A method for recovering gallium-indium alloy from gallium-based waste by acid leaching-vacuum distillation

Abstract

The present application relates to a kind of acid leaching-vacuum distillation recovery gallium base waste gallium indium alloy method, belong to the technical field of high value recovery of waste resources.The method of the present application is that gallium base waste is treated by low concentration inorganic acid to obtain Ga-In-Zn alloy, then, by the method of vacuum distillation, Ga-In alloy with higher purity is obtained on the vacuum furnace condensing cover, while Sn is enriched in the crucible at the bottom of the furnace, which provides further technical support for the subsequent recovery of Sn.The product obtained by the present application has high recovery rate and high purity.The present application is simple to operate, efficient and has high comprehensive recovery rate, and provides a new way for efficient and clean treatment and recovery of gallium-based liquid metal waste.

Description

Technical Field

[0001] This invention relates to a method for recovering gallium-indium alloy from gallium-based waste by acid leaching and vacuum distillation, belonging to the field of high-value recycling technology of waste resources. Background Technology

[0002] Gallium is a grayish-blue or silvery-white metal with a melting point of only 29.76°C, while indium is a silvery-white metal with a slight bluish tint. In nature, gallium and indium mainly coexist with bauxite or lead-zinc ore in the Earth's crust. As rare earth metals, they rarely have independent deposits. Furthermore, due to their low abundance in ores, most gallium and indium are recovered primarily as byproducts of aluminum and zinc production. Gallium is mainly used in semiconductor manufacturing, while indium is mainly used in the production of ITO sputtering targets.

[0003] Gallium-based liquid metals are a large class of emerging functional materials with unique physicochemical behaviors. They are mainly alloys of gallium and a series of other low-melting-point metals in specific proportions, such as Ga-In alloys, Ga-Sn alloys, and Ga-In-Sn alloys. These alloys are liquid at room temperature and possess properties such as high boiling point, high electrical conductivity, and high thermal conductivity. They also exhibit low-melting-point characteristics not found in conventional high-melting-point metals. Their malleability in the molten state allows for the rapid fabrication of functional electronic devices in various shapes. Besides their significant applications in high-power-density electronic chips, optoelectronic devices, and extreme heat dissipation in the defense sector, liquid metals are increasingly being applied to consumer electronics, photovoltaic power generation, energy storage, smart grids, high-performance batteries, engine systems, and hotspot switching. As a novel material with excellent thermal conductivity, liquid metals have brought about significant conceptual and technological changes in convection cooling, thermal interface materials, and phase change thermal control, breaking through the technological limits of traditional cooling principles and providing promising solutions for cooling numerous devices and equipment facing thermal barriers.

[0004] Gallium and indium are scarce metals with high demand from the technology industry, making research on their recycling and regeneration crucial. The waste generated from gallium-based liquid metal preparation processes and the aging of related products is rich in valuable metals such as gallium and indium, far exceeding their content in minerals. Considering the potential benefits they will bring, research on recovering valuable gallium and indium from these materials is of great practical significance.

[0005] This invention employs an acid leaching-vacuum distillation method to extract valuable metals gallium and indium from gallium-based waste. This process recovers and enriches gallium-indium alloys, while also enriching tin. The leachate generated during the acid leaching process contains small amounts of valuable metals, which can be recovered and regenerated through solvent extraction, resin adsorption, and alkaline leaching precipitation. This invention features a simple process flow, generates no waste gas or waste material, is clean and pollution-free, and achieves significant separation results. Summary of the Invention

[0006] To address the lack of existing processes for recovering valuable metals from gallium-based waste, this invention provides a method for recovering gallium-indium alloys from gallium-based waste using acid leaching and vacuum distillation. This method features a simple process flow, generates no waste gas or waste material, is clean and pollution-free, and achieves significant separation results. It provides a new approach for the recycling and utilization of gallium-based waste. This invention utilizes the following technical solution.

[0007] This invention discloses a method for recovering gallium-indium alloy from gallium-based waste using acid leaching and vacuum distillation, the specific steps of which are as follows:

[0008] (1) Take gallium-based waste and 0.05-1 mol / L inorganic acid, preferably 0.1-0.5 mol / L, and add them to a container at a liquid-solid ratio of 1-20:1 ml / g, preferably 5-20:1 ml / g, to obtain a ready-to-use mixture; the gallium-based waste contains gallium, indium, tin, zinc and oxygen;

[0009] (2) Stir the prepared mixture obtained in step (1) at a constant temperature of 20-50℃, preferably 25-40℃, for 10-60 minutes to obtain a mixed residue liquid;

[0010] (3) The mixed slag liquid obtained in step (2) is separated by a filtration device to obtain leaching residue, which is then dried to obtain Ga-In-Sn alloy.

[0011] (4) Place the gallium indium tin alloy obtained in step (3) into a vertical vacuum furnace, evacuate the air in the furnace to 1-10 Pa, and perform vacuum distillation at 1000-1300℃, preferably 1150-1250℃, and more preferably 1250℃. The temperature is kept constant for 30-240 min, preferably 55-100 min, and more preferably 58-65 min. The gallium indium alloy product is collected in the condenser, and Sn is enriched at the bottom of the furnace.

[0012] In industrial applications, step 3 can be performed in a water bath environment.

[0013] This invention discloses a method for recovering gallium-indium alloy from gallium-based waste by acid leaching and vacuum distillation, wherein the gallium-based waste includes gallium-based waste generated after the disposal of gallium-based liquid metal.

[0014] In this invention, the acid concentration and water bath temperature during the acid leaching process should not be too high, otherwise the leaching rate of the metals Ga and In to be recovered will increase, resulting in a decrease in the content of Ga and In in the raw materials entering the distillation process, and thus a decrease in the product recovery rate.

[0015] This invention discloses a method for recovering gallium-indium alloy from gallium-based waste using acid leaching and vacuum distillation; the gallium-based waste used contains the following components:

[0016] Gallium 65.65-71.38 wt.%;

[0017] Indium 11.90–13.95 wt.%;

[0018] Tin 9.56–11.42 wt.%;

[0019] Zinc 1.86–6.23 wt.%;

[0020] Oxygen content is less than or equal to 6.58 wt.%.

[0021] As a preferred embodiment, the present invention provides a method for recovering gallium-indium alloy from gallium-based waste using acid leaching-vacuum distillation; the gallium-based waste used contains the following components:

[0022] Gallium 68-71 wt.%;

[0023] Indium 12-13 wt.%;

[0024] Tin 10.5-11 wt.%;

[0025] Zinc 3-3.5 wt.%;

[0026] Oxygen 1-4 wt.%.

[0027] The gallium-based waste contains 65.65-71.38 wt.%, 11.90-13.95 wt.%, 9.56-11.42 wt.%, 1.86-6.23 wt.%, and 1.41-6.58 wt.%, respectively.

[0028] As a further preferred option, the contents of gallium, indium, tin, zinc, and oxygen in the gallium-based liquid metal waste are 68-71 wt.%, 12-13 wt.%, 10.5-11 wt.%, 3-3.5 wt.%, and 1-4 wt.%, respectively.

[0029] Step (1) The inorganic acid is selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid.

[0030] The small amount of valuable metals contained in the leachate of this invention can be separated and recovered by methods such as solvent extraction.

[0031] In the gallium-indium alloy obtained by this invention, under preferred conditions, the recovery rates of gallium and indium relative to the corresponding gallium and indium in the raw gallium-based waste can both reach over 90%, and the content of other elements in the obtained gallium-indium alloy, excluding gallium and indium, is less than or equal to 2 wt%.

[0032] The recovery rate of Sn can reach over 95%. Under preferred conditions, the content of other elements besides Sn is less than or equal to 2 wt%.

[0033] As one of the preferred processes, the present invention provides a method for recovering gallium-indium alloy from gallium-based waste by acid leaching and vacuum distillation, comprising the following steps:

[0034] (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture;

[0035] (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid;

[0036] (3) The mixed slag liquid obtained in step (2) is separated by a filtration device to obtain leaching residue, and then dried to obtain Ga-In-Sn alloy; the small amount of valuable metals contained in the leaching liquid can be separated and recovered by solvent extraction and other methods.

[0037] (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 1250℃. The constant temperature treatment is carried out for 60 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

[0038] The optimal process of this invention can achieve a gallium recovery rate of ≥95.5% and an indium recovery rate of ≥97.5%. At this point, the purity of Sn enriched at the bottom of the furnace is ≥98.2% and the Sn recovery rate is ≥99.5%.

[0039] The beneficial effects of this invention are: (1) This invention uses vacuum distillation to separate gallium-based waste acid leaching residue, achieving significant separation effect, and the metal volatilization temperature is lower than that under normal pressure conditions. In the obtained gallium-indium alloy, the recovery rates of gallium and indium relative to the corresponding gallium and indium in the raw material gallium-based liquid metal waste are both above 50%, and can reach above 90% after optimization. In the obtained gallium-indium alloy, the content of other elements besides gallium and indium is less than or equal to 2wt%. The recovery rate and purity of the gallium-indium alloy of this invention are far higher than those of the existing technology for separating complex zinc-indium-gallium-tin alloys.

[0040] (2) In this invention, tin and zinc are also enriched in different processes and areas, which facilitates further purification and recycling.

[0041] (3) This invention is the first to realize the efficient separation of Ga-In alloy and Sn by vacuum distillation for materials containing Ga-In-Sn alloy.

[0042] (4) This method has a simple process flow, high efficiency, and no waste gas pollution, providing a new approach for the recycling of gallium-based waste. Attached Figure Description

[0043] Figure 1 This is a flowchart of the process designed for this invention. Detailed Implementation

[0044] The present invention will be further described below with reference to specific embodiments.

[0045] Example 1: A method for recovering gallium-indium alloy from gallium-based waste using acid leaching and vacuum distillation.

[0046] In this embodiment, the contents of gallium, indium, tin, zinc and oxygen in the gallium-based waste are 70.12 wt.%, 12.03 wt.%, 10.76 wt.%, 3.24 wt.%, and 3.85 wt.%, respectively; the inorganic acid used is sulfuric acid.

[0047] The specific steps are as follows:

[0048] (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture;

[0049] (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid;

[0050] (3) The mixed slag solution obtained in step (2) is separated by a filtration device to obtain leaching residue, which is then dried to obtain Ga-In-Sn alloy. The small amount of valuable metals contained in the leaching solution can be separated and recovered by solvent extraction or other methods;

[0051] (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 1150℃. The constant temperature treatment is carried out for 60 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

[0052] In this embodiment, the mass percentage of gallium in the Ga-In alloy (gallium in the raw material, gallium-based waste) is 51.95%, and the mass percentage of indium in the Ga-In alloy (gallium in the raw material, gallium-based waste) is 63.26%. The total mass percentage of gallium and indium in the resulting Ga-In alloy is approximately 98.85 wt%. Sn is enriched at the bottom of the furnace, with a Sn recovery rate and purity of 95.52% and 28.57 wt%, respectively. (Under these temperature conditions, gallium and indium did not completely volatilize; the remaining Ga, In, and Sn coexisted at the bottom of the furnace.)

[0053] Example 2: A method for recovering gallium-indium alloy from gallium-based waste using acid leaching and vacuum distillation.

[0054] In this embodiment, the contents of gallium, indium, tin, zinc and oxygen in the gallium-based waste are 70.12 wt.%, 12.03 wt.%, 10.76 wt.%, 3.24 wt.%, and 3.85 wt.%, respectively; the inorganic acid used is sulfuric acid.

[0055] The specific steps are as follows:

[0056] (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture;

[0057] (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid;

[0058] (3) The mixed slag solution obtained in step (2) is separated by a filtration device to obtain leaching residue, which is then dried to obtain Ga-In-Sn alloy. The small amount of valuable metals contained in the leaching solution can be separated and recovered by solvent extraction or other methods;

[0059] (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 1200℃. The constant temperature treatment is carried out for 60 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

[0060] In this embodiment, the mass percentage of gallium in the Ga-In alloy (based on gallium waste) is 63.77%, and the mass percentage of indium in the Ga-In alloy (based on gallium waste) is 78.30%. The total mass percentage of gallium and indium in the resulting Ga-In alloy is approximately 98.33 wt%. Sn is enriched at the bottom of the furnace, with a Sn recovery rate of 96.88% and a Sn purity of 31.46 wt%. (Under these temperature conditions, gallium and indium did not completely volatilize; the remaining Ga, In, and Sn coexisted at the bottom of the furnace.)

[0061] Example 3: A method for recovering gallium-indium alloy from gallium-based waste using acid leaching and vacuum distillation.

[0062] In this embodiment, the contents of gallium, indium, tin, zinc and oxygen in the gallium-based waste are 70.12 wt.%, 12.03 wt.%, 10.76 wt.%, 3.24 wt.%, and 3.85 wt.%, respectively; the inorganic acid used is sulfuric acid.

[0063] The specific steps are as follows:

[0064] (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture;

[0065] (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid;

[0066] (3) The mixed slag solution obtained in step (2) is separated by a filtration device to obtain leaching residue, which is then dried to obtain Ga-In-Sn alloy. The small amount of valuable metals contained in the leaching solution can be separated and recovered by solvent extraction or other methods;

[0067] (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 1250℃. The constant temperature treatment is carried out for 60 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

[0068] In this embodiment, the mass percentage of gallium in the Ga-In alloy (gallium in the raw material, gallium-based waste) is 95.98%, and the mass percentage of indium in the Ga-In alloy (gallium in the raw material, gallium-based waste) is 97.70%. Therefore, the total mass percentage of gallium and indium in the resulting Ga-In alloy is approximately 98.79 wt%. Sn is enriched at the bottom of the furnace, with a Sn recovery rate and purity of 99.60% and 98.50 wt%, respectively.

[0069] Example 4: A method for recovering gallium-indium alloy from gallium-based waste using acid leaching and vacuum distillation.

[0070] In this embodiment, the contents of gallium, indium, tin, zinc and oxygen in the gallium-based waste are 70.12 wt.%, 12.03 wt.%, 10.76 wt.%, 3.24 wt.%, and 3.85 wt.%, respectively; the inorganic acid used is sulfuric acid.

[0071] The specific steps are as follows:

[0072] (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture;

[0073] (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid;

[0074] (3) The mixed slag solution obtained in step (2) is separated by a filtration device to obtain leaching residue, which is then dried to obtain Ga-In-Sn alloy. The small amount of valuable metals contained in the leaching solution can be separated and recovered by solvent extraction or other methods;

[0075] (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 1250℃. The constant temperature treatment is carried out for 90 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

[0076] In this embodiment, the mass percentage of gallium in the Ga-In alloy (gallium in the raw material, gallium-based waste) is 96.85%, and the mass percentage of indium in the Ga-In alloy (gallium in the raw material, gallium-based waste) is 98.63%. Therefore, the total mass percentage of gallium and indium in the resulting Ga-In alloy is approximately 98.64 wt%. Sn is enriched at the bottom of the furnace, with a Sn recovery rate and purity of 96.30% and 98.66 wt%, respectively. As can be seen from Examples 3 and 4, extending the vacuum distillation time not only increases energy consumption but also causes a decrease in the Sn recovery rate at the bottom of the furnace.

[0077] During the technology development process, the following solutions were also attempted:

[0078] Comparative Example 1: A method for recovering gallium-indium alloy from gallium-based waste using acid leaching-vacuum distillation.

[0079] In this comparative example, the contents of gallium, indium, tin, zinc, and oxygen in the gallium-based waste were 70.12 wt.%, 12.03 wt.%, 10.76 wt.%, 3.24 wt.%, and 3.85 wt.%, respectively; the inorganic acid used was sulfuric acid.

[0080] The specific steps are as follows:

[0081] (1) Take gallium-based waste and 3 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture;

[0082] (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid;

[0083] (3) The mixed slag solution obtained in step (2) is separated by a filtration device to obtain leaching residue, which is then dried to obtain Ga-In-Sn alloy. The small amount of valuable metals contained in the leaching solution can be separated and recovered by solvent extraction or other methods;

[0084] (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 1250℃. The constant temperature treatment is carried out for 90 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

[0085] In the Ga-In alloy obtained in this comparative example, the recovery rate of gallium relative to the raw material (gallium-based waste) was 80.23%, and the recovery rate of indium in the Ga-In alloy relative to the raw material was 81.35%. The mass percentage of gallium + indium in the resulting Ga-In alloy was approximately 98.63 wt%. Sn was enriched at the bottom of the furnace, with a Sn recovery rate and purity of 82.23% and 98.59 wt%, respectively. The Ga-In-Sn alloy obtained by treating with high-concentration sulfuric acid showed a significant decrease in the recovery rate of each element after vacuum distillation. This is because the excessively high acid concentration caused more metal elements to enter the liquid phase.

[0086] Comparative Example 2: A method for recovering gallium-indium alloy from gallium-based waste using acid leaching-vacuum distillation.

[0087] In this comparative example, the contents of gallium, indium, tin, zinc, and oxygen in the gallium-based waste were 70.12 wt.%, 12.03 wt.%, 10.76 wt.%, 3.24 wt.%, and 3.85 wt.%, respectively; the inorganic acid used was sulfuric acid.

[0088] The specific steps are as follows:

[0089] (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture;

[0090] (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid;

[0091] (3) The mixed slag solution obtained in step (2) is separated by a filtration device to obtain leaching residue, which is then dried to obtain Ga-In-Sn alloy. The small amount of valuable metals contained in the leaching solution can be separated and recovered by solvent extraction or other methods;

[0092] (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 800℃. The constant temperature treatment is carried out for 90 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

[0093] In the Ga-In alloy obtained in this comparative example, the recovery rate of gallium relative to the raw material (gallium-based waste) was 0, and the recovery rate of indium in the Ga-In alloy relative to the raw material was also 0 (gallium and indium are almost non-volatile at 800℃). The recovery rate and purity of Sn were 99.96% and 11.56 wt%, respectively (gallium, indium, and tin were co-enriched in the crucible at the bottom of the furnace, making it impossible to truly achieve efficient separation and recovery of Ga-In alloy and Sn).

[0094] Comparative Example 3: A method for recovering gallium-indium alloy from gallium-based waste using acid leaching-vacuum distillation.

[0095] In this comparative example, the contents of gallium, indium, tin, zinc, and oxygen in the gallium-based waste were 70.12 wt.%, 12.03 wt.%, 10.76 wt.%, 3.24 wt.%, and 3.85 wt.%, respectively; the inorganic acid used was sulfuric acid.

[0096] The specific steps are as follows:

[0097] (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture;

[0098] (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid;

[0099] (3) The mixed slag solution obtained in step (2) is separated by a filtration device to obtain leaching residue, which is then dried to obtain Ga-In-Sn alloy. The small amount of valuable metals contained in the leaching solution can be separated and recovered by solvent extraction or other methods;

[0100] (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 1500℃. The constant temperature treatment is carried out for 90 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

[0101] In the Ga-In alloy obtained in this comparative example, the recovery rate of gallium relative to the raw material (gallium-based waste) was 97.25%, and the recovery rate of indium in the Ga-In alloy relative to the raw material was 98.16%. The mass percentage of gallium + indium in the obtained Ga-In alloy was approximately 83.42 wt%. (Tin will also volatilize at this temperature and accumulate together with the gallium-indium alloy in the condensation pan, making it impossible to truly achieve efficient separation and recovery of Ga-In alloy and Sn).

Claims

1. A method for recovering gallium-indium alloy from gallium-based waste using acid leaching and vacuum distillation, characterized in that, Includes the following steps: (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a container at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture; the gallium-based waste contains gallium, indium, tin, zinc and oxygen; (2) Stir the prepared mixture obtained in step (1) at a constant temperature of 25-40℃ for 10-60 minutes to obtain a mixed residue liquid; (3) The mixed slag liquid obtained in step (2) is separated by a vacuum filter to obtain leaching residue, which is then dried to obtain gallium indium tin alloy; (4) Place the gallium indium tin alloy obtained in step (3) into a vertical vacuum furnace, evacuate the air in the furnace to 1-10 Pa, perform vacuum distillation at 1000-1300℃, keep the temperature constant for 30-240 min, collect the gallium indium alloy product in the condenser, and obtain Sn enrichment at the bottom of the furnace. In gallium-based waste, Gallium 65.65-71.38 wt.%; Indium 11.90~13.95 wt.%; Tin 9.56~11.42 wt.%; Zinc 1.86~6.23 wt.%; Oxygen is less than or equal to 6.58 wt.%.

2. The method for recovering gallium-indium alloy from gallium-based waste by acid leaching-vacuum distillation according to claim 1, characterized in that: In gallium-based waste, Gallium 68-71 wt.%; Indium 12-13 wt.%; Tin 10.5-11 wt.%; Zinc 3-3.5 wt.%; Oxygen 1-4 wt.%.

3. The method for recovering gallium-indium alloy from gallium-based waste by acid leaching-vacuum distillation according to claim 1, characterized in that: The inorganic acid is selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid.

4. The method for recovering gallium-indium alloy from gallium-based waste by acid leaching and vacuum distillation according to claim 1, characterized in that: Vacuum distillation was carried out at 1150-1250℃.

5. The method for recovering gallium-indium alloy from gallium-based waste by acid leaching and vacuum distillation according to claim 1, characterized in that: In gallium-indium alloys, the recovery rates of gallium and indium can reach over 90% compared to the corresponding gallium and indium in the raw gallium-based waste. In the resulting gallium-indium alloy, the content of other elements, excluding gallium and indium, is less than or equal to 2 wt%.

6. The method for recovering gallium-indium alloy from gallium-based waste by acid leaching-vacuum distillation according to claim 1, characterized in that: The recovery rate of Sn can reach over 95%, and the content of other elements is less than or equal to 2 wt%.

7. The method for recovering gallium-indium alloy from gallium-based waste by acid leaching and vacuum distillation according to claim 1, characterized in that: Includes the following steps: (1) Take gallium-based waste and 0.1 mol / L inorganic acid, add them to a beaker at a liquid-solid ratio of 5:1 ml / g to obtain a ready-to-use mixture; (2) Place the prepared mixture obtained in step (1) into a water bath, control the temperature of the water bath at 25°C, and stir at a constant temperature for 30 minutes to obtain a mixed residue liquid; (3) The mixed residue obtained in step (2) is separated by a filtration device to obtain leaching residue, which is dried to obtain gallium indium tin alloy; the small amount of valuable metal contained in the leaching solution is separated and recovered by solvent extraction. (4) The gallium indium tin alloy obtained in step (3) is placed in a vertical vacuum furnace, the air in the furnace is evacuated to 1-10 Pa, and vacuum distilled at 1250℃. The constant temperature treatment is carried out for 60 min, and the gallium indium alloy product is collected in the condenser. Sn enrichment is obtained at the bottom of the furnace.

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