Method for removing copper and extracting selenium from copper anode slime

Abstract

The invention discloses a method for removing copper and extracting selenium from copper anode slime, which comprises the following steps: leaching copper and selenium: mixing the copper anode slime, an acid solution containing sulfate radicals and an oxidizing agent to obtain a pulpified material, and leaching under the ultrasonic conditions that the reaction temperature is 50-80 DEG C and the ultrasonic power is 200-800 W to obtain a copper-selenium-rich solution and copper-selenium-removed slag, the oxidizing agent is 2KHSO5. KHSO4. K2SO4, and the pH value of the oxidizing agent is 7. A selenium precipitation agent is added into the copper-selenium-rich liquid, a reduction reaction is carried out under the ultrasonic conditions that the reduction temperature is 30-75 DEG C and the ultrasonic power is 150-600 W, selenium precipitation is carried out, crude selenium and copper-selenium-rich liquid are obtained, and the selenium precipitation agent is selected from at least one of hydroxylamine sulfate, hydroxylamine and hydroxylamine hydrochloride. According to the method, copper is separated from the copper anode slime and selenium is extracted from the copper anode slime only through a two-step method, the overall process is short, reaction conditions are mild, the treatment time is short, the operation environment is good, and energy consumption is low.

Description

Technical Field

[0001] The present invention relates to the technical field of extracting valuable elements from copper anode mud, and more particularly to a method for removing copper and extracting selenium from copper anode mud. Background Art

[0002] Copper anode slime is a key byproduct of copper electrolytic refining. Containing copper, selenium, gold, silver, and platinum group metals, it is considered an important secondary source for the recovery of valuable metals. To efficiently recover precious metals and platinum group metals from anode slime, it requires pretreatment to remove impurities, particularly copper and selenium.

[0003] Currently, methods for separating copper and selenium from copper anode slime are primarily categorized into two types: pyrolysis (sulfation or oxidative roasting) and hydrolysis. One prior art method uses a rotary kiln to roast copper anode slime to separate selenium. Selenium exists in the flue gas as selenium dioxide, while copper remains in the roasted sand. However, this method is poorly adaptable to the raw materials and generates large amounts of flue gas, including highly toxic gases such as selenium dioxide, which seriously pollute the environment. Furthermore, subsequent copper removal from the roasted sand and absorption of selenium dioxide require water, generating significant amounts of wastewater.

[0004] The wet separation method mainly uses acid / alkaline leaching, redox and other methods to leach impurities such as copper and selenium from the slag phase to the liquid phase and then separate them from the liquid in sequence. A technical method has proposed a fully wet method for the efficient separation and recovery of copper, selenium and tellurium from copper anode mud. This method extracts tellurium, selenium and copper step by step through sulfide leaching - oxygen pressure alkaline leaching - acid leaching - reduction - extraction. However, this method will also precipitate some silver ions in the form of silver sulfite during reduction and deselenization, resulting in the loss of metallic silver. At the same time, the use of oxygen pressure alkaline leaching has high requirements for equipment and is prone to severe corrosion. The entire process is long, and the cost of treating the waste liquid generated in the intermediate process is high.

[0005] There is also a technology that separates selenium through screening and washing-alkaline pressure oxidation leaching, and then recovers copper through sulfuric acid leaching. However, the reaction conditions of this method are relatively harsh, and copper and selenium separation can only be achieved at a higher temperature, which consumes a lot of energy.

[0006] The above methods all achieve separation of elements such as copper and selenium through multiple step-by-step extractions, which require long process flows, large amounts of reagents, and high equipment requirements. Therefore, these methods are technical problems that urgently need to be solved in this field.

[0007] Chinese Patent Document 1 (Application No.: 202310257119.6, Application Date: 2023.03.08) discloses a valuable metal recovery process based on Fenton reagent oxidation leaching of copper anode mud, comprising the following steps: (1) adding a quantitative amount of Fe 0The powder is continuously stirred in a mixture of sulfuric acid and hydrogen peroxide is quantitatively introduced to perform advanced oxidation leaching. After the leaching is completed, a first leachate and a first gold-rich leach residue are obtained; (2) chloride is added to the first leachate, and after precipitation and filtration, a second leachate and a second silver-rich leach residue are obtained; (3) sulfite is added to the second leachate, and after reaction, selenium, tellurium products and a third leachate are obtained; sodium thiosulfate is added to the second silver-rich leach residue to complex silver, and electrolytic recovery is obtained to obtain refined silver, and the liquid after electrolytic recovery is reused to complex the second silver-rich leach residue; (4) the third leachate is electrolytically recovered to obtain refined copper. In this scheme, Fenton's reagent is used as an oxidant, new ions are introduced in the separation process, and the separation is carried out in multiple steps, which still does not solve the above-mentioned problems. Summary of the Invention

[0008] In view of this, the present invention provides a method for removing copper and extracting selenium from copper anode mud with a short process, high element recovery rate, good separation effect and low energy consumption, so as to solve the problems in the prior art of separating elements such as copper and selenium by multiple step-by-step extraction, which has a long process flow, a large amount of reagent input and high requirements on equipment.

[0009] In a first aspect, the present application provides a method for removing copper and extracting selenium from copper anode mud, comprising the following steps:

[0010] Copper-selenium leaching: Copper anode mud, an acidic solution containing sulfate, and an oxidant are mixed to obtain a slurry, which is then leached under ultrasonic conditions at a reaction temperature of 50°C-80°C and an ultrasonic power of 200W-800W to obtain a copper-rich selenium solution and a copper-de-selenium slag. The oxidant is 2KHSO5·KHSO4·K2SO4, which decomposes under the promotion of ultrasound to generate hydrogen peroxide, oxygen, and oxygen free radicals, accelerating the leaching process of copper and selenium. The chemical reaction is as follows:

[0011]

[0012] Cu+H2O2=CuO+H2O

[0013] Se+2H2SO4=SeO2+2H2O+2SO2

[0014] Cu+H2SO4+[O]=CuSO4+H2O

[0015] CuO+H2SO4=CuSO4+H2O

[0016] Cu2Se+3H2SO4+3[O]=2CuSO4+SeO2+SO2+3H2O

[0017] SeO2+H2O=H2SeO3;

[0018] Reduction and selenium extraction: a selenium precipitating agent is added to the copper-rich selenium solution, and a reduction reaction occurs under ultrasonic conditions of a reduction temperature of 30°C-75°C and an ultrasonic power of 150W-600W to precipitate selenium to obtain crude selenium and a copper-rich liquid, wherein the selenium precipitating agent is selected from at least one of hydroxylamine sulfate, hydroxylamine, and hydroxylamine hydrochloride, and the chemical reaction is as follows:

[0019] H2SeO3+2(NH2OH)2·H2SO4=Se↓+2N2↑+7H2O+2H2SO4

[0020] H2SeO3+4NH2OH·HCl=Se↓+2N2↑+7H2O+4HCl

[0021]

[0022] In the present application, the main components of the copper anode mud are Cu 15% to 25%, As 4% to 10%, Sb 3% to 8%, Bi 1% to 6%, Te 1% to 6%, Se 2% to 8%, Au 0.2% to 0.3%, and Ag 5% to 10%.

[0023] Optionally, in copper-selenium leaching, the reaction temperature is independently selected from any value among 50° C., 60° C., 70° C., 80° C., or any range of values ​​between any two of the above points.

[0024] Optionally, in the slurry, the concentration of the oxidant is 6 g / L-61 g / L.

[0025] Optionally, the concentration of the oxidant is independently selected from any value among 6 g / L, 10 g / L, 20 g / L, 30 g / L, 40 g / L, 50 g / L, 61 g / L or any range of values ​​between any two of the above points.

[0026] Optionally, the copper-selenium leaching specifically includes the following steps: mixing copper anode mud and an acidic solution containing sulfate to obtain a first slurry, adding an oxidant to the first slurry, and mixing to obtain the slurry.

[0027] Optionally, the liquid-to-solid ratio of the acidic solution containing sulfate to the copper anode mud is 2:1 mL / g-6:1 mL / g.

[0028] Optionally, the liquid-to-solid ratio of the acidic solution containing sulfate to the copper anode slime is independently selected from any value among 2:1 mL / g, 3:1 mL / g, 4:1 mL / g, 5:1 mL / g, 6:1 mL / g, or any range between any two of the above points.

[0029] Optionally, the acidity of the acidic solution containing sulfate is 150 g / L-350 g / L.

[0030] Optionally, the acidity of the acidic solution containing sulfate is independently selected from any value among 150 g / L, 200 g / L, 250 g / L, 300 g / L, 350 g / L, or any range of values ​​between any two of the above points.

[0031] Specifically, the acidic solution containing sulfate radicals described in the present application is at least one of a sulfuric acid solution and a purified electrolyte solution.

[0032] Among them, the electrolyte purification liquid is a high-acid solution after the copper electrolyte is decoppered, arsenic, antimony and bismuth are decoated, and nickel is decoated, wherein the sulfuric acid concentration in the high-acid solution is 150g / L-350g / L, and a sulfuric acid solution of 150g / L-350g / L can also be used; the electrolyte purification liquid is used to provide acidity, and at the same time, in actual production, waste liquid can be reused to reduce production costs.

[0033] Optionally, the leaching conditions further include: a stirring rate of 300 rpm-500 rpm, and a reaction time of 1 h-3 h.

[0034] Optionally, the amount of the selenium precipitating agent added is 2-4 times the equivalent of the selenium content in the copper-rich selenium solution.

[0035] Optionally, the reduction reaction conditions further include:

[0036] The stirring rate is 300 rpm-500 rpm, and the reduction reaction time is 2 h-4 h.

[0037] In the present application, in the reduction process, the copper-selenium solution uses ultrasound to promote the selective reduction of selenium in the solution with hydroxylamine sulfate, hydroxylamine, or hydroxylamine hydrochloride, and crude selenium powder is obtained by filtration. The copper is completely enriched in the leachate (copper-containing leachate) and can be directly returned to the electrolytic production system.

[0038] Compared with the prior art, the present invention provides at least the following beneficial effects:

[0039] First, the present invention uses only two steps to separate copper and extract selenium from copper anode mud, with a short overall process flow, mild reaction conditions, short processing time, good operating environment, and low energy consumption;

[0040] Second, the ultrasonic-assisted acidic oxidation leaching process achieves 99% leaching rates for both selenium and copper. Selenium and copper are completely removed, resulting in a high enrichment ratio for precious metals, facilitating subsequent purification of precious metals from the leaching residue and achieving good comprehensive recovery benefits.

[0041] Third, the ultrasonic-assisted reduction selenium precipitation process does not require heating, has low energy consumption, and the selenium precipitation agent used does not produce other toxic and harmful gases during the reaction, has little corrosion to equipment, and is safe to operate. The selenium removal rate reaches 99%, and the purity of the recovered selenium reaches more than 96%.

[0042] Of course, any product implementing the present invention does not necessarily need to achieve all of the technical effects described above at the same time.

[0043] Further features and advantages of the present invention will become apparent from the following detailed description of exemplary embodiments of the present invention with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

[0045] Figure 1 It is a flow chart of the present invention. DETAILED DESCRIPTION

[0046] Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that unless otherwise specifically stated, the relative arrangement of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present invention.

[0047] The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.

[0048] Technologies, methods, and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods, and equipment should be considered part of the specification.

[0049] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not limiting. Therefore, other examples of the exemplary embodiments may have different values.

[0050] It should be noted that like reference numerals and letters refer to like items in the following figures, and therefore, once an item is defined in one figure, it need not be further discussed in subsequent figures.

[0051] The method for separating copper and selenium from copper anode mud used in the embodiment is as follows: Figure 1 As shown, the following steps are included:

[0052] (1) Copper and selenium leaching: Copper anode mud is leached with an oxidant and ultrasonic wave, and then filtered to obtain a copper-rich selenium solution and a copper-depleted selenium slag. In the ultrasonic wave-assisted leaching process, the oxidant 2KHSO5·KHSO4·K2SO4 can be decomposed to generate hydrogen peroxide, oxygen and oxygen free radicals under the promotion of ultrasonic wave, thereby accelerating the leaching process of copper and selenium. The main chemical reactions that occur are as follows:

[0053]

[0054] Cu+H2O2=CuO+H2O

[0055] Se+2H2SO4=SeO2+2H2O+2SO2

[0056] Cu+H2SO4+[O]=CuSO4+H2O

[0057] CuO+H2SO4=CuSO4+H2O

[0058] Cu2Se+3H2SO4+3[O]=2CuSO4+SeO2+SO2+3H2O

[0059] SeO2+H2O=H2SeO3;

[0060] (2) Reduction and selenium extraction: The copper-rich selenium solution is passed through a selenium precipitation agent and ultrasonic assisted, and filtered to obtain crude selenium and copper-rich liquid;

[0061] The copper-selenium leaching method specifically includes: mixing copper anode mud with purified electrolyte to obtain slurry, adding oxidant, and ultrasonic-assisted leaching to obtain copper-selenium-rich solution and copper-depleted selenium slag;

[0062] The reduction and selenium extraction process includes: adding a selenium precipitating agent to the copper-rich selenium solution, wherein the amount of the selenium precipitating agent added is 2-4 times the equivalent of the selenium content, applying ultrasonic wave to assist the reaction, and filtering after reduction to obtain crude selenium and copper-rich liquid;

[0063] The main chemical reactions that occur during the reduction process are as follows:

[0064] H2SeO3+2(NH2OH)2·H2SO4=Se↓+2N2↑+7H2O+2H2SO4

[0065] H2SeO3+4NH2OH·HCl=Se↓+2N2↑+7H2O+4HCl

[0066]

[0067] The copper-rich liquid obtained in this method is returned to the copper electrolysis system, the copper-de-selenium slag enters the precious metal extraction system, and the crude selenium enters the selenium refining system.

[0068] The content of each element in the copper anode mud treated in the following examples is shown in Table 1.

[0069] Table 1 Content of each element in copper anode mud (%)

[0070] element Cu As Sb Bi Te Se Au Ag Cl content 18.2 5.49 5.13 2.42 2.78 4.32 0.2518 7.743 0.83

[0071] Example 1

[0072] This embodiment provides a method for removing copper and extracting selenium from copper anode mud. The process is as follows: Figure 1 As shown, the specific steps include:

[0073] (1) 200 g of dried copper anode mud was dissolved in 800 mL of purified electrolyte solution, which was a high-acid solution after copper, arsenic, antimony and bismuth were removed from the copper electrolyte and the nickel was removed. The acidity of the purified electrolyte solution was 250 g / L. The solution was placed in an ultrasonic reactor at 60°C, and an oxidant 2KHSO5·KHSO4·K2SO4 was added. The total amount of the oxidant was 30.5 g. The ultrasonic power was 400 W and the stirring speed was 300 rpm. After reacting for 2 h, the copper-de-selenium slag and the copper-selenium-containing leaching solution were filtered. The copper-de-selenium slag was washed with water, dried and weighed. The slag weighed 153.7 g. The main components of the slag were (%): Cu 0.189, Ag 10.182, Au 0.329, As 0.036, Se 0.051, Te 3.433, Bi 2.961, Sb 6.524. At this time, the copper and selenium leaching rates are 99.2% and 99.1%, respectively, achieving efficient leaching of copper and selenium in the copper anode mud.

[0074] (2) The copper-selenium leaching solution obtained in step (1) was placed in an ultrasonic reactor at 60°C, 53.8g of hydroxylamine sulfate was added, and the stirring speed was set to 300rpm and the ultrasonic power was set to 300W. After 3 hours of reaction, 8.77g of crude selenium and a copper-containing leaching solution were obtained by filtration. The selenium recovery rate was 97.9%, and the purity of the recovered selenium was 96.4%. The contents of various elements in the crude selenium are shown in Table 2. The copper-containing leaching solution was fed to the electrolysis production line for reuse.

[0075] Table 2 Content of each element in crude selenium (%)

[0076] element Se Cu As Sb Bi Te Au Ag content 96.4 0.68 0.05 0.02 0.08 1.14 0.0003 0.0008

[0077] Example 2

[0078] This embodiment provides a method for removing copper and extracting selenium from copper anode mud. The process is as follows: Figure 1 As shown, the specific steps include:

[0079] (1) 200 g of dried copper anode mud was placed in a beaker, and the liquid-solid ratio was controlled to be 3:1 mL / g. The purified electrolyte solution with an acidity of 200 g / L was added (the purified electrolyte solution is a high-acid solution after the copper electrolyte is decoppered, dearsenicized, antimony-bismuthed, and denickeled). The oxidant 2KHSO5·KHSO4·K2SO4 was added, and the total amount of the oxidant added was 61 g. The slurry was placed in an ultrasonic reactor for reaction. The ultrasonic power was set to 800 W, the temperature was set to 80 ° C, and the stirring speed was set to 300 rpm. After the reaction was completed for 2 h, the copper-selenium-containing slag and the copper-selenium-containing leaching solution were filtered. The copper-selenium-containing slag was washed with water, dried and weighed. The slag weighed 149.2 g. The main components of the slag were calculated as the weight percentage of each element (%): Cu 0.053, Ag 10.382, Au 0.338, As 0.331, Se 0.047, Te 3.537, Bi At this time, the copper and selenium leaching rates are 99.8% and 99.2%, respectively, achieving efficient leaching of copper and selenium in copper anode mud.

[0080] (2) The copper-selenium leaching solution obtained in step (1) was placed in an ultrasonic reactor at 70° C., and 71.7 g of hydroxylamine sulfate was slowly and continuously added. The stirring speed was set to 300 rpm and the ultrasonic power was set to 400 W. After reacting for 3 hours, 8.83 g of crude selenium and a copper-containing leaching solution were filtered. The selenium recovery rate was 99.2%, the purity of the recovered selenium was 97.1%, and the contents of various elements in the crude selenium were shown in Table 3. Efficient separation and extraction of selenium was achieved, and the copper-containing leaching solution was fed to the electrolysis production line for reuse.

[0081] Table 3 Content of each element in crude selenium

[0082] element Se Cu As Sb Bi Te Au Ag content 97.1 0.59 0.04 0.03 0.07 0.98 0.0005 0.0007

[0083] Example 3

[0084] This embodiment provides a method for removing copper and extracting selenium from copper anode mud. The process is as follows: Figure 1 As shown, the specific steps include:

[0085] (1) 200 g of dried copper anode mud was placed in a beaker, and the liquid-solid ratio was controlled to be 3:1 mL / g. The purified electrolyte solution with an acidity of 150 g / L was added (the purified electrolyte solution is a high-acid solution after the copper electrolyte is decoppered, dearsenicized, antimony-bismuthed, and denickeled). The oxidant 2KHSO5·KHSO4·K2SO4 was added, and the total amount of the oxidant added was 61 g. The slurry was placed in an ultrasonic reactor for reaction. The ultrasonic power was set to 800 W, the temperature was set to 80 ° C, and the stirring speed was set to 300 rpm. After the reaction was completed for 2 h, the copper-selenium-containing slag and the copper-selenium-containing leaching solution were filtered. The copper-selenium-containing slag was washed with water, dried and weighed. The slag weighed 156.5 g. The main components of the slag were calculated as the weight percentage of each element (%): Cu 0.33, Ag 9.585, Au 0.319, As 0.204, Se 0.066, Te 3.39, Bi At this time, the copper and selenium leaching rates are 98.6% and 98.8%, respectively, achieving efficient leaching of copper and selenium in copper anode mud.

[0086] (2) The copper-selenium leaching solution obtained in step (1) was placed in an ultrasonic reactor at 70° C., and 64.5 g of hydroxylamine sulfate was slowly and continuously added. The stirring speed was set to 300 rpm and the ultrasonic power was set to 400 W. After reacting for 3 hours, 8.84 g of crude selenium and a copper-containing leaching solution were filtered. The selenium recovery rate was 98.7%, the purity of the recovered selenium was 96.5%, and the contents of various elements in the crude selenium were shown in Table 4. Efficient separation and extraction of selenium was achieved, and the copper-containing leaching solution was fed to the electrolysis production line for reuse.

[0087] Table 4 Content of each element in crude selenium

[0088] element Se Cu As Sb Bi Te Au Ag content 96.5 0.87 0.07 0.02 0.05 1.02 0.0008 0.001

[0089] Example 4

[0090] This embodiment provides a method for removing copper and extracting selenium from copper anode mud. The process is as follows: Figure 1 As shown, the specific steps include:

[0091] (1) 200 g of dried copper anode mud was placed in a beaker, and the liquid-solid ratio was controlled to be 3:1 mL / g. The purified electrolyte solution with an acidity of 350 g / L was added (the purified electrolyte solution is a high-acid solution after the copper electrolyte is decoppered, dearsenicized, antimonyized, and bismuthed, and denickeled). The oxidant 2KHSO5·KHSO4·K2SO4 was added, and the total amount of the oxidant added was 53 g. The slurry was placed in an ultrasonic reactor for reaction. The ultrasonic power was set to 800 W, the temperature was set to 80 ° C, and the stirring speed was set to 300 rpm. After the reaction was completed for 2 h, the copper-selenium-containing slag and the copper-selenium-containing leaching solution were filtered. The copper-selenium-containing slag was washed with water, dried, and weighed. The slag weighed 151.2 g. The main components of the slag were calculated as the weight percentage of each element (%): Cu 0.217, Ag 9.921, Au 0.331, As 0.212, Se 0.063, Te 3.51, Bi At this time, the copper and selenium leaching rates are 99.1% and 98.9%, respectively, achieving efficient leaching of copper and selenium in copper anode mud.

[0092] (2) The copper-selenium leaching solution obtained in step (1) was placed in an ultrasonic reactor at 70°C, and 59.2 g of hydroxylamine sulfate was slowly and continuously added. The stirring speed was set to 300 rpm and the ultrasonic power was set to 400 W. After reacting for 3 hours, 8.95 g of crude selenium and a copper-containing leaching solution were filtered. The selenium recovery rate was 99.6%, the purity of the recovered selenium was 96.1%, and the contents of various elements in the crude selenium were shown in Table 5. Efficient separation and extraction of selenium was achieved, and the copper-containing leaching solution was fed to the electrolysis production line for reuse.

[0093] Table 5 Content of each element in crude selenium

[0094] element Se Cu As Sb Bi Te Au Ag content 96.1 0.76 0.10 0.05 0.07 0.83 0.0004 0.0007

[0095] It can be seen from the above examples that the method for removing copper and extracting selenium from copper anode mud provided by the present invention achieves at least the following beneficial effects:

[0096] (1) This embodiment uses only a two-step process to separate copper and extract selenium from copper anode mud. The overall process is short, the reaction conditions are mild, the processing time is short, the operating environment is good, and the energy consumption is low.

[0097] (2) The ultrasonic-assisted acidic oxidation leaching process can achieve a leaching rate of selenium and copper of up to 99%, with complete removal of selenium and copper, a high enrichment ratio of precious metals, and convenient purification of precious metals in the subsequent leaching residue, with good comprehensive recovery benefits; the oxidant used does not produce other ions and does not introduce other impurities;

[0098] (3) The ultrasonic-assisted reduction selenium precipitation process does not require heating and has low energy consumption. The selenium precipitation agent used does not produce other toxic and harmful gases during the reaction, has little corrosion to the equipment, and is safe to operate. The selenium removal rate reaches 99%, and the purity of the recovered selenium reaches more than 96%.

[0099] Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the present invention. It should be understood by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the present invention. The scope of the present invention is defined by the appended claims.

Claims

1. A method for removing copper and extracting selenium from copper anode mud, characterized in that: The following steps are involved: Copper-selenium leaching: Copper anode mud, an acidic solution containing sulfate, and an oxidant are mixed to obtain a slurry, which is then leached under ultrasonic conditions at a reaction temperature of 50°C-80°C and an ultrasonic power of 200W-800W to obtain a copper-rich selenium solution and a copper-de-selenium slag. The oxidant is 2KHSO5·KHSO4·K2SO4. 2KHSO5·KHSO4·K2SO4 decomposes under the promotion of ultrasound to generate hydrogen peroxide, oxygen, and oxygen free radicals, accelerating the leaching process of copper and selenium. The chemical reaction is as follows: Cu+H2O2=CuO+H2O Se+2H2SO4=SeO2+2H2O+2SO2 Cu+H2SO4+[O]=CuSO4+H2O CuO+H2SO4=CuSO4+H2O Cu2Se+3H2SO4+3[O]=2CuSO4+SeO2+SO2+3H2O SeO2+H2O=H2SeO3; Reduction and selenium extraction: a selenium precipitating agent is added to the copper-rich selenium solution, and a reduction reaction occurs under ultrasonic conditions of a reduction temperature of 30°C-75°C and an ultrasonic power of 150W-600W to precipitate selenium to obtain crude selenium and a copper-rich liquid, wherein the selenium precipitating agent is selected from at least one of hydroxylamine sulfate, hydroxylamine, and hydroxylamine hydrochloride, and the chemical reaction is as follows: H2SeO3+2(NH2OH)2·H2SO4=Se↓+2N2↑+7H2O+2H2SO4 H2SeO3+4NH2OH·HCl=Se↓+2N2↑+7H2O+4HCl 2. The method according to claim 1, characterized in that In the slurry, the concentration of the oxidant is 6 g / L-61 g / L.

3. The method according to claim 1, characterized in that The liquid-to-solid ratio of the acidic solution containing sulfate to the copper anode mud is 2:1 mL / g-6:1 mL / g.

4. The method according to claim 1, wherein The acidity of the acidic solution containing sulfate radical is 150 g / L-350 g / L.

5. The method according to claim 1, wherein The leaching conditions also include: The stirring rate is 300 rpm-500 rpm, and the reaction time is 1 h-3 h.

6. The method according to claim 1, characterized in that The amount of the selenium precipitating agent added is 2-4 times the equivalent of the selenium content in the copper-rich selenium solution.

7. The method according to claim 1, characterized in that The conditions of the reduction reaction also include: The stirring rate is 300 rpm-500 rpm, and the reduction reaction time is 2 h-4 h.

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