Method for synergistically recovering gallium, germanium and indium and synchronously removing iron by constructing goethite nano composite material in situ based on ultrasonic waves

Abstract

The invention relates to a method for synergistically recovering gallium, germanium and indium and synchronously removing iron based on ultrasonic in-situ construction of a goethite nanocomposite, and belongs to the technical field of hydrometallurgy and industrial wastewater treatment. In order to solve the problem of efficiently and synchronously recovering scattered metal from an acid solution, the method comprises the following steps: under the action of an ultrasonic external field, adding an oxidizing agent into the acid solution containing Fe < 2 + >, Ga < 3 + >, Ge < 4 + > and In < 3 + >, adding a neutralizing agent at the same time, and accurately controlling the pH value of a reaction system within a range of 2.0-4.0 to oxidize Fe < 2 + > and promote iron to precipitate in a goethite (alpha-FeOOH) form; and gallium, germanium and indium in the solution are efficiently coprecipitated or adsorbed in the formed goethite carrier. According to the method, the traditional precipitation process is converted into in-situ defect engineering through the ultrasonic cavitation effect, mass transfer and reaction kinetics are remarkably enhanced, synergistic efficient recovery with the precipitation rates of iron, gallium, germanium and indium exceeding 99% is achieved, and the goethite-based nanocomposite rich in target metal and high in specific surface area is obtained.

Description

TECHNICAL FIELD

[0001] The application relates to a method for in-situ construction of goethite nanocomposites based on ultrasonic waves to cooperatively recover gallium, germanium and indium and simultaneously remove iron, and belongs to the technical fields of hydrometallurgy and industrial wastewater treatment. BACKGROUND

[0002] Gallium (Ga), germanium (Ge) and indium (In) are key rare metals, which are indispensable core materials for semiconductors, new-generation information technology, new energy and national defense industry. With the rapid development of high-tech industries, the demand for these metals continues to rise, however, their natural independent deposits are rare, and they mainly exist as associated components in bulk metal sulfide ores such as zinc, aluminum and lead, and are enriched in various component zinc sulfate solutions during the hydrometallurgical process. Therefore, efficient and economical recovery of these trace elements from secondary resources is of great significance to guarantee national resource security and supply chain stability.

[0003] Currently, the conventional methods for recovering gallium, germanium and indium from zinc sulfate solution mainly include solvent extraction, neutralization hydrolysis and tannin precipitation. Although solvent extraction has high selectivity for specific ions, the process is lengthy, and the direct extraction efficiency and kinetics of very low concentration ions are often poor. The neutralization hydrolysis method is rapid and has low investment, but has poor selectivity, resulting in low product grade and large amount of slag. The tannin precipitation method has strong selectivity for germanium, but is almost ineffective for Ga 3+ and In 3+ , and cannot achieve the cooperative recovery of multiple metals. These methods cannot fundamentally solve the problem of simultaneous, efficient and green recovery of multiple metals.

[0004] Goethite method (alpha-FeOOH) as a mature wet iron removal technology shows unique application potential. This method not only effectively removes iron, but also co-precipitates various cations and oxygen-containing anions in the solution through surface adsorption, chemical combination and even isomorphism replacement. This method has the ability to treat waste with waste and cooperatively recover multiple valuable metals. The existing literature records that the goethite method process is relatively simple, the reagent cost is low, and multiple impurities can be removed at the same time. However, the traditional goethite process has slow precipitation rate, coarse crystal growth, and easy wrapping or entraining impurities on the macro level, which limits the capture efficiency of trace metals and makes it unstable. On the micro level, the capture mechanism of different forms of metals is not clear, and the relationship between the carrier structure and the occurrence state of the target metal lacks systematic explanation, which leads to the lack of theoretical guidance for process control, and it is difficult to achieve the cooperative optimization of Ga, Ge and In three metals with different chemical properties. The existing technology focuses on the removal or recovery of a single or similar type of metal using goethite, and there is still a lack of effective solutions to the problem of cooperative recovery of complex systems such as Ga, Ge and In coexisting cations. SUMMARY

[0005] In order to solve the problem of efficient and simultaneous recovery of scattered metals from an acidic solution, the application provides a method for in-situ construction of goethite nanocomposite materials based on ultrasonic waves to cooperatively recover gallium, germanium and indium and simultaneously remove iron, the ultrasonic wave strengthens the goethite cooperative precipitation process, realizes efficient co-precipitation of the four-element system of iron, gallium, germanium and indium, drives the traditional precipitation reaction to a defect engineering strategy through an ultrasonic field, and in-situ constructs goethite-based composite adsorption materials with specific nanostructures and high surface activity at the same time of reaction; the strengthening mechanism of the ultrasonic wave and the capture form of the metal are systematically clarified from the macro-morphology and microstructure, so as to provide a solid theoretical and technical foundation for developing a new efficient, cooperative and controllable strategic metal recovery technology.

[0006] A method for in-situ construction of goethite nanocomposite materials based on ultrasonic waves to cooperatively recover gallium, germanium and indium and simultaneously remove iron, and the specific steps are as follows: Under the ultrasonic field and at a temperature of 313-368K, a slow micro-excess oxidizing agent is added to an acidic solution containing Fe 2+ , Ga 3+ , Ge 4+ and In 3+ to control the Fe 3+ concentration in the reaction system, and at the same time, a neutralizing agent is added to control the pH value of the reaction system to be 2.0-4.0 to make iron directional crystallization precipitate in the form of goethite, and at the same time, make gallium, germanium and indium co-precipitate or be adsorbed by goethite in the adsorption system during the precipitation process, solid-liquid separation is performed, and goethite nanocrystal composite materials are obtained.

[0007] Preferably, the acidic solution containing Fe 2+ , Ga 3+ , Ge 4+ and In 3+ contains zinc 120-150 g / L, iron 8-15 g / L, gallium 1-100 mg / L, germanium 1-100 mg / L and indium 50-200 mg / L.

[0008] Preferably, the ultrasonic wave frequency is 15-25 kHz, and the output power is 40-200 W.

[0009] Preferably, the oxidizing agent is one or more of oxygen, potassium permanganate, dichromate, manganese dioxide and hydrogen peroxide.

[0010] More preferably, the addition rate of the oxidizing agent is controlled to be lower than 1 g / L of the Fe 3+ concentration in the reaction system.

[0011] Preferably, the neutralizing agent is calcium oxide, zinc oxide, calcium hydroxide, sodium hydroxide, sodium carbonate, calcium carbonate, ammonium carbonate, potassium carbonate, ammonium bicarbonate or sodium bicarbonate.

[0012] Preferably, the neutralizing agent is calcium oxide, zinc oxide, calcium hydroxide, sodium hydroxide, sodium carbonate, calcium carbonate, ammonium carbonate, potassium carbonate, ammonium bicarbonate or sodium bicarbonate.

[0013] The present application is based on the principle of in-situ construction of goethite nanocomposites by ultrasonic waves to cooperatively recover gallium, germanium and indium and simultaneously remove iron: the process of cavitation bubble generation and its violent collapse in the solution is accompanied by the generation of transient extreme temperature and pressure, strong micro-jet and high activity free radicals, thereby remodeling the traditional goethite precipitation path from two levels of physical transport and chemical reaction; in the physical level, the cavitation micro-jet completely destroys the mass transfer boundary layer, so that Fe 2+ , Ga 3+ , Ge 4+ and In 3+ can be transported at high speed to the reaction interface. In the chemical level, a large number of hydroxyl radicals (·OH) are generated by the cleavage of water and hydrogen peroxide under cavitation, which provides a rapid oxidation power far beyond the conventional route (H2O + ·OH → ·OH + ·H, H2O2 + ·OH → 2·OH), thereby realizing efficient and uniform oxidation of Fe 2+ (Fe 2+ + ·OH → Fe 3+ + OH - ); this rapid and uniform oxidation hydrolysis promotes the instantaneous homogeneous nucleation of goethite (α-FeOOH), while the mechanical stress and micro-jet generated by cavitation inhibit the normal growth and ripening of the crystal, and instead induce a large number of lattice distortions and surface defects; the constructed nanometer goethite material rich in defects, high specific surface area and high surface hydroxyl density provides a carrier for multi-metal cooperative capture; for Ga 3+ , it is fixed by rapid combination with Fe 3+ sites on the surface of the carrier. For Ge 4+ existing in the form of Ge(OH)4, it forms stable Ge-O-Fe chemical bonds with the high-activity Fe-OH sites on the surface of the carrier. For In 3+ , the shortened diffusion path and abundant defect adsorption sites promote its surface hydrolysis and precipitation. Therefore, the ultrasonic field converts the traditional precipitation into a defect engineering for in-situ synthesis of functional materials, and finally realizes the near complete and simultaneous efficient recovery of iron, gallium, germanium and indium on a macroscopic scale.

[0014] The beneficial effects of the present application are: (1) The present application can realize the simultaneous and efficient precipitation of iron, gallium, germanium and indium under an ultrasonic external field, with a precipitation rate of more than 99%, solving the problem of difficult simultaneous and efficient recovery by traditional methods; (2) The cavitation effect of ultrasonic waves in the present application greatly accelerates the Fe 2+oxidation kinetics and Fe 3+ hydrolysis, nucleation process, shortens the reaction time, reduces the apparent activation energy; the process does not need to add specific organic extractant or precipitant, and is environment-friendly; (3) The present application is not simply waste slag removal, but through ultrasonic guided in-situ reaction, the traditional goethite precipitation process is changed into a defect engineering strategy, and a goethite-based nanocomposite material rich in lattice defects, high specific surface area and high surface activity is actively constructed; the target metal (Ga, Ge, In) is highly enriched in the carrier in the form of surface complexation, adsorption or trace solid solution, forming an intermediate product easy to separate and purify or directly resource utilization. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 SEM of the nanometer needle-shaped goethite-based composite material of Example 1; Figure 2 Mass spectrum of the nanometer needle-shaped goethite-based composite material of Example 1; Figure 3 BET graph of the nanometer needle-shaped goethite-based composite material of Example 1; Figure 4 XRD graph of the nanometer needle-shaped goethite-based composite material of Example 1 and Comparative Example 1; Figure 5 FT-RI graph of the nanometer needle-shaped goethite-based composite material of Example 1 and Comparative Example 1; Figure 6 SEM of the nanometer needle-shaped goethite-based composite material of Comparative Example 1; Figure 7 Mass spectrum of the nanometer needle-shaped goethite-based composite material of Comparative Example 1; Figure 8 BET graph of the nanometer needle-shaped goethite-based composite material of Comparative Example 1. DETAILED DESCRIPTION

[0016] The present application will be further described in conjunction with specific embodiments, but the protection scope of the present application is not limited to the described content.

[0017] Example 1: The acidic solution in this embodiment contains Zn 130 g / L, Fe(II) 10 g / L, Ga 0.1 g / L, Ge 0.1 g / L, In 0.2 g / L; A method for constructing goethite nanocomposite material in-situ based on ultrasonic wave to cooperatively recover gallium, germanium and indium and simultaneously remove iron, the specific steps are as follows: Under the ultrasonic field (frequency 20 kHz, output power 160 W), at a temperature of 358 K, Fe 2+ , Ga 3+ , Ge4+ and In 3+ A slow micro-excess of oxidizing agent (H2O2 solution with a concentration of 6wt.%, 1.2 times of the theoretical amount required for oxidizing Fe(II)) in the acidic solution of Fe(II) and In 3+ concentration of 0.05-0.06 g / L, and a neutralizer (slowly adding a 9 g / L ZnO suspension) is added to control the pH value of the reaction system to 3.5, so that iron is precipitated in the form of goethite, and gallium, germanium and indium are co-precipitated or adsorbed on the goethite in the system, followed by solid-liquid separation and drying of the solid to obtain the goethite nanocrystal composite material; The contents of Fe, Ga, Ge and In in the filtrate of the example are analyzed, and the precipitation rates of Fe, Ga, Ge and In are calculated to be 99.92%, 99.90%, 99.94% and 99.95%, respectively; The goethite nanocrystal composite material of the example is characterized, and the SEM image, mass spectrum, BET image, XRD image and FT-RI image are shown in Figures 1-5 As can be seen from the figures, under the action of the ultrasonic field, the phase, morphology and surface properties of the precipitate slag are synergistically transformed, which constitutes the core of the mechanism of efficient synergistic capture of metals; XRD and FT-IR analysis confirm that the precipitate is pure goethite phase without independent phases of target metals, and a Ge-O-Fe chemical bond characteristic peak appears at 983 cm -1 , indicating that Ge 4+ is firmly fixed by surface complexation; SEM and AFM show that the precipitate is composed of uniformly dispersed nanoparticles, forming a high-roughness, porous sponge-like three-dimensional structure. This structure is derived from the ultrasonic cavitation effect, which promotes the uniform nucleation of Fe 3+ and inhibits the excessive growth and agglomeration of particles; thus, the specific surface area (24.9 m 2 / g) and surface active site density of the carrier are greatly increased; the high-activity and high-accessibility nanostructure greatly promotes the rapid surface binding of Ga 3+ , efficient mass transfer and chemical bonding of Ge(OH)4 molecules, and diffusion and precipitation of In 3+ , and finally realizes the high-capacity, uniform and stable enrichment of the three metals on the surface of the carrier at the micro level.

[0018] Comparative Example 1: The difference from Example 1 is that there is no ultrasonic field, and only a conventional goethite precipitation reaction is performed; The precipitation rates of Fe, Ga, Ge and In of the comparative example are 94.22%, 96.60%, 96.13% and 95.96%, respectively; the XRD image, FT-RI image, SEM image, mass spectrum and BET image of the goethite slag of the comparative example are shown in Figures 4-8As can be seen from the figure, the conventional precipitation process is controlled by slow mass transfer and natural crystallization, the product presents dense agglomerates of impurity phase, the precipitate particles are coarse, the specific surface area is only 10.5 m 2 / g, the surface is smooth and the active sites are scarce, which seriously limits the diffusion of reactants and surface reaction, and the capture of metals mainly depends on limited physical adsorption, resulting in Ga 3+ , Ge(OH)4 molecules and In 3+ are difficult to be effectively fixed due to mass transfer resistance and insufficient active sites, and the overall synergistic recovery efficiency is bottlenecked; it is proved that the ultrasonic field has a significant effect on improving the precipitation efficiency and changing the product properties.

[0019] In this embodiment, the acidic solution contains Zn 130 g / L, Fe(II) 10 g / L, Ga 0.1 g / L, Ge 0.1 g / L, and In 0.2 g / L; A method for in-situ construction of goethite nanocomposite to synergistically recover gallium, germanium and indium and simultaneously remove iron based on ultrasonic waves, the specific steps are as follows: Under the ultrasonic field (frequency 20 kHz, output power 140 W) and at a temperature of 358 K, a slow micro-excess oxidizing agent (1 wt.% potassium permanganate solution, 1.25 times the theoretical amount required to oxidize Fe(II)) is added to the acidic solution containing Fe 2+ , Ga 3+ , Ge 4+ and In 3+ to control the Fe 3+ concentration in the reaction system to be 0.04-0.05 g / L, and at the same time, a neutralizing agent (7 g / L calcium oxide suspension is slowly added) is added to control the pH value of the reaction system to be 3.5 to make iron directional crystallization precipitate in the form of goethite, and at the same time, gallium, germanium and indium in the system are co-precipitated or adsorbed on goethite during the precipitation process, solid-liquid separation, and drying of the solid to obtain goethite nanocrystal composite material; The contents of iron, gallium, germanium and indium in the filtrate of this embodiment are analyzed, and the precipitation rates of Fe, Ga, Ge and In are calculated to be 99.76%, 99.82%, 99.14% and 99.01%, respectively; The goethite nanocrystal composite material of this embodiment is composed of uniformly dispersed nanoparticles, forming a high-roughness, porous sponge-like three-dimensional structure, and the ultrasonic cavitation effect promotes the uniform nucleation of Fe 3+ , and at the same time inhibits the excessive growth and agglomeration of particles; the high-activity and high-accessibility nanometer structure greatly promotes the rapid surface binding of Ga 3+ , the efficient mass transfer and chemical bonding of Ge(OH)4 molecules, and the diffusion and precipitation of In 3+ , and finally realizes the high-capacity, uniform and stable enrichment of the three metals on the surface of the carrier on a micro scale.

[0020] Example 3: The acidic solution in this example contains Zn 130 g / L, Fe(II) 10 g / L, Ga 0.1 g / L, Ge 0.1 g / L, In 0.2 g / L; A method for in-situ construction of goethite nanocomposite materials based on ultrasonic waves to cooperatively recover gallium, germanium, and indium and simultaneously remove iron, the specific steps being as follows: Under ultrasonic field (frequency 20 kHz, output power 180 W) and temperature 358 K, oxygen is slowly introduced into the acidic solution containing Fe 2+ , Ga 3+ , Ge 4+ , and In 3+ to control the Fe 3+ concentration in the reaction system to be 0.07-0.08 g / L, and a neutralizing agent (concentration 3 mol / L sodium hydroxide solution is slowly added) is added to control the pH value of the reaction system to be 2.5 to make iron precipitate in the form of goethite, and make gallium, germanium, and indium co-precipitate or be adsorbed by goethite in the precipitation process, solid-liquid separation, and drying of the solid to obtain goethite nanocrystal composite material; The contents of iron, gallium, germanium, and indium in the filtrate of this example are analyzed, and the precipitation rates of Fe, Ga, Ge, and In are calculated to be 99.81%, 99.34%, 99.50%, and 99.26%, respectively; The goethite nanocrystal composite material of this example is composed of uniformly dispersed nanoparticles, forms a high-roughness, porous sponge-like three-dimensional structure, and the ultrasonic cavitation effect promotes the uniform nucleation of Fe 3+ and simultaneously inhibits the excessive growth and agglomeration of particles; the high-activity and high-accessibility nanometer structure greatly promotes the rapid surface combination of Ga 3+ , efficient mass transfer and chemical bonding of Ge(OH)4 molecules, and diffusion and precipitation of In 3+ , and finally realizes high-capacity, uniform, and stable enrichment of the three metals on the surface of the carrier on a micro scale.

[0021] Example 4: The acidic solution in this example contains Zn 130 g / L, Fe(II) 10 g / L, Ga 0.1 g / L, Ge 0.1 g / L, In 0.2 g / L; A method for in-situ construction of goethite nanocomposite materials based on ultrasonic waves to cooperatively recover gallium, germanium, and indium and simultaneously remove iron, the specific steps being as follows: Under ultrasonic field (frequency 20 kHz, output power 200 W) and temperature 358 K, oxygen is slowly introduced into the acidic solution containing Fe 2+ , Ga 3+ , Ge 4+ , and In 3+a slow micro-excess of oxidizing agent (a 1.2wt.% potassium dichromate solution, 1.3 times the theoretical amount required to oxidize Fe(II)) in the acidic solution to control the Fe 3+ concentration of 0.03-0.04 g / L, and a neutralizing agent (slowly added 6 g / L calcium carbonate suspension) was added to control the pH value of the reaction system to 3.0 to make iron precipitate in the form of goethite, and make gallium, germanium and indium co-precipitate or be adsorbed by goethite in the system during precipitation, and then the solid-liquid separation was performed, and the goethite nanocrystal composite material was obtained after drying the solid; The contents of iron, gallium, germanium and indium in the filtrate were analyzed, and the precipitation rates of Fe, Ga, Ge and In were calculated to be 99.32%, 99.18%, 99.06% and 98.86%, respectively. The goethite nanocrystal composite material of the example is composed of uniformly dispersed nanoparticles, forms a high-roughness, porous sponge-like three-dimensional structure, and the ultrasonic cavitation effect promotes the uniform nucleation of Fe 3+ , and inhibits the excessive growth and agglomeration of particles; the high-activity and high-accessibility nanostructure greatly promotes the rapid surface combination of Ga 3+ , the efficient mass transfer and chemical bonding of Ge(OH)4 molecules, and the diffusion and precipitation of In 3+ , and finally realizes the high-capacity, uniform and stable enrichment of the three metals on the surface of the carrier on a micro scale.

[0022] Example 5: The acidic solution of the example contains Zn 130 g / L, Fe(II) 10 g / L, Ga 0.1 g / L, Ge 0.1 g / L and In 0.2 g / L; A method for in-situ construction of goethite nanocomposite to cooperatively recover gallium, germanium and indium and simultaneously remove iron based on ultrasonic waves, and the specific steps are as follows: Under the ultrasonic field (frequency 20 kHz, output power 100 W) and at a temperature of 358 K, a slow micro-excess of oxidizing agent (a 0.8wt.% manganese dioxide suspension, 1.15 times the theoretical amount required to oxidize Fe(II)) was added to the acidic solution containing Fe 2+ , Ga 3+ , Ge 4+ and In 3+ to control the Fe 3+ concentration of 0.06-0.08 g / L, and a neutralizing agent (slowly added 4 mol / L sodium carbonate solution) was added to control the pH value of the reaction system to 3.5 to make iron precipitate in the form of goethite, and make gallium, germanium and indium co-precipitate or be adsorbed by goethite in the system during precipitation, and then the solid-liquid separation was performed, and the goethite nanocrystal composite material was obtained after drying the solid; The contents of iron, gallium, germanium and indium in the filtrate of this embodiment were analyzed, and the precipitation rates of Fe, Ga, Ge and In were calculated to be 98.21%, 98.03%, 97.99% and 97.96%, respectively. The goethite nanocrystal composite material of this embodiment is composed of uniformly dispersed nanoparticles, forming a high-roughness, porous sponge-like three-dimensional structure. The ultrasonic cavitation effect promotes the uniform nucleation of Fe 3+ , while inhibiting the excessive growth and agglomeration of particles; the high-activity, high-accessibility nanostructure greatly promotes the rapid surface binding of Ga 3+ , efficient mass transfer and chemical bonding of Ge(OH)4 molecules, and diffusion and precipitation of In 3+ , ultimately achieving high-capacity, uniform and stable enrichment of the three metals on the surface of the carrier at the micro level.

[0023] In this embodiment, the acidic solution contains Zn 130 g / L, Fe(II) 10 g / L, Ga 0.1 g / L, Ge 0.1 g / L and In 0.2 g / L; A method for in-situ construction of goethite nanocomposite material based on ultrasonic waves to cooperatively recover gallium, germanium and indium and simultaneously remove iron, the specific steps are as follows: Under the ultrasonic field (frequency 20 kHz, output power 80 W) and at a temperature of 358 K, a slow micro-excess oxidizing agent (H2O2 solution with a concentration of 6 wt.%, 1.2 times the theoretical amount required to oxidize Fe(II)) is added to the acidic solution containing Fe 2+ , Ga 3+ , Ge 4+ and In 3+ to control the Fe 3+ concentration in the reaction system to be 0.06-0.08 g / L. At the same time, a neutralizing agent (slowly add ammonium bicarbonate solution with a concentration of 3 mol / L) is added to control the pH value of the reaction system to be 4.0, so that iron is directionally crystallized and precipitated in the form of goethite, and gallium, germanium and indium are co-precipitated or adsorbed on the goethite in the system during the precipitation process. After solid-liquid separation, the solid is dried to obtain the goethite nanocrystal composite material; The contents of iron, gallium, germanium and indium in the filtrate of this embodiment were analyzed, and the precipitation rates of Fe, Ga, Ge and In were calculated to be 99.23%, 99.25%, 98.31% and 97.66%, respectively. The goethite nanocrystal composite material of this embodiment is composed of uniformly dispersed nanoparticles, forming a high-roughness, porous sponge-like three-dimensional structure. The ultrasonic cavitation effect promotes the uniform nucleation of Fe 3+ , while inhibiting the excessive growth and agglomeration of particles; the high-activity, high-accessibility nanostructure greatly promotes the rapid surface binding of Ga 3+rapid surface binding, efficient mass transfer and chemical bonding of Ge(OH)4 molecules, and In 3+ diffusion and precipitation, and ultimately achieve microscopically high-capacity, uniform and stable enrichment of the three metals on the surface of the carrier.

[0024] The specific embodiments of the application are described in detail above, but the application is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the application.

Claims

1. A method for the synergistic recovery of gallium, germanium, and indium, and simultaneous iron removal, based on in-situ ultrasonic construction of goethite nanocomposite materials, characterized in that, The specific steps are as follows: Under an ultrasonic field and a temperature of 313-368K, an atmosphere containing Fe was created. 2+ Ga 3+ 、Ge 4+ and In 3+ Slowly add a small excess of oxidant to an acidic solution to control the Fe content in the reaction system. 3+ Concentration, and at the same time, a neutralizing agent is added to control the pH value of the reaction system to 2.0-4.0, so that iron crystallizes and precipitates in the form of goethite, while gallium, germanium and indium are co-precipitated or goethite adsorbs gallium, germanium and indium in the system during the precipitation process, and solid-liquid separation is obtained to obtain goethite nanocrystalline composite material.

2. The method for synergistic recovery of gallium, germanium, and indium, and simultaneous iron removal, based on in-situ ultrasonic construction of goethite nanocomposite materials according to claim 1, characterized in that: The ultrasonic frequency is 15-25 kHz, and the output power is 40-200 W.

3. The method for synergistic recovery of gallium, germanium, and indium, and simultaneous iron removal, based on in-situ ultrasonic construction of goethite nanocomposite materials according to claim 1, characterized in that: The oxidant is one or more of oxygen, potassium permanganate, dichromate, manganese dioxide, and hydrogen peroxide.

4. The method for synergistic recovery of gallium, germanium, and indium, and simultaneous iron removal, based on in-situ ultrasonic construction of goethite nanocomposite materials according to claim 1, characterized in that: Controlling Fe in the reaction system 3+ The concentration is below 1 g / L.

5. The method for synergistic recovery of gallium, germanium, and indium, and simultaneous iron removal, based on in-situ ultrasonic construction of goethite nanocomposite materials according to claim 1, characterized in that: The neutralizing agent is calcium oxide, zinc oxide, calcium hydroxide, sodium hydroxide, sodium carbonate, calcium carbonate, ammonium carbonate, potassium carbonate, ammonium bicarbonate, or sodium bicarbonate.

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