A method and apparatus for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement slag.

Abstract

This invention relates to a method and apparatus for ultrasonically enhanced leaching of gallium and germanium from zinc powder replacement slag. The method includes the following steps: S1, drying and grinding the zinc powder replacement slag block into zinc powder replacement slag powder, adding a low-concentration sulfuric acid solution, sealing, introducing oxygen, heating, stirring, ultrasonicating, and filtering to separate a first-stage acid leaching slag and a first-stage acid leaching solution; S2, mixing the first-stage acid leaching slag with a high-concentration sulfuric acid solution, sealing, introducing oxygen, heating, stirring, ultrasonicating, and filtering to separate a second-stage acid leaching slag and a second-stage acid leaching solution; S3, drying the second-stage acid leaching slag to obtain the zinc powder replacement slag from which gallium and germanium are leached. Compared with the prior art, this invention, by combining a series of process conditions such as oxygen pressure, ultrasonication, and stirring, greatly improves the leaching efficiency of gallium and germanium. It also has the advantages of simple equipment, convenient control, and low pollution, making it suitable for traditional continuous industrial production and providing valuable reference for the leaching of other elements.

Description

Technical Field

[0001] This invention relates to the field of metallurgical technology, and in particular to a method and apparatus for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement slag. Background Technology

[0002] Gallium (Ga) and germanium (Ge) are rare dispersed metals. Ge is mainly used in high-tech fields such as infrared optics, aerospace, high-frequency and ultra-high-frequency electronics, fiber optic communication, and solar cells, and also has wide applications in chemical catalysts and biomedicine. Ga and its compounds have been widely used in large-scale integrated circuits, aerospace, and energy.

[0003] The abundance of rare and dispersed metal elements Ga and Ge in the Earth's crust is 10 -6 ~10 -9 At the level of minerals, Ga and Ge are often dispersed in various carriers during geological evolution, making it difficult for them to form independent mineral deposits in nature. Most countries in the world recover Ga and Ge from associated minerals, coal mines, and secondary resources. The mineral distribution of Ga and Ge elements in the Earth's crust is related to the following types of genesis: (1) The ionic radii (atomic radii) of Ga and Ge are similar to those of associated elements, resulting in their co-occurrence in rocks or minerals. (2) Ga and Ge ions replace other ions in the crystal lattice, forming relatively stable compounds. (3) Adsorption occurs in sedimentary rocks. Therefore, Ga and Ge mainly exist in the Earth's crust as isomorphous, adsorbed, and fine-grained independent minerals. Because their electronic configuration, valence, electronegativity, atomic radius, and valence radius are similar to those of elements such as zinc and iron, Ga and Ge mostly occur as isomorphous minerals in sphalerite, earth minerals, and iron ore. Under strong reducing conditions, tetravalent Ge ions are easily reduced to divalent Ge ions, which can then enter the sphalerite lattice and accumulate. Metallic Ga, due to its crystal structure and covalent bonds being highly similar to zinc, is more likely to enter the sphalerite lattice. Therefore, lead-zinc polymetallic sulfide ores are the main raw materials for the industrial extraction of Ga and Ge.

[0004] Common methods for leaching rare metals from minerals include: (1) wet processes: atmospheric pressure acid leaching, high pressure sulfuric acid leaching, sulfuric acid aging, and alkali leaching. (2) pyrometallurgical processes: fumigation volatilization and vacuum distillation. (3) combined pyrometallurgical-wet processes: reduction separation-corrosion and alkali fusion-acid leaching. However, these methods generally suffer from low leaching rates, high requirements for temperature and pH, small processing volumes, high zinc volatilization rates, and difficulties in treating waste residues and used reagents, resulting in environmental pollution. Given the special nature of Ga and Ge in lead-zinc ores, Ga and Ge exist in isomorphous, adsorbed, or fine-particle independent mineral forms, exhibiting stable chemical properties, making them difficult to effectively leach using atmospheric pressure acid leaching or pyrometallurgical methods. The form and manner of Ga and Ge's existence, and whether they interact with added reagents, significantly affect the ease of extraction of Ga and Ge after leaching.

[0005] Ga and Ge are dispersed in zinc leaching residue, making extraction difficult. Studies have shown that ultrasound can effectively increase the leaching rate of Ga and Ge. Ultrasound is a type of sound wave, belonging to mechanical waves, generated by the vibration of matter in a propagation medium at high frequencies, ranging from 20kHz to 1000kHz. It consists of a series of compressed longitudinal waves with alternating compression and rarefaction, and can propagate effectively in media such as gas, liquid, solid, and solid solutions. Due to the interaction between ultrasound and the contact medium, rapid changes in phase and amplitude occur during propagation, causing alterations in the physicochemical, biological, or state properties of the propagation medium. It can also accelerate reaction processes and produce a series of effects, including mechanical, physical-thermal, chemical, electrical, and biological effects. These effects are generally categorized into three basic actions: thermal, mechanical, and cavitation. The application of ultrasound in medicine, military, industry, and agriculture is increasing, bringing more and more breakthroughs and conveniences. Currently, some simple ultrasonic equipment is used in industry for smelting, degassing, purification, waste treatment, deposition, extraction, leaching, catalysis, and synthesis, all with good results.

[0006] Patent CN114032397A discloses a method for ultrasonically enhanced reduction leaching of germanium-containing dust from lead-zinc smelting. This invention involves adding lead-zinc smelting dust to an acid leaching solution to obtain leaching system A, where germanium sulfides, alkali metal germanates, and germanium monoxide are introduced. A reducing agent is then added to leaching system A for reduction leaching to obtain leaching system B, where hexagonal germanium and amorphous germanium dioxide are reduced to germanium monoxide and leached into system B. Leaching system B is then subjected to ultrasonically enhanced reduction leaching to obtain leaching system C, where tetragonal germanium dioxide is reduced to germanium monoxide and leached into system C. Solid-liquid separation is performed in leaching system C to obtain a leachate and a leaching residue, from which germanium is extracted. This invention increases the germanium leaching rate by 20%, reaching over 90%, achieving deep and efficient germanium leaching. However, this invention suffers from drawbacks such as complex operation, demanding conditions, and varying degrees of ultrasonic treatment at different locations in the acid leaching solution, which are unfavorable for industrial production. Summary of the Invention

[0007] The purpose of this invention is to overcome the defects of the prior art by providing a method and apparatus for ultrasonically enhanced leaching of gallium and germanium from zinc powder replacement slag.

[0008] The objective of this invention can be achieved through the following technical solutions:

[0009] One of the technical solutions of the present invention is to provide a method for ultrasonically enhanced leaching of gallium and germanium from zinc powder replacement slag, comprising the following steps:

[0010] S1. The zinc powder replacement slag block is dried and ground into zinc powder replacement slag powder. A low-concentration sulfuric acid solution is added, and after sealing, oxygen is introduced. The mixture is heated, stirred, ultrasonicated, and filtered to separate the first stage of acid leaching slag and the first stage of acid leaching solution.

[0011] S2. Mix the first acid leaching residue obtained in step S1 with a high-concentration sulfuric acid solution, seal it, introduce oxygen, heat, stir, sonicate, and filter to separate the second acid leaching residue and the second acid leaching solution.

[0012] S3. Dry the second acid leaching residue obtained in step S2 to obtain zinc powder replacement residue for leaching gallium and germanium.

[0013] Furthermore, in step S1, the zinc powder replacing the slag powder has a mesh size of 100 to 400 mesh.

[0014] Furthermore, in step S1, the concentration of the low-concentration sulfuric acid solution is 20 g / L, and the ratio of low-concentration sulfuric acid to zinc powder replacing slag powder is (5 mL: 1 g) to (20 mL: 1 g).

[0015] Furthermore, in step S1, the concentration of the high-concentration sulfuric acid solution is 200 g / L, and the ratio of the high-concentration sulfuric acid to the first stage acid leaching residue is (5 mL: 1 g) to (20 mL: 1 g).

[0016] Furthermore, in steps S1 and S2, the oxygen pressure is 0.65 MPa, the heating temperature is 0–1000 °C, and the stirring and ultrasonic reaction time is 1–24 h.

[0017] Furthermore, in steps S1 and S2, the stirring speed is 400–1000 r / min.

[0018] Furthermore, in steps S1 and S2, the ultrasonic power is 1–1000 W and the ultrasonic frequency is 20 kHz.

[0019] The second technical solution of the present invention provides an apparatus for ultrasonically enhanced leaching of gallium and germanium from zinc powder replacement slag, and implements the method for ultrasonically enhanced leaching of gallium and germanium from zinc powder replacement slag as described in the first technical solution above, comprising:

[0020] The reaction apparatus includes a reaction vessel body, a reaction vessel liner disposed within the reaction vessel body, a heating sleeve disposed outside the reaction vessel liner, a thermocouple for monitoring the temperature inside the reaction vessel liner, an oxygen valve for purging oxygen into the reaction vessel liner, and a pressure sensor probe for monitoring the pressure inside the reaction vessel liner.

[0021] A stirring device, used to stir materials placed inside the lining of a reaction vessel;

[0022] An ultrasonic device, comprising an ultrasonic wire disposed on the inner wall of the reactor liner and a plurality of ultrasonic generators connected to the ultrasonic wire.

[0023] The ultrasonic wire is an ultrasonic action device that releases ultrasonic power and ultrasonic frequency transmitted from an ultrasonic generator, acting on the mixed solution that is in direct or indirect contact with the ultrasonic wire.

[0024] Furthermore, the lining of the reactor is made of polytetrafluoroethylene or Hastelloy.

[0025] Furthermore, the stirring device includes a magnetically coupled stirrer, a linkage shaft, and a stirring paddle connected in sequence, with the stirring paddle extending from the top of the reactor body into the reactor liner.

[0026] Furthermore, the magnetically coupled stirrer and pressure sensor probe are both connected to a multi-functional controller, which is used to set pressure thresholds and stirring parameters. The ultrasonic generator is connected to an ultrasonic controller, which is used to adjust ultrasonic power, ultrasonic time, and ultrasonic action mode.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) This invention utilizes the effect of Fe during oxygen pressure leaching. 3+ It is easily hydrolyzed in non-acidic environments, and under high-pressure oxygen conditions, Fe can be hydrolyzed. 3+ Reduced to Fe 2+ Fe enters the gypsum 3+ The reduced content of Ga and Ge, which are isomorphically incorporated into the zinc ferrite lattice, leads to better enrichment and thus improves the leaching rate. Ultrasonic vibrations generated by an ultrasonic device further refine the zinc powder replacement slag, increasing the reaction contact area between the slag and the acid solution, reducing the liquid-solid interface layer, and improving the leaching efficiency of Ga and Ge. Furthermore, a magnetically coupled stirrer at the top of the reactor continuously agitates the acid leaching solution within the reactor. Ultrasonic stimulation first breaks down the zinc powder replacement slag, exposing fine particles embedded in the minerals, ultimately achieving a good leaching effect. Finally, separation is achieved through filtration, thus realizing the efficient leaching of Ga and Ge from the acid leaching slag.

[0029] (2) This invention has the advantages of simple equipment, convenient control and low pollution. It is suitable for continuous industrial production of traditional acid leaching of Ga and Ge, and has certain reference value for the leaching of other elements such as Cu and Fe. Attached Figure Description

[0030] Figure 1 This is a cross-sectional view of the device of the present invention.

[0031] Figure 2 This is a side view of the structure of the generating device and the ultrasonic device in the device of the present invention.

[0032] Figure 3 This is a schematic diagram of the apparatus structure for the filtration section in the method of the present invention.

[0033] Figure 4 The values ​​represent the leaching rates of Ga and Ge under different ultrasonic powers in Example 1.

[0034] Figure 5 The leaching rates of Ga (Fig. a) and Ge (Fig. b) of slag powder replaced by 150-mesh zinc powder were determined with and without ultrasonic treatment.

[0035] Figure 6 The leaching rates of Ga (Fig. a) and Ge (Fig. b) of 400-mesh zinc powder replacing slag powder with and without ultrasonic treatment.

[0036] The markings in the image are as follows:

[0037] 1 is a magnetically coupled stirrer, 2 is a linkage shaft, 3 is a reactor lid, 4 is a thermocouple, 5 is a stirring paddle, 6 is a reactor body, 7 is a heating sleeve, 8 is an ultrasonic wire, 9 is an ultrasonic generator, 10 is a reactor liner, 11 is a vacuum filtration generating bottle, 12 is a filter screen, 13 is a filtrate collection bottle, 14 is a vacuum tube, 15 is a pressure controller, 16 is a multi-functional controller, 17 is a pressure sensor probe, and 18 is an ultrasonic controller. Detailed Implementation

[0038] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0039] In the following embodiments and comparative examples, unless otherwise specified, the raw materials or processing techniques are all conventional commercially available raw materials or conventional processing techniques in the art. Furthermore, unless otherwise specified, the functional components or structures are all conventional components or conventional structures used in the art to achieve the corresponding functions.

[0040] Example 1:

[0041] like Figure 1-3 The diagram shows an apparatus for ultrasonically enhanced leaching of gallium and germanium from zinc powder replacement slag. It includes a reaction unit, a stirring device, an ultrasonic device, and a filtration device connected to the reaction unit. The reaction unit includes a reaction vessel 6, a reaction vessel liner 10 inside the reaction vessel 6, a heating sleeve 7 surrounding the reaction vessel liner 10, a K-type thermocouple 4 inserted through the reaction vessel cover 3 for temperature measurement, an oxygen valve 19 installed in the reaction vessel cover 3 for oxygen supply, and a pressure sensor probe 17 inserted through the reaction vessel cover 3 for pressure measurement. The ultrasonic device includes an ultrasonic wire 8 installed on the inner wall of the reaction vessel liner 10 and several ultrasonic generators 9 connected to the ultrasonic wire 8. The stirring device includes a magnetically coupled stirrer 1, a linkage shaft 2, and a stirring paddle 5 connected in sequence. The stirring paddle 5 extends from the reaction vessel cover 3 into the reaction vessel liner 10. The filtration apparatus includes a filtrate collection bottle 13, a filtration generating bottle 11 mounted on and sealed to the filtrate collection bottle 13, a filter screen 12 positioned between the filtrate collection bottle 13 and the filtration generating bottle 11, a vacuum tube 14 mounted on the filtration generating bottle 11, and a pressure controller 15 connected to the vacuum tube 14. A pressure sensor probe 17 and a magnetically coupled stirrer 1 are connected to a multi-functional controller 16, and an ultrasonic generator 9 is connected to an ultrasonic controller 18. The reactor lining is made of polytetrafluoroethylene (PTFE) or Hastelloy.

[0042] Based on the above apparatus, a method for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement residue is provided, comprising the following steps:

[0043] S1. The zinc powder replacement slag blocks were dried and weighed, and the initial Ga and Ge contents were measured by ICP. Elemental analysis was performed by SEM and EPMA to observe the distribution of major elements, and the main phase composition was observed by XRD. The dried zinc powder replacement slag blocks were ground into 150-mesh and 400-mesh zinc powder replacement slag powders, and the particle size was statistically analyzed using a particle size analyzer. 30g of zinc powder replacement slag was placed in the lining 10 of the reaction vessel, and sulfuric acid solution (20g / L concentration, 300mL) was added. The reaction vessel lid 3 was then sealed, and high-purity oxygen at 0.65MPa was introduced. The pressure was monitored by the pressure sensor probe 17 to ensure that the pressure reached the predetermined value. After confirming that there was no air leakage inside the reaction vessel body 6, the heating sleeve 7 was connected to the power supply for heating, so that the reaction vessel body 6 was heated to the set temperature values ​​(250℃, 500℃, 1000℃). The temperature inside the reaction vessel body 6 was monitored by the K-type thermocouple 4. When the temperature reached the predetermined value, the magnetic stirrer 1 was started by the multi-functional controller 16, and the stirring speed was set to 650r / min. DC power was applied to the ultrasonic controller 18, and the ultrasonic power of the ultrasonic generator 9 was set to 1000W and the ultrasonic frequency to 20kHz. The reaction time was 6 hours. After the predetermined reaction time is over, open the oxygen valve 19 to release the gas. When the pressure reaches 0 MPa, open the reactor lid 3, remove the reactor liner 10, and pour the acid leaching solution after the reaction into the filtration generating bottle 11. Use the pressure controller 15 to provide a negative pressure environment for filtration. Collect the first stage of acid leaching solution in the filtrate collection bottle 13 and collect the first stage of acid leaching residue in the filtration generating bottle 11.

[0044] S2. After crushing the first acid leaching residue into a cake shape, put it back into the reactor liner 10 and mix it with sulfuric acid of 200g / mL concentration. The ratio of the amount used to the first acid leaching residue is 20mL:1g. Repeat the remaining steps of S1 to finally obtain the second acid leaching residue and the second acid leaching solution.

[0045] S3. The second stage acid leaching residue is dried and weighed, and the residual Ga and Ge content is detected by ICP, and then the Ga and Ge leaching rates are calculated.

[0046] Compared with existing technologies, this embodiment improves the leaching rate by adding high-purity oxygen, an ultrasonic device, and a magnetically coupled stirrer. In conventional hydrometallurgical zinc refining, zinc ferrite is formed during the roasting of zinc sulfide concentrate, and Ga and Ge enter the zinc ferrite lattice in an isomorphic manner; however, during oxygen pressure leaching, due to Fe... 3+ It is easily hydrolyzed in non-acidic environments, and under high-pressure oxygen conditions, Fe can be hydrolyzed. 3+ Reduced to Fe 2+ Fe enters the gypsum 3+The reduced content of Ga resulted in better enrichment of Ga, thereby improving the leaching rate. Under the ultrasonic action of an ultrasonic device, the zinc powder replacement slag / powder was ground and broken, exposing the fine particles embedded in the minerals. This increased the contact area with the acid solution and reduced the solid-liquid cross-section, thus improving the leaching efficiency of Ga and Ge. Furthermore, the magnetically coupled stirrer 1 at the top of the reactor body 6 further increased the contact area between the zinc powder replacement slag and the acid solution, and finally, the zinc powder replacement slag and the acid leaching solution were separated by filtration, thereby achieving the leaching of Ga and Ge from the zinc powder replacement slag.

[0047] like Figure 4 As shown, the leaching rates of Ga and Ge under different ultrasonic powers are all above 91% in the range of 0–1000 W. The leaching rate increases with increasing ultrasonic power. This indicates that ultrasound improves the leaching efficiency of Ga and Ge in zinc powder displacement slag.

[0048] like Figure 5 The figures show the leaching rates of Ga (Fig. a) and Ge (Fig. b) of 150-mesh zinc powder-substituted slag powder under ultrasonic treatment (with and without ultrasonic treatment). As can be seen from the figures, the leaching rates of Ga and Ge under ultrasonic treatment and at temperatures ranging from 250℃ to 1000℃ are significantly higher than those under ultrasonic treatment.

[0049] like Figure 6 The figures show the leaching rates of Ga (Fig. a) and Ge (Fig. b) of 400-mesh zinc powder replacing slag powder with and without ultrasonic treatment. As can be seen from the figures, the leaching rates of Ga and Ge under ultrasonic treatment and at temperatures ranging from 250℃ to 1000℃ are significantly higher than those without ultrasonic treatment.

[0050] And according to Figure 5 and Figure 6 This indicates that the method is applicable to zinc powder replacement slag powder with a mesh size of 150 to 400, demonstrating that the method is applicable to a wide range of mesh sizes for zinc powder replacement slag powder.

[0051] Comparative Example 1:

[0052] The majority of the components are the same as in Example 1, except that no ultrasonic device is added.

[0053] An apparatus for leaching gallium and germanium from zinc powder displacement slag includes a reaction device and a stirring device and a filtration device connected to the reaction device. The reaction device includes a reaction vessel 6, a reaction vessel liner 10 disposed inside the reaction vessel 6, a heating sleeve 7 disposed around the reaction vessel liner 10, a K-type thermocouple 4 inserted through the reaction vessel cover 3 for temperature measurement, an oxygen valve 19 disposed on the reaction vessel cover 3 for oxygen supply, and a pressure sensor probe 17 inserted through the reaction vessel cover 3 for pressure measurement. The stirring device includes a magnetically coupled stirrer 1, a linkage shaft 2, and a stirring paddle 5 connected in sequence, with the stirring paddle 5 extending from the reaction vessel cover 3 into the reaction vessel liner 10. The filtration device includes a filtrate collection bottle 13, a filtration generating bottle 11 disposed on and sealed to the filtrate collection bottle 13, a filter screen 12 disposed between the filtrate collection bottle 13 and the filtration generating bottle 11, a vacuum tube 14 disposed on the filtration generating bottle 11, and a pressure controller 15 connected to the vacuum tube 14. The pressure sensor probe 17 and the magnetically coupled stirrer 1 are connected to the multi-function controller 16.

[0054] Based on the above apparatus, a method for leaching gallium and germanium from zinc powder displacement residue is provided, comprising the following steps:

[0055] S1. The zinc powder replaced slag block was dried and weighed, and the initial Ga and Ge contents were measured by ICP. Elemental analysis was performed by SEM and EOMA to observe the distribution of the main elements, and the main phase composition was observed by XRD. The dried zinc powder replacement slag was ground into 150-mesh and 400-mesh zinc powder replacement slag powders. Particle size was analyzed using a particle size analyzer. 30g of each zinc powder replacement slag powder was placed in the liner 10 of the reaction vessel, and sulfuric acid solution (20g / L concentration, 300mL) was added. The reaction vessel lid 3 was then sealed, and high-purity oxygen at 0.65MPa was introduced. The pressure was monitored using a pressure sensor probe 17 to ensure the pressure reached the predetermined value. After confirming there was no air leakage inside the reaction vessel 6, the heating sleeve 7 was connected to the power supply to heat the reaction vessel 6 to the set temperatures (200℃, 500℃, and 1000℃). The temperature inside the reaction vessel 6 was monitored using a K-type thermocouple 4. Once the predetermined temperature was reached, the magnetic stirrer 1 was activated via the multi-functional controller 16 to begin stirring, with the stirring speed set to 650r / min. The reaction time was 6 hours. After the predetermined reaction time is over, open the oxygen valve 19 to release the gas. When the pressure reaches 0 MPa, open the reactor lid 3, remove the reactor liner 10, and pour the acid leaching solution after the reaction into the filtration generating bottle 11. Use the pressure controller 15 to provide a negative pressure environment for filtration. Collect the first stage of acid leaching solution in the filtrate collection bottle 13 and collect the first stage of acid leaching residue in the filtration generating bottle 11.

[0056] S2. After crushing the first acid leaching residue into a cake shape, put it back into the reactor liner 10 and mix it with sulfuric acid of 200g / mL concentration. The ratio of the amount used to the first acid leaching residue is 20mL:1g. Repeat the remaining steps of S1 to finally obtain the second acid leaching residue and the second acid leaching solution.

[0057] S3. The second stage acid leaching residue is dried and weighed, and the residual Ga and Ge content is detected by ICP, and then the Ga and Ge leaching rates are calculated.

[0058] like Figure 5 and 6 As shown, the leaching rates of Ga and Ge are lower under conditions without ultrasound than under conditions with ultrasound.

[0059] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement slag, characterized in that, The following apparatus is used, the apparatus comprising: The reaction apparatus includes a reaction vessel body (6), a reaction vessel liner (10) disposed inside the reaction vessel body (6), a heating sleeve (7) disposed outside the reaction vessel liner (10), a thermocouple (4) for monitoring the temperature inside the reaction vessel liner (10), an oxygen valve (19) for purging oxygen into the reaction vessel liner (10), and a pressure sensor probe (17) for monitoring the pressure inside the reaction vessel liner (10). A stirring device for stirring materials placed inside the liner (10) of a reactor; An ultrasonic device, comprising an ultrasonic wire (8) disposed on the inner wall of the reactor liner (10) and a plurality of ultrasonic generators (9) connected to the ultrasonic wire (8). The method includes the following steps: S1. The zinc powder replacement slag block is dried and ground into zinc powder replacement slag powder. A low-concentration sulfuric acid solution is added, and after sealing, oxygen is introduced. The mixture is heated, stirred, ultrasonicated, and filtered to separate the first stage of acid leaching slag and the first stage of acid leaching solution. The concentration of the low-concentration sulfuric acid solution is 20 g / L, and the ratio of low-concentration sulfuric acid to zinc powder replacing slag powder is (5 mL: 1 g) ~ (20 mL: 1 g). S2. Mix the first acid leaching residue obtained in step S1 with a high-concentration sulfuric acid solution, seal it, introduce oxygen, heat, stir, sonicate, and filter to separate the second acid leaching residue and the second acid leaching solution. The concentration of the high-concentration sulfuric acid solution is 200 g / L, and the ratio of the high-concentration sulfuric acid to the first stage acid leaching residue is (5 mL: 1 g) ~ (20 mL: 1 g). S3. Dry the second acid leaching residue obtained in step S2 to obtain zinc powder replacement residue for leaching gallium and germanium. In steps S1 and S2, the oxygen pressure is 0.65 MPa, the heating temperature is 250~1000℃, and the stirring and ultrasonic reaction time is 1~24 h.

2. The method for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement slag according to claim 1, characterized in that, In step S1, the zinc powder replacing the slag powder has a mesh size of 100~400 mesh.

3. The method for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement slag according to claim 1, characterized in that, In steps S1 and S2, the stirring speed is 400~1000 r / min.

4. The method for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement slag according to claim 1, characterized in that, In steps S1 and S2, the ultrasonic power is 1~1000 W and the ultrasonic frequency is 20 kHz.

5. The method for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement slag according to claim 1, characterized in that, The reactor liner (10) is made of polytetrafluoroethylene or Hastelloy.

6. The method for ultrasonically enhanced leaching of gallium and germanium from zinc powder displacement slag according to claim 1, characterized in that, The stirring device includes a magnetically coupled stirrer (1), a linkage shaft (2) and a stirring paddle (5) connected in sequence. The stirring paddle (5) extends from the top of the reactor body (6) into the reactor liner (10).

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