Ultrasonic treatment method of high-impurity copper anode slime

Abstract

The application relates to an ultrasonic treatment method of high-impurity copper anode slime. The ultrasonic treatment method is realized through hierarchical ultrasonic strengthening and synergistic leaching. In the first-stage leaching, hydrogen peroxide-oxygen-rich air composite oxidants are combined with ultrasonic cavitation effects to realize efficient oxidation leaching of arsenic, antimony and bismuth; in the second-stage leaching, sulfuric acid-sodium sulfite mixed leaching agents are used to remove harmful impurities such as arsenic, antimony and bismuth under ultrasonic strengthening, and to efficiently enrich valuable metals such as gold, silver, selenium and tellurium, so that the treatment period is shortened, energy consumption and reagent consumption are reduced, resource comprehensive utilization is improved, and the method is suitable for efficient separation and resource recovery of high-impurity copper anode slime containing refractory impurities such as arsenic, antimony and bismuth and valuable metals such as gold, silver, selenium and tellurium.

Description

Technical Field

[0001] This invention belongs to the field of non-ferrous metal hydrometallurgical technology, specifically relating to an ultrasonic treatment method for high-impurity copper anode mud. Background Technology

[0002] Copper anode slime is an important intermediate material in the electrolytic refining of crude copper. It is rich in rare and precious metals such as gold and silver, as well as rare and dispersed metals such as selenium and tellurium, and is a key strategic resource. With the diversification of copper raw materials, its impurity composition has become more complex, with an increase in the content of harmful impurities such as arsenic, antimony, and bismuth, forming high-impurity copper anode slime, which faces many bottlenecks in its treatment.

[0003] Traditional processes such as sulfation and oxidative roasting-sulfuric acid leaching have problems such as poor raw material adaptability, dispersion of valuable metals, low leaching efficiency, and long reaction cycles. Although the existing microwave-pressurized acid leaching combined process improves efficiency, it has poor selectivity for leaching oxide impurities, and the high-pressure operation requires high-performance equipment, consumes a lot of energy, and poses high safety risks. The all-wet step-by-step leaching process is cumbersome, consumes a lot of reagents, and has a low recovery rate of rare and dispersed metals.

[0004] Ultrasonic technology, relying on cavitation, mechanical vibration, and thermal effects, has significant advantages in enhancing leaching, accelerating the process, and reducing reaction severity. It has already been applied in some metallurgical fields. However, there are no reports on specific processes for targeted removal of impurities and efficient enrichment of valuable metals in high-impurity copper anode slime. Developing adaptable, efficient, and environmentally friendly treatment methods has significant industrial application value. Summary of the Invention

[0005] To address the shortcomings of existing processes for treating high-impurity copper anode slime, this invention provides an ultrasonic treatment method. Through staged ultrasonic-enhanced synergistic leaching, harmful impurities such as arsenic, antimony, and bismuth are selectively removed, while valuable metals such as gold, silver, selenium, and tellurium are efficiently enriched. This shortens the treatment cycle, reduces energy and reagent consumption, improves resource utilization, and balances economic efficiency with environmental friendliness.

[0006] This application provides an ultrasonic treatment method for high-impurity copper anode slime, comprising the following steps: (1) The high-pollution copper anode mud is crushed, ball-milled and sieved to obtain fine powder. Deionized water and dilute sulfuric acid are added to the fine powder and the slurry is adjusted to a mass concentration of 15%-25% and pH 1.5-2.5. After stirring evenly, a pretreated slurry is obtained. (2) The pretreated slurry obtained in step (1) is placed into an ultrasonic device, and a composite oxidant is added for primary ultrasonic enhanced oxidation leaching; after the reaction is completed, solid and liquid are separated to obtain primary leachate and primary leach residue. The composite oxidant is a mixture of hydrogen peroxide and oxygen-enriched air; (3) The primary leaching residue obtained in step (2) is mixed with sulfuric acid-sodium sulfite at a liquid-solid ratio of 8-12:1 (mL:g) to obtain a mixed leaching agent and then subjected to secondary ultrasonic-enhanced selective leaching. After the reaction is completed, the solid and liquid are separated to obtain secondary leaching solution and secondary leaching residue. The mass concentration of the mixed leachate is 10%-20%; The sulfuric acid-sodium sulfite mixed leaching agent has a sulfuric acid concentration of 100-200 g / L, a sodium sulfite concentration of 50-80 g / L, and a pH of 1.0-1.5. (4) The pH of the primary leachate was adjusted to 4.5-5.5 with lime milk and stirred at 70-80℃ for 60 min. After neutralization, hydrolysis and filtration, the arsenic-antimony-bismuth composite residue was obtained. The secondary leachate was added with sodium bisulfite and reduced at 50-60℃ for 40-60 min. After filtration, crude selenium powder was obtained. The filtrate was reduced with iron powder to obtain crude tellurium powder. The secondary leachate residue was leached by cyanidation or chlorination to recover gold and silver precious metals.

[0007] Furthermore, in step (2), the composite oxidant is added by first adding hydrogen peroxide and stirring for 30 minutes, and then introducing oxygen-enriched air; the amount of hydrogen peroxide added is 1.2-1.5 times the total molar amount of arsenic, antimony and bismuth in the slurry, and the oxygen-enriched air introduction rate is 0.5-1.0 L / (L·h).

[0008] Furthermore, in step (2), the frequency of the first-stage ultrasonic enhanced oxidation leaching is 8-40kHz, the power is 300-500W, the reaction temperature is 40-60℃, the stirring speed is 200-300r / min, and the reaction time is 60-90min.

[0009] Furthermore, in step (3), the ultrasonic frequency of the secondary ultrasonic-enhanced selective leaching is 60-80kHz, the power is 500-700W, the temperature is 60-80℃, the stirring time is 300-400r / min, and the reaction time is 90-120min.

[0010] Furthermore, in step (3), the concentration of sulfuric acid in the sulfuric acid-sodium sulfite is 100-200 g / L, the concentration of sodium sulfite is 50-80 g / L, and the amount added is 1.1-1.3 times the total molar amount of selenium and tellurium in the slurry.

[0011] Furthermore, in step (1), the high-impregnation copper anode mud contains 800-1300 g / t of gold, 2.5%-6.0% of silver, 7%-15% of copper, 0.5%-6% of nickel, 2.5%-5% of selenium, 1.5%-3% of tellurium, 3%-8% of arsenic, 2%-5% of antimony, and 3%-3% of bismuth.

[0012] Furthermore, the ball milling in step (1) is performed using an air jet mill for 30-60 minutes.

[0013] Furthermore, the fine powder in step (1) has a specific surface area of ​​0.8-1.2 m². 2 / g.

[0014] Furthermore, the neutralization and hydrolysis process in step (4) is as follows: lime milk is added to the primary leachate to adjust the pH value to 4.5-5.5, the temperature is raised to 70-80℃, and the mixture is stirred for 60 minutes to form stable hydroxide or oxide precipitates of arsenic, antimony, and bismuth.

[0015] Furthermore, the reduction process of the secondary leachate in step (4) is as follows: sodium bisulfite is added to the secondary leachate as a reducing agent, the reduction temperature is 50-60℃, the reaction time is 40-60min, and after the reduction is completed, crude selenium powder is obtained by filtration, and iron powder is added to the filtrate to reduce it to obtain crude tellurium powder.

[0016] Beneficial effects 1. High processing efficiency: Through the enhanced effect of graded ultrasonic waves, the entire processing cycle is shortened to 3-4 hours, compared with 6-8 hours of traditional microwave-pressure leaching process, the processing efficiency is improved by more than 50%; 2. Thorough removal of impurities: The removal rate of harmful impurities such as arsenic, antimony, and bismuth all reach over 92%, effectively solving the technical bottleneck of deep separation of impurities in high-impurity copper anode mud, and creating favorable conditions for subsequent precious metal recovery. 3. High recovery rate of valuable metals: The enrichment rate of gold and silver is increased by more than 45%, the selenium recovery rate reaches more than 90%, and the tellurium recovery rate reaches more than 85%, which significantly improves the comprehensive utilization value of resources; 4. Green and economical process: The atmospheric pressure and medium-low temperature reaction conditions reduce equipment investment and energy consumption, and reduce reagent consumption by 20%-30%; impurities are rendered harmless and recycled, and waste emissions meet environmental protection standards, balancing economic efficiency and environmental protection. 5. Strong raw material adaptability: It can process high-impurity copper anode mud with different impurity contents without adjusting the core process parameters, which solves the problem of poor raw material adaptability of traditional processes and has broad industrial application prospects.

[0017] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit this application. Detailed Implementation

[0018] The embodiments of this application will now be described in more detail. While embodiments of this application are shown below, it should be understood that this application can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to make this application more thorough and complete, and to fully convey the scope of this application to those skilled in the art.

[0019] Core principle: 1. Graded Ultrasonic Synergistic Enhancement: The graded mode of "low-frequency ultrasonic enhancement for impurity removal + high-frequency ultrasonic enhancement for valuable metal leaching" is adopted. The strong cavitation effect of low-frequency ultrasonic waves (28-40kHz) can destroy the passivation film on the surface of anode mud particles and promote the reaction of composite oxidant with impurities such as arsenic, antimony, and bismuth. The fine vibration effect of high-frequency ultrasonic waves (60-80kHz) can enhance the selective reaction of leaching agent with selenium and tellurium, improve leaching efficiency and selectivity, and solve the technical problems of low impurity removal and low enrichment rate of valuable metals with single ultrasonic frequency.

[0020] 2. Synergistic design of composite oxidant and leaching agent: The first-stage leaching uses a hydrogen peroxide-oxygen-enriched air composite oxidant, combined with the ultrasonic cavitation effect, to achieve efficient oxidative leaching of arsenic, antimony, and bismuth; the second-stage leaching uses a sulfuric acid-sodium sulfite mixed leaching agent, under ultrasonic enhancement, to selectively leach selenium and tellurium, avoiding the loss of gold and silver, and solving the problem of high dispersion of valuable metals in traditional processes.

[0021] 3. Mild reaction conditions and green process: The entire process is carried out under normal pressure, and the reaction temperature does not exceed 80°C. Compared with high-pressure leaching, it significantly reduces equipment requirements and energy consumption. Through targeted removal of impurities and graded recovery of valuable metals, reagent consumption and waste emissions are reduced.

[0022] Unless otherwise specified, all reagents and materials used in the following examples were purchased from the market.

[0023] The technical solution of this application is as follows: An ultrasonic treatment method for high-impurity copper anode slime includes the following steps: (1) Pretreatment: The high-impurity copper anode mud is crushed, ball-milled, and passed through a 200-300 mesh sieve to obtain fine powder; deionized water is added to adjust the slurry to a mass concentration of 15%-25%, and dilute sulfuric acid is used to adjust the pH to 1.5-2.5, and the mixture is stirred evenly. The raw material contains 800-1300 g / t of gold, 2.5%-6.0% of silver, 7%-15% of copper, 0.5%-6% of nickel, 2.5%-5% of selenium, 1.5%-3% of tellurium, 3%-8% of arsenic, 2%-5% of antimony, and 1%-3% of bismuth. The ball milling is carried out using an air jet mill for 30-60 min, and the specific surface area of ​​the fine powder is 0.8-1.2 m². 2 / g, increasing the contact area for subsequent leaching reactions.

[0024] (2) Primary ultrasonic enhanced oxidative leaching: The pretreated slurry is fed into an ultrasonic reactor and a composite oxidant (a mixture of hydrogen peroxide and oxygen-enriched air) is added. The amount of hydrogen peroxide is 1.2-1.5 times the total molar amount of arsenic, antimony and bismuth.

[0025] The composite oxidant was added as follows: hydrogen peroxide was added first and stirred for 30 minutes before oxygen-enriched air was introduced to avoid a decrease in oxidation efficiency caused by direct mixing of hydrogen peroxide and oxygen-enriched air. The ultrasonic frequency was 28-40 kHz, the power was 300-500 W, and an intermittent working mode (5 minutes on / 1 minute off) was adopted to reduce the impact of local high temperatures generated by ultrasonic cavitation on the stability of the oxidant. The temperature was 40-60℃, the stirring speed was 200-300 r / min, and the reaction time was 60-90 minutes. Solid-liquid separation yielded a primary leachate and a primary leachate residue, which were used for the targeted removal of arsenic, antimony, and bismuth.

[0026] (3) Secondary ultrasonic-enhanced selective leaching: Add sulfuric acid-sodium sulfite mixed leaching agent (sulfuric acid 100-200 g / L, sodium sulfite 50-80 g / L, pH 1.0-1.5) to the primary leaching residue, adjusting the slurry to a mass concentration of 12%-20%. The amount of sodium sulfite added is 1.1-1.3 times the total molar amount of selenium and tellurium in the slurry, ensuring that selenium and tellurium enter the leachate in the form of selenite and tellurite, while simultaneously inhibiting the dissolution of gold and silver. The liquid-solid ratio of the primary leaching residue to the sulfuric acid-sodium sulfite mixed leaching agent is (8-12):1 (mL:g). The ultrasonic frequency is 60-80 kHz, the power is 500-700 W, the temperature is 60-80℃, the stirring rate is 300-400 r / min, and the reaction time is 90-120 min. Solid-liquid separation yields a secondary leachate and a secondary leachate residue, which efficiently leach selenium and tellurium while inhibiting the dissolution of gold and silver.

[0027] (4) Recovery of valuable metals: The pH of the primary leachate is adjusted to 4.5-5.5 with lime milk, and the temperature is raised to 70-80℃. The stirring time is 60 min, and the neutralization and hydrolysis cause arsenic, antimony, and bismuth to form stable hydroxide or oxide precipitates, resulting in arsenic-antimony-bismuth composite slag, achieving harmlessness and resource utilization. Sodium bisulfite (reducing agent) is added to the secondary leachate, and the reduction temperature is 50-60℃, with a reaction time of 40-60 min. After the reaction, the filtrate is filtered to obtain crude selenium powder; the filtrate is reduced with iron powder to obtain crude tellurium powder. The secondary leachate slag is then leached by cyanidation or chlorination to recover gold and silver precious metals.

[0028] The specific implementation plan is as follows: Example 1 (1) Pretreatment: Take the target high-impurity copper anode mud (containing 822.6 g / t of gold, 3.62% of silver, 12.68% of copper, 5.88% of nickel, 3.13% of selenium, 1.669% of tellurium, 5.2% of arsenic, 3.5% of antimony, and 2.1% of bismuth), crush it, and then ball mill it with an air jet mill for 45 min. After passing it through a 250-mesh sieve, a specific surface area of ​​1.0 m² is obtained. 2 / g of anode mud fine powder. Take 100g of this fine powder, add deionized water to adjust the slurry to a mass concentration of 20%, adjust the pH to 2.0 with dilute sulfuric acid, and stir evenly to obtain the pretreated slurry.

[0029] (2) Primary ultrasonic enhanced oxidative leaching: The pretreated slurry was fed into an ultrasonic leaching reactor, and 12 mol / L hydrogen peroxide solution was added (the amount added was 1.3 times the total molar amount of arsenic, antimony, and bismuth). After stirring for 30 min, oxygen-enriched air was introduced at a rate of 0.8 L / (L·h). The ultrasonic equipment was turned on, and the frequency was controlled at 35 kHz and the power at 400 W. The intermittent mode of "working for 5 min and stopping for 1 min" was adopted to maintain the reaction temperature at 50 ℃ and the stirring speed at 250 r / min. After reacting for 75 min, the mixture was filtered to obtain the primary leaching solution and the primary leaching residue. The test results showed that the leaching rates of arsenic, antimony, and bismuth reached 93.5%, 95.2%, and 96.8%, respectively.

[0030] (3) Secondary ultrasonic-enhanced selective leaching: A sulfuric acid-sodium sulfite mixed leaching agent (sulfuric acid concentration 150 g / L, sodium sulfite concentration 65 g / L) was added to the primary leaching residue, and the slurry was adjusted to a mass concentration of 16%. The liquid-to-solid ratio was controlled at 10:1 (mL:g), and the pH was adjusted to 1.2. The slurry was then fed into an ultrasonic leaching reactor. The ultrasonic frequency was set to 70 kHz, the power to 600 W, the reaction temperature to 70 ℃, and the stirring speed to 350 r / min. After reacting for 105 min, the mixture was filtered to obtain the secondary leaching solution and the secondary leaching residue. The results showed that the leaching rates of selenium and tellurium were 91.2% and 86.5%, respectively.

[0031] (4) Recovery of valuable metals: Lime milk was added to the primary leaching solution to adjust the pH to 5.0, the temperature was raised to 75℃ and stirred for 60 min, and the arsenic-antimony-bismuth composite slag was obtained by filtration; Sodium bisulfite (concentration of 120 g / L, 1 ml added) was added to the secondary leaching solution, and the reaction was carried out at 55℃ for 50 min, and the crude selenium powder with a purity of 95.3% was obtained by filtration; 3.5 g of iron powder was added to the filtrate, and the reaction was carried out at 50℃ for 45 min, and the crude tellurium powder with a purity of 94.8% was obtained by filtration; Gold and silver were recovered from the secondary leaching slag by cyanide leaching process, with a gold recovery rate of 99.2% and a silver recovery rate of 99.5%.

[0032] Example 2 (1) Pretreatment: Take high-impurity copper anode mud (gold 880g / t, silver 2.8%, copper 13.5%, nickel 5.6%, selenium 2.7%, tellurium 0.55%, arsenic 3.8%, antimony 2.5%, bismuth 1.5%), crush it, and then ball mill it for 30 min using an air jet mill. Then pass it through a 200-mesh sieve (specific surface area 0.8m²). 2 / g), add deionized water to adjust the slurry concentration to 15%, and adjust the pH to 1.5 with sulfuric acid to obtain the pretreated slurry.

[0033] (2) Primary ultrasonic oxidation leaching: Add hydrogen peroxide (1.2 times the total molar amount of arsenic, antimony, and bismuth), stir for 30 min, and then introduce oxygen-enriched air (0.5 L / (L·h)). Ultrasonic leaching is performed at 28 kHz, 300 W (intermittent mode), 40 °C, and 200 r / min for 60 min. The primary leachate and residue are obtained by filtration. The leaching rates of arsenic, antimony, and bismuth are 92.1%, 93.8%, and 95.5%, respectively.

[0034] (3) Secondary ultrasonic selective leaching: Add sulfuric acid-sodium sulfite mixture (100 g / L sulfuric acid, 50 g / L sodium sulfite) to the primary leaching residue, adjust the slurry to a mass concentration of 12%, liquid-solid ratio of 8:1 (mL:g), and pH 1.0. Ultrasonic reaction at 60 kHz, 500 W, 60 ℃, and 300 r / min for 90 min, filter to obtain secondary leaching solution and residue, with selenium and tellurium leaching rates of 90.3% and 85.2%, respectively.

[0035] (4) Recovery: The pH of the primary leachate was adjusted to 4.5 with lime milk and reacted at 70℃ for 60 min to obtain arsenic-antimony-bismuth residue; the secondary leachate was reduced with sodium bisulfite (concentration of 120 g / L, 1.2 ml added) at 50℃ for 40 min to obtain crude selenium with a purity of 94.5%; 2.9 g of iron powder was added to the filtrate and reduced at 50℃ for 40 min to obtain crude tellurium with a purity of 94.2%; the secondary leachate residue was cyanided and leached, and the gold and silver recovery rates were 99.0% and 99.3%, respectively.

[0036] Example 3 (1) Pretreatment: Take high-impurity copper anode mud containing 1120 g / t gold, 3.9% silver, 12.5% ​​copper, 4.6% nickel, 3.4% selenium, 1.55% tellurium, 7.5% arsenic, 4.8% antimony, and 2.8% bismuth, crush it, and then ball mill it with an air jet mill for 60 min. Then pass it through a 300-mesh sieve (specific surface area 1.2 m²). 2 / g); add deionized water to adjust the slurry to a mass concentration of 25%, and adjust the pH to 2.5 with sulfuric acid to obtain the pretreated slurry.

[0037] (2) Primary ultrasonic oxidation leaching: Add hydrogen peroxide at a total molar amount of arsenic, antimony and bismuth of 1.5 times, stir for 30 min and then introduce oxygen-enriched air at 1.0 L / (L·h); react for 90 min under the conditions of 40 kHz, 500 W ultrasonic (intermittent mode), 60 ℃ and 300 r / min stirring, and filter to obtain primary leachate and residue. The leaching rates of As, Sb and Bi reached 94.2%, 96.5% and 97.3% respectively.

[0038] (3) Secondary ultrasonic selective leaching: Add sulfuric acid (200 g / L)-sodium sulfite (80 g / L) mixture, adjust the slurry to a mass concentration of 20%, liquid-solid ratio of 12:1 (mL:g), and pH 1.5; react for 120 min under ultrasonic conditions of 80 kHz, 700 W, 80 ℃, and 400 r / min stirring, and filter to obtain secondary leachate and residue. The leaching rates of Se and Te are 92.5% and 87.8%, respectively.

[0039] (4) Recovery: The pH of the primary leachate was adjusted to 5.5 with lime milk and reacted at 80℃ for 60 min to obtain arsenic-antimony-bismuth residue; the secondary leachate was reduced with sodium bisulfite (concentration of 120 g / L, added in 1.4 ml) (60℃, 60 min) to obtain crude selenium with a purity of 95.8%; the filtrate was reduced with iron powder 3.6 g (60℃, 50 min) to obtain crude tellurium with a purity of 95.5%; the secondary leachate residue was cyanide leaching, and the recovery rates of Au and Ag reached 99.3% and 99.6%, respectively.

[0040] Comparative Example 1 Using the high-impurity copper anode mud from Example 1 as raw material, a comparative experiment was conducted using the existing microwave-pressure acid leaching process (CN103509953B): microwave acid leaching (2450MHz, 800W, 20min), and pressure acid leaching (1.0MPa, 175℃, 5h). The results showed that the leaching rates of arsenic, antimony, and bismuth were 82.3%, 85.1%, and 88.5%, respectively; the leaching rates of selenium and tellurium were 80.2% and 75.3%, respectively; and the recovery rates of gold and silver were 98.5% and 98.8%, respectively. The processing cycle was 6.5h. Compared with Example 1 of this invention, the impurity leaching rate of this invention is increased by 10-12 percentage points, the selenium and tellurium leaching rates are increased by 10-11 percentage points, and the processing cycle is shortened by 61.5%, which is significantly better than the existing process.

[0041] The various embodiments of this application have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or improvement of the technology in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. An ultrasonic treatment method for high-impurity copper anode mud, characterized in that, Includes the following steps: (1) The high-pollution copper anode mud is crushed, ball-milled and sieved to obtain fine powder. Deionized water and dilute sulfuric acid are added to the fine powder and the slurry is adjusted to a mass concentration of 15%-25% and pH 1.5-2.

5. After stirring evenly, a pretreated slurry is obtained. (2) The pretreated slurry obtained in step (1) is placed into an ultrasonic device, and a composite oxidant is added for primary ultrasonic enhanced oxidation leaching; after the reaction is completed, solid and liquid are separated to obtain primary leachate and primary leach residue. The composite oxidant is a mixture of hydrogen peroxide and oxygen-enriched air; (3) The primary leaching residue obtained in step (2) is mixed with sulfuric acid-sodium sulfite at a liquid-solid ratio of 8-12:1 (mL:g) to obtain a mixed leaching agent and then subjected to secondary ultrasonic-enhanced selective leaching. After the reaction is completed, the solid and liquid are separated to obtain secondary leaching solution and secondary leaching residue. The mass concentration of the mixed leachate is 10%-20%; The sulfuric acid-sodium sulfite mixed leaching agent has a sulfuric acid concentration of 100-200 g / L, a sodium sulfite concentration of 50-80 g / L, and a pH of 1.0-1.

5. (4) The pH of the primary leachate was adjusted to 4.5-5.5 with lime milk, stirred at 70-80℃ for 60 min, and after neutralization, hydrolysis and filtration, arsenic-antimony-bismuth composite residue was obtained. Sodium bisulfite is added to the secondary leachate, and the solution is reduced at 50-60℃ for 40-60 minutes. After filtration, crude selenium powder is obtained. Iron powder is added to the filtrate to reduce it and crude tellurium powder is obtained. The secondary leachate residue is then leached by cyanidation or chlorination to recover gold and silver precious metals.

2. The ultrasonic treatment method according to claim 1, characterized in that, In step (2), the composite oxidant is added by first adding hydrogen peroxide and stirring for 30 minutes, and then introducing oxygen-enriched air. The amount of hydrogen peroxide added is 1.2-1.5 times the total molar amount of arsenic, antimony and bismuth in the slurry, and the oxygen-enriched air introduction rate is 0.5-1.0 L / (L·h).

3. The ultrasonic treatment method according to claim 1, characterized in that, In step (2), the frequency of the first-stage ultrasonic enhanced oxidation leaching is 8-40kHz, the power is 300-500W, the reaction temperature is 40-60℃, the stirring speed is 200-300r / min, and the reaction time is 60-90min.

4. The ultrasonic treatment method according to claim 1, characterized in that, In step (3), the ultrasonic frequency of the secondary ultrasonic-enhanced selective leaching is 60-80kHz, the power is 500-700W, the temperature is 60-80℃, the stirring time is 300-400r / min, and the reaction time is 90-120min.

5. The ultrasonic treatment method according to claim 1, characterized in that, In step (3), the concentration of sulfuric acid in the sulfuric acid-sodium sulfite mixture is 100-200 g / L, the concentration of sodium sulfite is 50-80 g / L, and the amount added is 1.1-1.3 times the total molar amount of selenium and tellurium in the slurry.

6. The ultrasonic treatment method according to claim 1, characterized in that, The high-impurity copper anode mud contains 800-1300g / t of gold, 2.5%-6.0% of silver, 7%-15% of copper, 0.5%-6% of nickel, 2.5%-5% of selenium, 1.5%-3% of tellurium, 3%-8% of arsenic, 2%-5% of antimony, and 3%-3% of bismuth.

7. The ultrasonic treatment method according to claim 1, characterized in that, The ball milling in step (1) is performed using an air jet mill for 30-60 minutes.

8. The ultrasonic treatment method according to claim 1, characterized in that, The fine powder in step (1) has a specific surface area of ​​0.8-1.2 m². 2 / g.

9. The ultrasonic treatment method according to claim 1, characterized in that, The neutralization and hydrolysis process in step (4) is as follows: lime milk is added to the primary leachate to adjust the pH value to 4.5-5.5, the temperature is raised to 70-80℃, and the mixture is stirred for 60 minutes to form stable hydroxide or oxide precipitates of arsenic, antimony, and bismuth.

10. The ultrasonic treatment method according to claim 1, characterized in that, The reduction process of the secondary leachate in step (4) is as follows: sodium bisulfite is added to the secondary leachate as a reducing agent, the reduction temperature is 50-60℃, the reaction time is 40-60min, and after the reduction is completed, crude selenium powder is obtained by filtration, and iron powder is added to the filtrate to reduce it to obtain crude tellurium powder.