25g/L after electrodeposition; the solution I after electrodeposition is carried out at a current density of 700A/m²Performing two-stage cyclone electrodeposition to obtain a solution II after electrodeposition, wherein the copper concentration is 5 g/L; the solution II after electrodeposition is carried out at the current density of 800A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching residue is added with NaOH with the concentration of 200g/L, NaNO₃Stirring and leaching for 6h at the temperature of 80 ℃ with the concentration of 15g/L and the liquid-solid ratio of 8:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are 95% and 90% respectively; leaching the lead-tin leaching solution at the current density of 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 5

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 700 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5 hours at the temperature of 60 ℃ with the sulfuric acid concentration of 200g/L and the liquid-solid ratio of 2:1, filtering to obtain leachate and leaching residue, and analyzing the leachate to obtain 41.5g/L copper concentration and 89.4% leaching rate; the obtained leachate is treated at a current density of 400A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 34 g/L; the solution I after electrodeposition is carried out at a current density of 500A/m²Performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 15g/L after electrodeposition; the solution II after electrodeposition is carried out at the current density of 600A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching residue is added with NaOH with the concentration of 200g/L, NaNO₃Stirring and leaching for 2h at the temperature of 100 ℃ with the concentration of 40g/L and the liquid-solid ratio of 10:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are 95.2% and 90.5% respectively; will be provided withThe current density of the lead-tin leaching solution is 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 6

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 800 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5 hours at the temperature of 60 ℃ with the sulfuric acid concentration of 200g/L and the liquid-solid ratio of 2:1, filtering to obtain leachate and leaching residues, and analyzing the leachate with the copper concentration of 20g/L and the leaching rate of 50%; the obtained leachate is treated at a current density of 600A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 15 g/L; the solution I after electrodeposition is carried out at a current density of 700A/m²Performing two-stage cyclone electrodeposition to obtain a solution II after electrodeposition, wherein the copper concentration is 5 g/L; the solution II after electrodeposition is carried out at the current density of 800A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching residue is added with NaOH with the concentration of 200g/L, NaNO₃Stirring and leaching for 2h at the temperature of 100 ℃ with the concentration of 40g/L and the liquid-solid ratio of 10:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are respectively 95.2% and 90.5%; leaching the lead-tin leaching solution at the current density of 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 7

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 700 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5 hours at the temperature of 60 ℃ with the sulfuric acid concentration of 90g/L and the liquid-solid ratio of 6:1, filtering to obtain leachate and leaching residues, and analyzing the leachate to obtain the copper concentration of 15g/L and the leaching rate of 35%; the obtained leachate is treated at a current density of 400A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 15 g/L; the solution I after electrodeposition is carried out at a current density of 500A/m²Performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 15g/L after electrodeposition; the solution after electrodeposition IIAt a current density of 600A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching residue is added with NaOH with the concentration of 200g/L, NaNO₃Stirring and leaching for 2h at the temperature of 100 ℃ with the concentration of 40g/L and the liquid-solid ratio of 10:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are respectively 95.2% and 90.5%; leaching the lead-tin leaching solution at the current density of 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 8

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 700 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5 hours at the temperature of 60 ℃ with the sulfuric acid concentration of 200g/L and the liquid-solid ratio of 2:1, filtering to obtain leachate and leaching residue, and analyzing the leachate to obtain 41.5g/L copper concentration and 89.4% leaching rate; the obtained leachate is treated at a current density of 400A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 34 g/L; the solution I after electrodeposition is carried out at a current density of 500A/m²Performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 15g/L after electrodeposition; the solution II after electrodeposition is carried out at the current density of 600A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching the leaching residue under stirring at the temperature of 100 ℃ for 2h and with the concentration of NaOH of 200g/L and the liquid-solid ratio of 10:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are respectively 50% and 40%; leaching the lead-tin leaching solution at the current density of 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 9

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 700 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5h at the sulfuric acid concentration of 200g/L, the liquid-solid ratio of 2:1 and the temperature of 60 ℃, filtering to obtain leaching solution and leaching residue, and analyzing the copper concentration of the leaching solution41.5g/L, and the leaching rate is 89.4 percent; the obtained leachate is treated at a current density of 400A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 34 g/L; the solution I after electrodeposition is carried out at a current density of 500A/m²Performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 15g/L after electrodeposition; the solution II after electrodeposition is carried out at the current density of 600A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching residue is treated with NaOH with the concentration of 200g/L, NaSO₄The concentration is 40g/L, the liquid-solid ratio is 10:1, stirring leaching is carried out for 2h at 100 ℃, and lead-tin leaching liquid and noble metal materials are obtained after filtering, wherein the leaching rates of lead and tin are respectively 15.2% and 90.5%; leaching the lead-tin leaching solution at the current density of 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 10

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 700 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5 hours at the temperature of 60 ℃ with the sulfuric acid concentration of 200g/L and the liquid-solid ratio of 2:1, and filtering to obtain leachate, wherein the copper concentration of the leachate is 41.5g/L and the leaching rate is 89.4 percent; the obtained leachate is treated at a current density of 400A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 34 g/L; the solution I after electrodeposition is carried out at a current density of 500A/m²Performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 15g/L after electrodeposition; the solution II after electrodeposition is carried out at the current density of 600A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching residue is treated with NaOH with the concentration of 200g/L, NaNO₃The concentration is 50g/L, the liquid-solid ratio is 10:1, stirring leaching is carried out for 2h at 100 ℃, and lead-tin leaching liquid and noble metal materials are obtained after filtering, wherein the leaching rates of lead and tin are respectively 84.7 percent and 80.5 percent; leaching the lead-tin leaching solution at the current density of 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 11

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 700 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5 hours at the temperature of 60 ℃ with the sulfuric acid concentration of 200g/L and the liquid-solid ratio of 2:1, filtering to obtain leachate and leaching residue, and analyzing the leachate to obtain 41.5g/L copper concentration and 89.4% leaching rate; the obtained leachate is treated at a current density of 400A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 34 g/L; the solution I after electrodeposition is carried out at a current density of 500A/m²And performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 15g/L after electrodeposition. Leaching residue is treated with NaOH with the concentration of 200g/L, NaNO₃The concentration is 40g/L, the liquid-solid ratio is 10:1, stirring leaching is carried out for 2h at 100 ℃, and lead-tin leaching liquid and noble metal materials are obtained after filtering, wherein the leaching rates of lead and tin are respectively 95.2% and 90.5%; leaching the lead-tin leaching solution at the current density of 600A/m²And (3) performing cyclone electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part for open circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 12

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 700 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5 hours at the temperature of 60 ℃ with the sulfuric acid concentration of 200g/L and the liquid-solid ratio of 2:1, filtering to obtain leachate and leaching residue, and analyzing the leachate to obtain 41.5g/L copper concentration and 89.4% leaching rate; the obtained leachate is treated at a current density of 600A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I with copper concentration of 25g/L after electrodeposition; the solution I after electrodeposition is carried out at a current density of 800A/m²Performing two-stage cyclone electrodeposition to obtain a solution II after electrodeposition, wherein the copper concentration is 5 g/L; the solution II after electrodeposition is carried out at the current density of 550A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 5 g/L. Leaching residue is added with NaOH with the concentration of 200g/L, NaNO₃Stirring and leaching for 2h at the temperature of 100 ℃ with the concentration of 40g/L and the liquid-solid ratio of 10:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are respectively 95.2% and 90.5%; leaching the lead-tin leaching solution at the current density of 600A/m²Downward swirlingAnd (3) electrodepositing to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part, opening a circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

Example 13

And (3) putting the aired materials into a rotary kiln, introducing air into the rotary kiln, drying and oxidizing and roasting the materials at the roasting temperature of 700 ℃ for 0.5h, and then air-cooling the materials. Stirring the obtained calcine for 5 hours at the temperature of 60 ℃ with the sulfuric acid concentration of 200g/L and the liquid-solid ratio of 2:1, filtering to obtain leachate and leaching residue, and analyzing the leachate to obtain 41.5g/L copper concentration and 89.4% leaching rate; the obtained leachate is treated at a current density of 400A/m²Next, carrying out first-stage cyclone electrodeposition to obtain a solution I after electrodeposition, wherein the copper concentration is 34 g/L; the solution I after electrodeposition is carried out at a current density of 500A/m²Performing two-stage cyclone electrodeposition to obtain a solution II with copper concentration of 15g/L after electrodeposition; the solution II after electrodeposition is carried out at the current density of 600A/m²Then three-stage cyclone electrodeposition is carried out to obtain the solution III after electrodeposition with copper concentration of 0.5 g/L. Leaching residue is added with NaOH with the concentration of 200g/L, NaNO₃Stirring and leaching for 2h at the temperature of 100 ℃ with the concentration of 40g/L and the liquid-solid ratio of 10:1, and filtering to obtain a lead-tin leaching solution and a precious metal material, wherein the leaching rates of lead and tin are respectively 95.2% and 90.5%; leaching the lead-tin leaching solution at the current density of 700A/m²And (3) performing electrodeposition to obtain a soldering tin product, returning the liquid after electrodeposition to an alkaline leaching part to open a circuit to precipitate lead and tin, returning the obtained lead and tin slag to an oxidizing roasting or pyrogenic process system, and delivering the liquid after lead and tin precipitation to wastewater treatment.

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the invention adopts a short-process oxidizing roasting-leaching-electrodeposition process to fully separate and extract copper and lead and tin in the scrap copper electrolytic anode mud and remove arsenic, nickel and other impurity elements in the leachate of the scrap copper electrolytic anode mud. And (3) enriching precious metal elements such as gold, silver, platinum, palladium and the like in the leaching residue, and separating and extracting the precious metals after impurity removal treatment. The method has the advantages of short pretreatment process of the anode mud, high copper leaching rate, high direct recovery rate and high cathode copper grade, and can be directly sold; the lead and tin are recovered to obtain a soldering tin product which can be directly sold; impurity elements such as part of arsenic, nickel and the like are removed in advance, so that the burden of impurity removal in the subsequent precious metal recovery process is effectively reduced; the consumption of process reagents is low; the electrodeposition process is sealed operation, has no acid mist and has good working environment.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for recovering valuable metals in scrap copper electrolysis anode mud is characterized by comprising the following steps:

carrying out oxidizing roasting and acid leaching treatment on the scrap copper electrolytic anode mud in sequence to obtain copper-containing acid leaching solution and acid leaching residue;

carrying out electrodeposition treatment on the copper-containing pickle liquor for multiple times to obtain cathode copper;

and carrying out alkaline leaching treatment on the acid leaching residue to obtain lead-tin alkaline leaching solution and precious metal residue.

2. The recycling method according to claim 1, further comprising: carrying out electrodeposition treatment on the lead-tin alkaline leaching solution to obtain a solution after tin soldering and tin electrodeposition;

preferably, after the tin electrodeposition liquid is obtained, the recovery method further comprises the step of performing precipitation treatment on part of lead and tin remained in the tin electrodeposition liquid to obtain lead and tin slag.

3. The recovery method according to claim 1, wherein the oxidizing roasting temperature is 400-700 ℃ and the time is 0.5-2.0 h;

preferably, the oxidizing roasting temperature is 600-700 ℃, and the time is 0.5-1 h.

4. The recovery method according to claim 1, wherein the acid leaching treatment is performed with sulfuric acid having a concentration of 100 to 200g/L, more preferably 150 to 200 g/L;

preferably, the liquid-solid ratio of the acid leaching treatment is 2-5: 1;

preferably, the temperature of the acid leaching treatment is 60-80 ℃;

preferably, the acid leaching treatment is carried out for 0.1-5 h under the stirring condition.

5. The recovery process of claim 1, wherein subjecting the copper-containing pickle liquor to a plurality of electrodeposition treatments to obtain cathode copper comprises:

carrying out first electrodeposition treatment on the copper-containing acid leaching solution to obtain cathode copper I and copper electrodeposition solution I;

carrying out secondary electrodeposition treatment on the copper electrodeposition solution I to obtain cathode copper II and copper electrodeposition solution II;

carrying out third electrodeposition treatment on the copper electrodeposition liquid II to obtain cathode copper III and copper electrodeposition liquid III;

preferably, the concentration of copper in the copper-containing pickle liquor is 40-50 g/L, and the current density of the first electrodeposition treatment is 400-500A/m²The concentration of copper in the copper electrodeposition solution I is 30-35 g/L;

preferably, the current density of the second electrodeposition treatment is 500-700A/m²The concentration of copper in the copper electrodeposition liquid II is 10-15 g/L;

preferably, the current density of the third electrodeposition treatment is 600-800A/m²And the concentration of copper in the copper electrodeposition liquid III is 0.5-1.0 g/L.

6. The recovery method according to claim 1, wherein NaOH and NaNO are used₃The mixed solution of (a) is subjected to the alkaline leaching treatment,

preferably, the concentration of NaOH is 150-200 g/L, and the NaNO is₃The concentration of (A) is 15-40 g/L;

preferably, the liquid-solid ratio of the alkaline leaching treatment is 5-10: 1;

preferably, the temperature of the alkaline leaching treatment is 80-100 ℃;

preferably, the alkaline leaching treatment is carried out for 2-6 h under the stirring condition.

7. The recovery method according to claim 2, wherein the current density is controlled to 400 to 600A/m in the electrodeposition treatment of the lead-tin alkali immersion liquid²Thus obtaining the solder.

8. The recovery method according to any one of claims 1 to 7, wherein the cathode copper is obtained, and simultaneously copper arsenic slag and copper electrodeposition liquid are obtained, and the copper arsenic slag is returned to the oxidizing roasting process or sent to a pyrometallurgical system for treatment;

preferably, the copper electrodeposition solution is returned to the acid leaching step.

9. The recovery method according to claim 2, wherein a part of the post-tin-electrodeposition solution is returned to the alkaline leaching step;

preferably, the lead-tin slag is returned to the oxidizing roasting process or treated in a pyrometallurgical system.

10. The recovery method according to claim 1, wherein the electrodeposition treatment is a cyclone electrodeposition treatment or a turbulent electrodeposition treatment;

preferably, before the acid leaching residue is subjected to alkaline leaching treatment, the recovery method further comprises: washing the acid leaching residue; more preferably, water is flushed multiple times.

11. A recovery unit of valuable metal in scrap copper electrolysis anode mud, characterized in that, recovery unit includes:

the device comprises an oxidizing roasting unit (10) and an acid leaching unit (20) which are sequentially communicated, wherein the acid leaching unit (20) comprises a copper-containing acid leaching liquid outlet and an acid leaching residue outlet;

a copper electrodeposition unit (30), wherein the copper electrodeposition unit (30) comprises a plurality of electrodeposition cells which are communicated in sequence, and the outlet of the immersion liquid containing copper acid is communicated with the inlet of a first electrodeposition cell in the plurality of electrodeposition cells which are communicated in sequence;

the inlet of the alkaline leaching unit (40) is communicated with the acid leaching residue outlet, and the alkaline leaching unit (40) comprises a lead-tin alkaline leaching solution outlet and a precious metal residue outlet.

12. The recycling apparatus according to claim 11, wherein the temperature of the oxidizing roasting unit (10) is controlled to 400-700 ℃, and the acid leaching unit (20) contains sulfuric acid with a concentration of 100-200 g/L;

preferably, the temperature of the acid leaching unit (20) is controlled to be 60-80 ℃;

preferably, the solid-to-liquid ratio of the acid leaching unit (20) is controlled to be 2-5: 1;

preferably, the pickling unit further comprises a stirring member for stirring the pickling material.

13. The recycling apparatus according to claim 11, further comprising: a tin electrodeposition unit (50), wherein an inlet of the tin electrodeposition unit (50) is communicated with the lead-tin alkaline leaching solution outlet;

preferably, the tin electrodeposition unit (50) further comprises a tin post-electrodeposition liquid outlet, and the recovery apparatus further comprises:

and the inlet of the lead-tin precipitation unit (60) is communicated with the liquid outlet after tin electrodeposition.

14. The recycling apparatus according to claim 11, wherein the number of the electrodeposition cells is 2 to 5, preferably 2 to 3.

15. A recovery device according to claim 11, characterized in that the copper electrowinning cell (30) further comprises:

a copper arsenic slag outlet which is communicated with the inlet of the oxidizing roasting unit (10) or communicated with a pyrometallurgical system; and/or

And the liquid outlet after copper electrodeposition is communicated with the inlet of the acid leaching unit (20).

16. The recovery apparatus according to claim 13, wherein the post tin electrodeposition liquid outlet communicates with an inlet of the alkaline leaching unit (40);

preferably, the alkaline leaching unit (40) contains NaOH and NaNO₃The mixed solution of (1);

preferably, the concentration of NaOH is 150-200 g/L, and the NaNO is₃The concentration of (A) is 150-400 g/L;

preferably, the liquid-solid ratio of the alkaline leaching unit (40) is 5-10: 1;

preferably, the temperature of the alkaline leaching unit (40) is 80-100 ℃;

preferably, the alkaline leaching unit (40) further comprises a stirring member.

17. A recovery device according to claim 13, characterized in that the lead-tin precipitation unit (60) further comprises a lead-tin slag outlet communicating with the inlet of the oxidizing-roasting unit (10) or with a pyrometallurgical system.

18. A recycling apparatus according to claim 11, characterized in that the recycling apparatus further comprises a washing filter unit (70), the washing filter unit (70) being arranged between the acid sludge outlet and the inlet of the alkaline leaching unit (40);

preferably, the precious metal slag outlet is in communication with a precious metal extraction device (80).