A method and device for leaching gallium and germanium from zinc leaching residue by using a strong magnetic field and composite ultrasonic

Abstract

The application relates to a method and device for leaching gallium and germanium from zinc leaching residue by using a strong magnetic field and composite ultrasonic waves, which comprises the following steps: S1, drying and grinding zinc powder replacement residue cakes to obtain zinc powder replacement residue powder; S2, mixing the zinc powder replacement residue powder obtained in the step S1 with low-concentration sulfuric acid, sealing, heating, inputting oxygen, stirring, ultrasonic treatment in a magnetic field environment, and filtering to obtain first-stage acid leaching residue and first-stage acid leaching solution; S3, mixing the first-stage acid leaching residue obtained in the step S2 with high-concentration sulfuric acid, sealing, heating, inputting oxygen, stirring, ultrasonic treatment in a magnetic field environment, and filtering to obtain second-stage acid leaching residue and second-stage acid leaching solution; and S4, drying the second-stage acid leaching residue obtained in the step S3 to obtain zinc powder replacement residue for leaching gallium and germanium. Compared with the prior art, the application combines oxygen pressure, ultrasonic waves, a magnetic field and stirring and other process conditions, so that more metal elements are exposed from the inside of the zinc powder replacement residue, and the leaching efficiency is improved.

Description

Technical Field

[0001] This invention relates to the field of metallurgical technology, and in particular to a method and apparatus for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication. Background Technology

[0002] Gallium (Ga) and germanium (Ge) are important strategic resources used in many high-tech fields, such as semiconductors, infrared optics, biomedicine, and catalysts. To date, no independent Ga or Ge ores have been found in nature, but these rare metals can be recovered as byproducts from the metallurgical processes of non-ferrous metal ores, such as zinc, lead, and aluminum mines.

[0003] Zinc concentrate is a typical byproduct of the hydrometallurgical zinc recovery process. It usually contains Zn, SiO2, Cu, Fe and Pb as the main elements, and 0.2-0.5 wt.% Ge and 0.3-0.4 wt.% Ga. Ga and Ge exist in free or bound forms with Fe and SiO2. Ga and Ge are difficult to separate and recover from these compounds. The current industrial process for recovering Ga and Ge from zinc concentrate needs to be optimized, especially since the recovery rate of Ge is very low.

[0004] Common methods for leaching rare metals in 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 ore, Ga and Ge exist in isomorphous, adsorbed, and fine-particle independent mineral forms, with stable chemical properties, making it difficult to effectively leach them using atmospheric pressure acid leaching or pyrometallurgical methods. Ga and Ge are relatively dispersed in zinc leaching residues, making extraction difficult. The form and manner of Ga and Ge's existence, and whether they interact with added reagents, have a significant impact on the ease of extraction of Ga and Ge after leaching. Therefore, there is an urgent need for a method and apparatus to improve the leaching rate of Ga and Ge without being affected by external reagents.

[0005] Studies have shown that the energy generated by a 1T magnetic field is 11.2 J / mol, which is negligible compared to the activation energy of conventional chemical reactions. However, when the magnetic field strength is sufficiently high, reaching tens of T, the interaction energy between the magnetic field and reactant molecules can reach tens of joules, which is sufficient to significantly affect some conventional chemical reactions. Ultrasound is a type of sound wave, belonging to mechanical waves, generated by the high-frequency vibration of matter in a propagation medium. When ultrasound waves of 20–1000 kHz interact with matter, they cause rapid changes in phase, amplitude, etc., leading to alterations in the physicochemical, biological, or state properties of the propagation medium, or accelerating these alterations, resulting in a series of effects such as mechanical, physical-thermal, chemical, electrical, and biological effects. These effects can be generally attributed to three basic actions: thermal effects, mechanical effects, and cavitation effects. Summary of the Invention

[0006] The purpose of this invention is to overcome the defects of the prior art by providing a method and apparatus for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] One of the technical solutions of the present invention is to provide a method for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication, comprising the following steps:

[0009] S1. Dry and grind the zinc powder-displaced slag cake to obtain zinc powder-displaced slag powder;

[0010] S2. The zinc powder replacement slag obtained in step S1 is mixed with low-concentration sulfuric acid and sealed. Under a magnetic field environment, it is heated, oxygen is introduced, and it is stirred and ultrasonicated. After filtration, the first acid leaching slag and the first acid leaching solution are obtained.

[0011] S3. The first acid leaching residue obtained in step S2 is mixed with high-concentration sulfuric acid and sealed. Under a magnetic field environment, it is heated, oxygen is introduced, and it is stirred and ultrasonicated. After filtration, the second acid leaching residue and the second acid leaching solution are obtained.

[0012] S4. Dry the second acid leaching residue obtained in step S3 to obtain zinc powder replacement residue for leaching gallium and germanium.

[0013] Furthermore, in step S2, the concentration of low-concentration sulfuric acid 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).

[0014] Furthermore, in step S3, the concentration of high-concentration sulfuric acid is 200 g / L, and the ratio of high-concentration sulfuric acid to the first stage acid leaching residue is (5 mL: 1 g) to (20 mL: 1 g).

[0015] Furthermore, in steps S2 and S3, the magnetic field strength is 1–40 T; the heating temperature is 0–1000 °C; the oxygen pressure is 0.65 MPa; the stirring speed is 1–2000 r / min; the ultrasonic power is 1–1000 W; and the ultrasonic frequency is 20 kHz.

[0016] The second technical solution of the present invention provides an apparatus for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication. The method for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication, as described in the first technical solution above, includes a reaction apparatus, a stirring device for agitating materials within the reaction apparatus, an ultrasonic device, and a magnetic field generating device for providing a strong magnetic field to the reaction apparatus.

[0017] The reaction apparatus includes a reaction vessel body, a reaction vessel liner disposed within the reaction vessel body, a heating jacket disposed outside the reaction vessel liner, a thermocouple for measuring the temperature of the reaction vessel liner, a pressure sensor probe for measuring the pressure of the reaction vessel liner, and an oxygen valve for purging oxygen.

[0018] The ultrasonic device includes an ultrasonic wire disposed on the inner wall of the reactor liner and an ultrasonic generator connected to the ultrasonic wire.

[0019] 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.

[0020] Furthermore, the stirring device includes a magnetically coupled stirrer, a stirring paddle, and a linkage shaft connecting the magnetically coupled stirrer and the stirring paddle.

[0021] Furthermore, the linkage shaft is also fitted with a shaft protective sleeve and a shaft protective bracket. The shaft protective sleeve directly protects the linkage shaft, providing a certain degree of cushioning when subjected to external impact. The shaft protective bracket provides support for the linkage shaft and protects components mounted on it, such as vacuum seals and test gauges, which are susceptible to sensitivity loss due to external impact.

[0022] Furthermore, the magnetic field generating device includes a superconducting magnet.

[0023] Furthermore, the magnetic field generating device also includes a self-circulating water chiller connected to the superconducting magnet and used for cooling the superconducting magnet.

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

[0025] Furthermore, the ultrasonic device is also connected to an ultrasonic controller, which is used to adjust the ultrasonic power, ultrasonic time, ultrasonic mode, etc.; the magnetically coupled stirrer is also connected to a multi-functional controller, which is used to adjust the stirring speed, stirring time, etc.; the super magnetic conductor is also connected to a magnetic field controller, which is used to adjust the magnetic field strength and detect the magnetic field strength in real time, etc.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) Studies have shown that the energy generated by a 1T magnetic field is 11.2J / mol, which is negligible compared to the activation energy of conventional chemical reactions. However, when the magnetic field strength is sufficiently large, reaching tens of T, the interaction between the magnetic field and reactant molecules can reach tens of joules, which is sufficient to significantly affect some conventional chemical reactions. Therefore, this invention adds a superconducting magnet to the outside of the reaction vessel, so that the zinc powder replacement slag is subjected to Lorentz force, magnetization force, magnetization energy, and magnetic torque under the action of a strong magnetic field. This accelerates the flow of the acid leaching solution, breaks down complex mineral structures, and reduces the solid-liquid interface layer, thereby exposing more metal elements from the inside of the zinc powder replacement slag. Under the action of a magnetic field, both the thermodynamics and kinetics of the reaction are promoted. On the one hand, Fe 2+ It is more easily oxidized to Fe 3+ On the other hand, ZnO, which is paramagnetic under zero field, will transform into ferromagnetic under 12T. The ability of a magnetic field to generate a reaction can change the order and mechanism of the reaction. Under different magnetic field strengths, elements will accumulate at different locations. Therefore, by using a magnetically coupled stirrer to drive the acid leaching solution to be continuously stirred in the reaction vessel, and finally separated by suction filtration, Ga and Ge in the acid leaching residue can be leached efficiently.

[0028] (2) Ultrasound is a type of sound wave, belonging to mechanical waves. It is generated by the vibration of matter at a high frequency in the propagation medium. When ultrasound of 20-1000kHz interacts with matter, it causes rapid changes in phase and amplitude, which in turn causes changes in the physicochemical, biological, or state properties of the propagation medium, or accelerates the process of such changes, resulting in a series of effects such as mechanical, physical-thermal, chemical, electrical, and biological effects. These effects can be generally attributed to the following three basic actions: thermal action, mechanical action, and cavitation action. Compared with the large-scale production of steel enterprises, the recycling and processing of rare and precious metals is significantly smaller, so the application of ultrasound in the recycling of rare and precious metals is also more applicable. On the one hand, ultrasound-assisted enhancement can replace the pretreatment of solid samples. Ultrasound promotes and assists in accelerating some reaction steps, such as dissolution and leaching. On the other hand, ultrasound can improve the leaching rate while shortening the leaching time. Therefore, by first breaking the zinc powder replacement slag with ultrasound, the fine particles mixed in the minerals are exposed, and finally a good leaching effect can be achieved. Based on the above, ultrasonic and magnetic fields are coupled to achieve efficient leaching of Ga and Ge from acid leaching residue.

[0029] (3) The present invention has the advantages of simple equipment, convenient control and low pollution. The present invention adopts the method and device for oxygen pressure leaching of Ga and Ge under magnetic field coupled ultrasonic field, which is suitable for the continuous industrial production of traditional acid leaching of Ga and Ge, and also has certain reference value for the leaching of other elements such as Cu and Fe. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the device for oxygen pressure leaching of Ga and Ge under a magnetic field coupled with an ultrasonic field, as shown in Example 1.

[0031] Figure 2 for Figure 1 Enlarged view of a portion of point a.

[0032] Figure 3 This is a schematic diagram of the vacuum filtration device.

[0033] Figure 4 The leaching rates of Ga and Ge under the same temperature, different magnetic field strengths, and ultrasonic power in Example 1 are given.

[0034] Figure 5 The images show SEM images of the zinc powder replacement slag powder in Example 1 under different magnetic fields and ultrasonic powers. Image a shows the zinc powder replacement slag powder; image b shows the second stage of acid leaching slag powder under a temperature of 250℃, a magnetic field strength of 20T, and an ultrasonic power of 1000W; image c shows the second stage of acid leaching slag powder under a temperature of 250℃, a magnetic field strength of 40T, and an ultrasonic power of 1000W.

[0035] Figure 6The leaching rates of Ga and Ge at different temperatures with the same magnetic field strength and ultrasonic power are shown in Example 1.

[0036] Figure 7 The leaching rates of Ga and Ge in zinc powder replacement slag powder with the same magnetic field strength and ultrasonic power but different mesh sizes in Example 1 are shown at different temperatures.

[0037] Figure 8 This is a schematic diagram of the apparatus for oxygen pressure leaching of Ga and Ge under a magnetic field in Example 2.

[0038] Figure 9 for Figure 8 A magnified view of section b.

[0039] Figure 10 The leaching rates of Ga and Ge at different temperatures under the same magnetic field strength in Example 2 are given.

[0040] Figure 11 The figures show the leaching rates of Ga (Fig. a) and Ge (Fig. b) for different zinc powder replacement slag mesh sizes in Example 2.

[0041] The markings in the image are as follows:

[0042] 1 is the reaction apparatus, 1-1 is the reaction vessel body, 1-2 is the reaction vessel liner, 1-3 is the heating jacket, 1-4 is the thermocouple, 1-5 is the pressure sensor probe, and 1-6 is the oxygen valve.

[0043] 2 is the stirring device, 2-1 is the magnetic coupler, 2-2 is the linkage shaft, 2-3 is the stirring paddle, 2-4 is the shaft protective sleeve, and 2-5 is the shaft protective frame;

[0044] 3 represents the ultrasonic device, 3-1 represents the ultrasonic wire, and 3-2 represents the ultrasonic generator;

[0045] 4 is the magnetic field generating device, 4-1 is the self-circulating water chiller, 4-1-1 is the water inlet, and 4-1-2 is the water outlet;

[0046] 5 is the vacuum filtration device, 5-1 is the funnel, 5-2 is the waste liquid collection bottle, 5-3 is the guide tube, and 5-4 is the vacuum filtration controller. Detailed Implementation

[0047] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0048] 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.

[0049] Example 1:

[0050] like Figure 1-3 The diagram shows a schematic of a device for oxygen pressure leaching of Ga and Ge under a magnetic field coupled with an ultrasonic field. The device includes a reaction apparatus 1, a stirring device 2 for agitating the materials within the reaction apparatus 1, an ultrasonic device 3, a magnetic field generator 4 for providing a strong magnetic field to the reaction apparatus 1, and a filtration device 5. The reaction apparatus 1 includes a reaction vessel body 1-1, a reaction vessel liner 1-2 located within the reaction vessel body 1-1, a heating jacket 1-3 located outside the reaction vessel liner 1-2, a K-type thermocouple 1-4 for measuring the temperature of the reaction vessel liner 1-2, a pressure sensor probe 1-5 for measuring the pressure of the reaction vessel liner 1-2, and an oxygen valve 1-6 for oxygen supply. The reaction vessel liner 1-2 is made of polytetrafluoroethylene (PTFE) or Hastelloy material, both of which are acid-resistant and high-temperature resistant materials. The stirring device 2 includes a magnetically coupled stirrer 2-1, a stirring paddle 2-3, and a linkage shaft 2-2 connecting the magnetically coupled stirrer 2-1 and the stirring paddle 2-3. The linkage shaft 2-2 is also fitted with a shaft protective sleeve 2-4 and a shaft protective frame 2-5. The shaft protective sleeve 2-4 directly protects the linkage shaft 2-2, providing a certain buffering force when subjected to external impact. The shaft protective frame 2-5 provides support for the linkage shaft 2-2 and protects components on the linkage shaft 2-2, such as vacuum seals and test gauges, which are susceptible to sensitivity loss due to external impact. The ultrasonic device 3 includes an ultrasonic wire 3-1 installed on the inner wall of the reactor liner 1-2 and an ultrasonic generator 3-2 connected to the ultrasonic wire 3-1. The magnetic field generating device 4 includes a superconducting magnet and a self-circulating water chiller 4-1 connected to the superconducting magnet and used for cooling the superconducting magnet. The self-circulating water chiller 4-1 includes an inlet 4-1-1 and an outlet 4-1-2. The filtration device 5 includes a funnel 5-1, a waste liquid collection bottle 5-2 sealed to the funnel, a conduit 5-3 provided on the waste liquid collection bottle 5-2, and a filtration controller 5-4 connected to the conduit 5-3.

[0051] The ultrasonic device 3 is also connected to an ultrasonic controller, which is used to adjust the ultrasonic power, ultrasonic time, ultrasonic mode, etc.; the magnetically coupled stirrer 2-1 is also connected to a multi-functional controller, which is used to adjust the stirring speed, stirring time, etc.; the super magnetic conductor is also connected to a magnetic field controller, which is used to adjust the magnetic field strength and detect the magnetic field strength in real time.

[0052] Based on the above apparatus, a method for oxygen pressure leaching of Ga and Ge under a magnetic field coupled with an ultrasonic field is provided, comprising the following steps:

[0053] (1) The zinc powder replacement slag cake was dried in an oven to remove residual moisture and weighed. Simultaneously, the original Ga and Ge contents were measured by ICP, and elemental analysis was performed by SEM and EPMA to observe the distribution of major elements. The main phase composition was observed by XRD. The zinc powder replacement slag cake was then ground to obtain 150-mesh and 400-mesh zinc powders, and the particle size was statistically analyzed using a particle size analyzer.

[0054] (2) Turn on the self-circulating water cooler 4-1 of the superconducting magnet to pre-cool the superconducting magnet. Set the magnetic field strength to 10T, 20T and 40T respectively through the magnetic field controller.

[0055] 30g of zinc powder was placed in the lining 1-2 of the reactor, and 300mL of 20g / L sulfuric acid was added. After sealing, high-purity oxygen at 0.65MPa was introduced, and the pressure was monitored through pressure sensor probe 1-5 to ensure that the pressure reached the predetermined value and that there was no air leakage in the reactor lining 1-2. The heating mantle 1-3 was heated to the predetermined temperatures of 200℃, 250℃, 500℃, and 1000℃, and monitored through K-type thermocouple 1-4. The stirring speed was set to 650r / min using the multi-function controller, and the magnetic coupler stirrer 2-1 was turned on for stirring. The ultrasonic power of the ultrasonic generator 3-2 was set to 300W, 600W, 900W, and 1000W respectively, and the ultrasonic frequency was set to 20kHz using the ultrasonic controller, and the ultrasonic generator 3-2 was turned on. The reaction time was 6 hours. After the reaction is complete, the temperature is lowered to room temperature, and then the oxygen valve 1-6 is slowly opened to restore the normal pressure state of the reactor body 1-1. The mixed solution in the reactor liner 1-2 is taken out and poured into the funnel 5-1 of the suction filtration device 5. The suction filtration controller 5-4 is turned on to remove the air in the waste liquid collection bottle 5-2 through the conduit 5-3, so that the mixed solution in the funnel 5-1 undergoes solid-liquid separation. The first stage of acid leaching solution is collected in the waste liquid collection bottle 5-2, and the first stage of acid leaching residue is collected in the funnel 5-1.

[0056] (3) Weigh the first acid leaching residue and mix it with sulfuric acid with a ratio of 10 mL: 1 g and a concentration of 200 g / L. Repeat step (2) to obtain the second acid leaching solution and the second acid leaching residue.

[0057] (4) The second acid leaching residue is dried and weighed after the moisture is removed. Then it is sent to ICP to measure the residual Ga and Ge content, and then the Ga and Ge leaching rate is calculated.

[0058] like Figure 4Figure 1 shows the leaching rates of Ga (Fig. a) and Ge (Fig. b) at 250℃, different magnetic field strengths, and ultrasonic powers. As can be seen from the figures, under the same magnetic field strength, the leaching rates of both Ga and Ge increase with increasing ultrasonic power; similarly, under the same ultrasonic power, the leaching rates of both Ga and Ge also increase with increasing magnetic field strength, indicating that the leaching rates of both Ga and Ge are directly proportional to both ultrasonic power and magnetic field strength.

[0059] like Figure 5 The images show SEM images of zinc powder replacement slag under different magnetic fields and ultrasonic powers. Image a shows the zinc powder replacement slag, which has a complex morphology and an unclean surface, indicating that the ore did not react and Ga and Ge are still present in the leaching residue. Image b shows the second stage acid leaching residue of the zinc powder replacement slag under a temperature of 250℃, a magnetic field strength of 20T, and an ultrasonic power of 1000W. Image c shows the second stage acid leaching residue of the zinc powder replacement slag under a temperature of 250℃, a magnetic field strength of 40T, and an ultrasonic power of 1000W. The second stage acid leaching residue in both images has a simple particle morphology and a clean surface, indicating that most of the metals in the raw material minerals have reacted and entered the solution. The leaching residue mainly consists of simple particles and clean surfaces. Furthermore, the filter residue under a strong magnetic field of 40T combined with ultrasonic treatment has a finer and more uniform particle size, and the original slag grains are very dense, solid, and large in volume. The results demonstrate the effect of zinc powder replacing slag powder on the crushing of solid materials and the inhibition of solid slag growth under the combined influence of a strong magnetic field and ultrasound. This indicates that ultrasound is highly beneficial in promoting solid-liquid reactions, thus promoting the participation of Ge and other metal elements in the acid leaching reaction and their entry into the solution. Simultaneously, it also shows that the strong magnetic field and ultrasonic field acting on the solid-liquid reaction interface open the inclusions and prevent the hydrolysis of Ge ions and their reverse entry into the slag.

[0060] like Figure 6 As shown, the leaching rates of Ga and Ge at different temperatures under a magnetic field strength of 40T and an ultrasonic power of 900W are as follows. With the increase of temperature, the leaching rates of Ga and Ge show an upward trend. The highest leaching rate of Ga is about 97% at 1000℃, and the highest leaching rate of Ge is about 96% at 1000℃.

[0061] like Figure 7 As shown, under a magnetic field strength of 40T and an ultrasonic power of 900W, the leaching rates of Ga (Fig. a) and Ge (Fig. b) of zinc powder replacement slag with different mesh sizes at different temperatures are as follows: the leaching rates of Ga and Ge in 150 mesh and 400 mesh zinc powder replacement slag are both above 90%.

[0062] In summary, the method and apparatus for oxygen pressure leaching of Ga and Ge from zinc powder replacement slag under a strong magnetic field coupled with an ultrasonic composite field, as described in the above embodiments, adds a strong superconducting magnet to the outside of the reactor and an ultrasonic device to the bottom of the reactor. The zinc powder replacement slag is first broken up by magnetic field and ultrasound, exposing the fine particles mixed in the minerals, and finally achieving a highly efficient leaching effect of Ga and Ge.

[0063] Comparative Example 1:

[0064] It is largely the same as Example 1, except that the ultrasonic device 3 is omitted.

[0065] like Figure 3 , 8 Figure -9 shows a schematic diagram of the apparatus for oxygen pressure leaching of Ga and Ge under a magnetic field. It includes a reaction device 1, a stirring device 2 for agitating the materials within the reaction device 1, a magnetic field generator 4 for providing a strong magnetic field to the reaction device 1, and a filtration device 5. The reaction device 1 includes a reaction vessel body 1-1, a reaction vessel liner 1-2 located within the reaction vessel body 1-1, a heating jacket 1-3 located outside the reaction vessel liner 1-2, a K-type thermocouple 1-4 for measuring the temperature of the reaction vessel liner 1-2, a pressure sensor probe 1-5 for measuring the pressure of the reaction vessel liner 1-2, and an oxygen valve 1-6 for oxygen supply. The reaction vessel liner 1-2 is made of polytetrafluoroethylene (PTFE) or Hastelloy material, both of which are acid-resistant and high-temperature resistant materials. The stirring device 2 includes a magnetically coupled stirrer 2-1, a stirring paddle 2-3, and a linkage shaft 2-2 connecting the magnetically coupled stirrer 2-1 and the stirring paddle 2-3. The linkage shaft 2-2 is also fitted with a shaft protective sleeve 2-4 and a shaft protective frame 2-5. The shaft protective sleeve 2-4 directly protects the linkage shaft 2-2, providing a certain buffering force when subjected to external impact. The shaft protective frame 2-5 provides support for the linkage shaft 2-2 and protects components mounted on the linkage shaft 2-2, such as vacuum seals and test gauges, which are susceptible to sensitivity loss due to external impact. The magnetic field generating device 4 includes a superconducting magnet and a self-circulating water chiller 4-1 connected to the superconducting magnet and used for cooling the superconducting magnet. The self-circulating water chiller 4-1 includes an inlet 4-1-1 and an outlet 4-1-2. The filtration device 5 includes a funnel 5-1, a waste liquid collection bottle 5-2 sealed to the funnel, a conduit 5-3 provided on the waste liquid collection bottle 5-2, and a filtration controller 5-4 connected to the conduit 5-3.

[0066] The magnetically coupled stirrer 2-1 is also connected to a multi-functional controller, which is used to adjust the stirring speed, stirring time, etc.; the super magnetic conductor is also connected to a magnetic field controller, which is used to adjust the magnetic field strength and detect the magnetic field strength in real time.

[0067] Based on the above apparatus, a method for oxygen pressure leaching of Ga and Ge under a magnetic field is provided, comprising the following steps:

[0068] (1) The zinc powder replacement slag cake was dried in an oven to remove residual moisture and weighed. Simultaneously, the original Ga and Ge contents were measured by ICP, and elemental analysis was performed by SEM and EPMA to observe the distribution of major elements. The main phase composition was observed by XRD. The zinc powder replacement slag cake was then ground to obtain 150-mesh and 400-mesh zinc powders, and the particle size was statistically analyzed using a particle size analyzer.

[0069] (2) Turn on the self-circulating water cooler 4-1 of the superconducting magnet to pre-cool the superconducting magnet. Set the magnetic field strength to 10T, 20T and 40T respectively through the magnetic field controller.

[0070] 30g of zinc powder was placed in the lining 1-2 of the reactor, and 300mL of 20g / L sulfuric acid was added. After sealing, high-purity oxygen at 0.65MPa was introduced, and the pressure was monitored through pressure sensor probe 1-5 to ensure that the pressure reached the predetermined value and that there was no air leakage in the reactor lining 1-2. The heating mantle 1-3 was heated to the predetermined temperatures of 200℃, 250℃, 500℃, and 1000℃, and monitored through K-type thermocouple 1-4. The stirring speed was set to 650r / min using the multi-function controller, and the magnetic stirrer 2-1 was turned on for stirring. The reaction time was 6 hours. After the reaction is complete, the temperature is lowered to room temperature, and then the oxygen valve 1-6 is slowly opened to restore the normal pressure state of the reactor body 1-1. The mixed solution in the reactor liner 1-2 is taken out and poured into the funnel 5-1 of the suction filtration device 5. The suction filtration controller 5-4 is turned on to remove the air in the waste liquid collection bottle 5-2 through the conduit 5-3, so that the mixed solution in the funnel 5-1 undergoes solid-liquid separation. The first stage of acid leaching solution is collected in the waste liquid collection bottle 5-2, and the first stage of acid leaching residue is collected in the funnel 5-1.

[0071] (3) Weigh the first acid leaching residue and mix it with sulfuric acid with a ratio of 10 mL: 1 g and a concentration of 200 g / L. Repeat step (2) to obtain the second acid leaching solution and the second acid leaching residue.

[0072] (4) The second acid leaching residue is dried and weighed after the moisture is removed. Then it is sent to ICP to measure the residual Ga and Ge content, and then the Ga and Ge leaching rate is calculated.

[0073] like Figure 10The figure shows the leaching rates of Ga and Ge at 400 mesh under different temperatures and a magnetic field strength of 40T. As can be seen from the figure, the leaching rates of Ga and Ge increase in the reaction temperature range of 200–500℃, and decrease in the reaction temperature range of 500–1000℃. The highest leaching rates are observed at 500℃, approximately 88% and 87% for Ga and Ge, respectively. This is consistent with the leaching rates in Example 1. Figure 6 In comparison, the leaching rates of Ga and Ge without ultrasonic treatment were significantly lower than those with ultrasonic treatment.

[0074] like Figure 11 As shown, under a magnetic field strength of 40T, the leaching rates of Ga (Fig. a) and Ge (Fig. b) of zinc-substituted slag powder with different mesh sizes at different temperatures are obtained. Both 150-mesh and 400-mesh zinc-substituted slag powders can achieve leaching rates of over 80% for Ga and Ge under a magnetic field strength and at temperatures ranging from 200 to 1000°C. This is consistent with Example 1. Figure 7 In comparison, the leaching rates of Ga and Ge without ultrasonic treatment were significantly lower than those with ultrasonic treatment.

[0075] Comparative Example 2:

[0076] The majority of the components are the same as in Example 1, except that the magnetic field generator 4 is omitted.

[0077] like Figure 4 As shown, when the magnetic field strength is 0T, the leaching rates of Ga and Ge are both below 90%, which is lower than the leaching rates under different magnetic field strengths.

[0078] 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 device for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication, characterized in that, It includes a reaction device (1), a stirring device (2) for stirring the materials in the reaction device (1), an ultrasonic device (3), and a magnetic field generator (4) for providing a strong magnetic field to the reaction device (1). The reaction apparatus (1) includes a reaction vessel body (1-1), a reaction vessel liner (1-2) disposed inside the reaction vessel body (1-1), a heating jacket (1-3) disposed outside the reaction vessel liner (1-2), a thermocouple (1-4) for measuring the temperature of the reaction vessel liner (1-2), a pressure sensor probe (1-5) for measuring the pressure of the reaction vessel liner (1-2), and an oxygen valve (1-6) for oxygen supply. The ultrasonic device (3) includes an ultrasonic wire (3-1) disposed on the inner wall of the reactor liner (1-2) and an ultrasonic generator (3-2) connected to the ultrasonic wire (3-1). The process of extracting gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication using the aforementioned apparatus includes the following steps: S1. Dry and grind the zinc powder-displaced slag cake to obtain zinc powder-displaced slag powder; S2. The zinc powder replacement slag obtained in step S1 is mixed with low-concentration sulfuric acid and sealed. Under a magnetic field environment, it is heated, oxygen is introduced, and it is stirred and ultrasonicated. After filtration, the first acid leaching slag and the first acid leaching solution are obtained. S3. The first acid leaching residue obtained in step S2 is mixed with high-concentration sulfuric acid and sealed. Under a magnetic field environment, it is heated, oxygen is introduced, and it is stirred and ultrasonicated. After filtration, the second acid leaching residue and the second acid leaching solution are obtained. S4. Dry the second acid leaching residue obtained in step S3 to obtain zinc powder replacement residue for leaching gallium and germanium. In step S2, the concentration of low-concentration sulfuric acid 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). In step S3, the concentration of high-concentration sulfuric acid is 200 g / L, and the ratio of high-concentration sulfuric acid to the first stage acid leaching residue is (5 mL: 1 g) ~ (20 mL: 1 g). In steps S2 and S3, the magnetic field strength is 1~40 T; the heating temperature is 0~1000℃; the oxygen pressure is 0.65 MPa; the stirring speed is 1~2000 r / min; the ultrasonic power is 1~1000 W; and the ultrasonic frequency is 20 kHz.

2. The apparatus for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication according to claim 1, characterized in that, The stirring device (2) includes a magnetically coupled stirrer (2-1), a stirring paddle (2-3), and a linkage shaft (2-2) connecting the magnetically coupled stirrer (2-1) and the stirring paddle (2-3).

3. The apparatus for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication according to claim 2, characterized in that, The linkage shaft (2-2) is also fitted with a shaft protective sleeve (2-4) and a shaft protective bracket (2-5).

4. The apparatus for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication according to claim 1, characterized in that, The magnetic field generating device (4) includes a superconducting magnet.

5. The apparatus for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication according to claim 4, characterized in that, The magnetic field generating device (4) also includes a self-circulating water chiller (4-1) connected to the superconducting magnet and used for cooling the superconducting magnet.

6. The apparatus for leaching gallium and germanium from zinc leaching residue using a strong magnetic field combined with ultrasonication according to claim 1, characterized in that, The reactor lining (1-2) is made of polytetrafluoroethylene or Hastelloy.

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