Process for enriching gallium with converter dust

Abstract

This invention provides a method for enriching gallium using converter ash, comprising the following steps: S1: removing iron particles from the converter ash to obtain gallium-rich material; S2: leaching the gallium-rich material from step S1 with a leaching agent to obtain a gallium leaching solution; S3: reducing the gallium leaching solution from step S2 with a reducing agent to obtain a reduced gallium leaching solution; S4: extracting the reduced gallium leaching solution from step S3 to obtain a gallium-containing organic phase; S5: back-extracting the gallium-containing organic phase from step S4 to obtain a gallium-containing aqueous phase; S6: treating the gallium-containing aqueous phase from step S5 to obtain a gallium-containing precipitate, dissolving the gallium-containing precipitate with alkali, and then electrolyzing it to obtain metallic gallium. This invention utilizes unique raw materials with high gallium content, a short gallium enrichment process, and good impurity removal effect. Simultaneously, the generated byproducts have high purity and good economic value.

Description

Technical Field

[0001] This invention relates to the field of gallium extraction, and more specifically to a method for enriching gallium using converter ash. Background Technology

[0002] Gallium, a rare and dispersed metal, is an important strategic resource. A series of compound semiconductor materials, electron optical materials, novel functional materials, special alloys, and organometallic compounds prepared using gallium metal as a matrix are crucial foundational materials for modern high-tech fields such as computers, communications, aerospace, new energy, medicine and healthcare, and military industries. Approximately 90% of the world's gallium is recovered from the production of alumina, forming a mature industrial chain. Gallium is also enriched during zinc smelting and in coal ash, but the extraction of gallium from these two raw materials has not been industrialized due to the long extraction process and high costs.

[0003] The Panxi region has a wide variety of valuable metals. Gallium is associated with elements such as V, Fe, and Ti in Panxi minerals. Currently, gallium extraction research mainly uses vanadium extraction tailings as raw material. However, due to the complex composition of vanadium extraction tailings, direct acid leaching has a low leaching rate, high acid consumption, and generates a large number of unusable byproducts. Furthermore, the entire process route is very long. Therefore, this route has not actually been put into industrial production.

[0004] A method for extracting gallium from vanadium extraction tailings was reported in CN 106957963 A, but it has not been industrialized due to its lack of economic viability. Additionally, the enrichment of gallium using alumina seed mother liquor was reported in CN113249596A. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a method for enriching gallium using converter ash.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention provides a method for enriching gallium using converter ash, comprising the following steps:

[0008] S1: Remove iron particles from converter ash to obtain gallium-rich material;

[0009] S2: Leach the gallium-rich material from step S1 with a leaching agent to obtain a gallium leaching solution;

[0010] S3: Reduce the gallium leaching solution from step S2 using a reducing agent to obtain a reduced gallium leaching solution;

[0011] S4: Extract the reduced gallium leaching solution from step S3 to obtain a gallium-containing organic phase;

[0012] S5: Back-extract the gallium-containing organic phase from step S4 to obtain a gallium-containing aqueous phase;

[0013] S6: The gallium-containing aqueous phase in step S5 is processed to obtain a gallium-containing precipitate. After the gallium-containing precipitate is dissolved in alkali, it is electrolyzed to obtain metallic gallium.

[0014] Further, step S1 includes the following steps:

[0015] S1-1: Remove the oxides on the surface of the iron particles by dry grinding or wet grinding to completely dissociate the iron beads. The dissociation process takes 5-30 minutes.

[0016] S1-2: Iron particles are removed by dry or wet magnetic separation, wherein the working magnetic field strength of the magnetic separator is (0.6-40)×10 5 A / m.

[0017] Further, in step S2, the gallium-rich material is mixed with the leaching agent, wherein,

[0018] The leaching agent is a 2-8 mol / L hydrochloric acid solution, the mass ratio of the leaching agent to the gallium-rich material is (2-30):1, the leaching temperature is 30-90℃, and the leaching time is 0.5-10h.

[0019] Furthermore, in step S3, the reducing agent is one or more of carbon monoxide, hydrogen, vitamin C, pure iron powder, and reduced iron powder.

[0020] Furthermore,

[0021] The amount of carbon monoxide and / or hydrogen introduced is 30-150% of the molar mass of trivalent iron in the gallium leaching solution;

[0022] The amount of vitamin C, pure iron powder, or reduced iron powder added is 70-120% of the molar mass of trivalent iron in the gallium leaching solution;

[0023] The purity of pure iron powder is >99%.

[0024] Furthermore, in the extraction process of step S4, the volume ratio of the organic phase to the aqueous phase is 1:(0.5-10), the organic phase includes an extractant and a diluent, wherein the volume of the extractant accounts for less than 60% of the volume of the organic phase, and the amount of the diluent added accounts for at least 40% of the volume of the organic phase.

[0025] Furthermore,

[0026] The extractant is one or more of TBP, P204, N235, P507, TOPO, and neodecanoic acid, and different extractants are combined in any proportion.

[0027] The diluent is sulfonated kerosene or industrial kerosene.

[0028] Further, in step S5, the pH of the back-extraction aqueous phase is 5-10, wherein,

[0029] The solution in the aqueous phase of the back-extraction is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and pure water in any proportion.

[0030] Furthermore, in step S5, the gallium-containing precipitate is gallium hydroxide.

[0031] Furthermore, the mass content of each component in the converter ash is as follows: 10-30% Fe, 50-80% Fe2O3, 0-5% SiO2, 1-9% MnO, and the remainder is any combination of Na2O, MgO, CaCO3, Al2O3, TiO2, V2O5, Cr2O3, ZnO, PbO, CuO, NiO, chlorides, and sulfides, with a total content of less than 20%.

[0032] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0033] The raw materials for gallium extraction in this invention are unique, with high gallium content, a short gallium enrichment process, and good impurity removal effect. At the same time, the by-products produced have high purity and good economic value. Attached Figure Description

[0034] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 This is a schematic flowchart of the method for enriching gallium using converter ash according to the present invention. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be further described in detail below with reference to specific examples and the accompanying drawings.

[0037] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0038] The main components of the gallium extraction raw material converter ash involved in this invention have the following mass content: 10-30% Fe, 50-80% Fe2O3, 0-5% SiO2, 1-9% MnO, and the remainder being any combination of Na2O, MgO, CaCO3, Al2O3, TiO2, V2O5, Cr2O3, ZnO, PbO, CuO, NiO, chlorides, and sulfides, with a total content of less than 20%. The content of elemental gallium in the converter ash is 100-500 g / t.

[0039] like Figure 1 As shown, the present invention provides a method for enriching gallium using converter ash, comprising the following steps:

[0040] S1: Remove iron particles from the converter ash to obtain gallium-rich material. Step S1 specifically includes the following steps:

[0041] S1-1: Remove the oxides on the surface of the iron particles by dry or wet grinding to completely dissociate the iron beads. The dissociation process takes 5-30 minutes.

[0042] Converter ash particles are generally small, all below 3mm. Water mist is sometimes used for dust removal, resulting in a moisture content of 0-10% in the ash. Due to the accumulation of converter dust, the surface of the iron particles is oxidized. Therefore, pretreatment requires grinding to remove the oxides and completely separate the iron particles. This separation can be done dry or wet, depending on the subsequent magnetic separation method (dry or wet separation). The separation process generally takes a maximum of 30 minutes to avoid excessively fine particles, high energy consumption, or excessive dust generation and raw material loss during dry magnetic separation.

[0043] S1-2: Iron particles are removed by dry or wet magnetic separation, wherein the working magnetic field strength of the magnetic separator is (0.6-40)×10 5 A / m.

[0044] After dissociation, the particles undergo magnetic separation pretreatment to improve gallium enrichment. Magnetic separation can be dry or wet. To avoid excessive gallium loss during separation, wet separation can be chosen. There are many types of magnetic separators; this invention does not limit the type, but the operating magnetic field strength of the separator needs to be (0.6-40)×10⁻⁶. 5 Between A and m. The magnetic field strength is adjusted according to the degree of Fe dissociation. After magnetic separation, the gallium content of the gallium-rich material can reach 140-700 g / t. This step can remove elemental iron.

[0045] S2: Leach the gallium-rich material from step S1 with a leaching agent to obtain a gallium leaching solution.

[0046] Gallium-rich material (after removing elemental iron) is mixed with a leaching agent, which is a 2-8 mol / L hydrochloric acid solution. The mass ratio of leaching agent to gallium-rich material (i.e., liquid-solid ratio) is (2-30):1. The leaching temperature is 30-90℃, and the leaching time is 0.5-10 hours. During leaching, the solution can be stirred, allowed to stand, or shaken. After leaching, the gallium leaching rate can reach 90-99%. After leaching, the residue can be separated from the leachate by methods such as vacuum filtration, pressure filtration, and centrifugation, but is not limited to these methods.

[0047] S3: Use a reducing agent to reduce the gallium leaching solution from step S2 to obtain a reduced gallium leaching solution.

[0048] After leaching, vitamin C, a reducing agent, can be added to the gallium leaching solution. During the dissolution process, stirring and heating can be used to accelerate the dissolution rate of vitamin C in the leaching solution, but the heating temperature (i.e., the temperature required for the reduction reaction) must be less than 70°C, preferably 5-70°C. Pure iron powder, a reducing agent, can also be added to the leaching solution. The purity of the iron powder must be above 99%. Stirring and heating can be carried out simultaneously with the addition of iron powder, and the heating temperature is not limited. Reducing iron powder can also be added to the leaching solution.

[0049] In addition to adding reducing substances to the leaching solution, one or more reducing gases, such as carbon monoxide and hydrogen, can also be introduced into the leaching solution in a mixed form. In a preferred embodiment, the reducing gas can be a mixed gas after impurity removal produced in other processes, and the gas not consumed in the reduction of ferric iron in the gallium leaching solution can be reused. The amount of reducing substances and reducing gases added varies depending on the content of ferric iron in the gallium leaching solution. The amount of vitamin C, pure iron powder, or reduced iron powder added is 70-120% of the molar mass of ferric iron in the gallium leaching solution, and the amount of carbon monoxide and / or hydrogen introduced is 30-150% of the molar mass of ferric iron in the gallium leaching solution. In a preferred embodiment, the reducing agent is added for reduction until more than 80% of the iron in the gallium leaching solution is ferrous iron.

[0050] S4: Extract the reduced gallium leachate from step S3 to obtain a gallium-containing organic phase.

[0051] The reduced gallium leaching solution needs to be extracted immediately. During the extraction process, the volume ratio of the organic phase to the aqueous phase is 1:(0.5-10). The organic phase includes an extractant and a diluent. The volume of the extractant is less than 0.6% of the organic phase volume, and the amount of diluent added is at least 40% of the organic phase volume. The extractant can be one or more of the following: TBP (tributyl phosphate), P204 (di(2-ethylhexyl) phosphate), N235 (trioctylamine), P507 (2-ethylhexyl phosphate mono-2-ethylhexyl ester), TOPO (tri-n-octylphosphine oxide), and neodecanoic acid. When using a mixed extractant, different extractants can be combined in any proportion, but the volume of the extractant should be less than 60% of the total organic phase volume. The diluent can be sulfonated kerosene or other types of industrial kerosene.

[0052] Extraction methods are not limited to laboratory equipment or industrial extraction tanks, extraction towers, and centrifugal extractors. Depending on the proportion of the active ingredient (i.e., the extractant) in the organic phase and the organic-to-aqueous phase ratio, the extraction process can be divided into 1-3 stages. Over 98% of gallium can be extracted into the organic phase. Extraction is stopped when the gallium recovery rate reaches 98% or higher. After extraction, the raffinate can be used to produce products such as ferric chloride and ferrous chloride.

[0053] S5: Back-extract the gallium-containing organic phase from step S4 to obtain a gallium-containing aqueous phase.

[0054] Gallium-containing organic phases are back-extracted, with the pH of the back-extraction aqueous phase controlled at 5-10. The gallium recovery rate after back-extraction precipitation can reach over 95%. The solution in the back-extraction aqueous phase can be one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, or pure water, mixed in any proportion. The back-extraction process consists of 1-5 stages, depending on the effective extractant in the organic phase used. Back-extraction is stopped when the gallium recovery rate reaches over 97%. The gallium after back-extraction exists in the form of gallium hydroxide, with a gallium content of 40-54 wt%.

[0055] S6: The gallium-containing aqueous phase in step S5 is processed to obtain a gallium-containing precipitate. After the gallium-containing precipitate is dissolved in alkali, it is electrolyzed to obtain metallic gallium.

[0056] Gallium after stripping exists in the form of solid gallium hydroxide. Gallium hydroxide is dissolved in an alkaline solution, and the alkaline solution is electrolyzed to finally obtain metallic gallium that conforms to GB / T 1475-2022.

[0057] Example 1

[0058] The gallium extraction raw material involved in this embodiment—converter ash—has the following main components by mass: 30% Fe, 50% Fe2O3, 1% SiO2, and 2% MnO. The remainder is a mixture of Na2O, MgO, CaCO3, Al2O3, TiO2, V2O5, Cr2O3, ZnO, PbO, CuO, NiO, chlorides, and sulfides, totaling 17%. The gallium content of the converter ash is 500 g / t.

[0059] The converter ash particles are all below 3mm and have a moisture content of 5%. The ball mill is the separation device in this embodiment. An appropriate amount of water is added for wet grinding, which takes 30 minutes to completely separate the iron balls.

[0060] The dissociated particles are pretreated by magnetic separation to improve gallium enrichment. In this embodiment, wet magnetic separation is used, with a working magnetic field strength of 1×10⁻⁶. 5 A / m. After magnetic separation, the gallium content of the gallium-rich material can reach 550 g / t. This step essentially removes elemental iron, yielding the gallium-rich material.

[0061] Gallium-rich material (after removing elemental iron) was mixed with a 4 mol / L hydrochloric acid solution. The liquid-to-solid ratio was controlled at 5:1. After the addition was complete, the mixture was heated to 50°C and leached for 4 hours. The solution could be stirred during leaching to obtain a gallium leaching solution. After leaching, the gallium leaching rate reached 98%. After leaching, the residue was separated from the leaching solution by centrifugation.

[0062] After leaching, vitamin C is added to the gallium leaching solution. During the dissolution process, stirring and heating are carried out at 40°C. The amount of vitamin C added is 70% of the molar mass of ferric iron in the gallium leaching solution. Simultaneously, a mixture of carbon monoxide and hydrogen in any proportion is introduced, with the amount of this mixture being 30% of the molar mass of ferric iron in the gallium leaching solution.

[0063] The reduced gallium leaching solution needs to be extracted immediately. In the extraction process, the volume ratio of the organic phase to the aqueous phase is 2:1. The effective extractants in the organic phase are TBP, P2O4, and N235, and the diluent is sulfonated kerosene. The proportion (volume ratio) of the effective extractants in the organic phase is 1:1:1, but they account for 50% of the total organic phase volume. The amount of diluent added accounts for 50% of the organic phase volume. The extraction device is an industrial extraction tank. The extraction process is a single-stage process, and over 98% of the gallium can be extracted into the organic phase. After extraction, the raffinate can be used to produce products such as ferric chloride and ferrous chloride.

[0064] The gallium-containing organic phase was then back-extracted, with the pH of the back-extraction aqueous phase controlled at 5. The gallium recovery rate after back-extraction precipitate reached over 95%. The solution in the back-extraction aqueous phase consisted of sodium hydroxide and pure water. The back-extraction process was a three-stage process. The gallium after back-extraction existed in the form of gallium hydroxide, with a gallium content of 45 wt%. The obtained gallium-rich raw material could be dissolved in alkali and then electrolyzed to finally obtain metallic gallium conforming to GB / T1475-2022.

[0065] Example 2

[0066] The gallium extraction raw material involved in this embodiment—converter ash—has the following main components by mass: 10% Fe, 70% Fe2O3, 5% SiO2, and 9% MnO. The remainder is a mixture of Na2O, MgO, CaCO3, Al2O3, TiO2, V2O5, Cr2O3, ZnO, PbO, CuO, NiO, chlorides, and sulfides, totaling 6%. The gallium content of the converter ash is 100 g / t.

[0067] The converter ash particles are all below 3mm and have a moisture content of 10%. The ball mill is the dissociation device in this embodiment. Due to the high moisture content, no water needs to be added, and it is directly dry-ground for 20 minutes to dissociate the iron balls.

[0068] The dissociated particles are pretreated by magnetic separation to improve gallium enrichment. In this embodiment, dry magnetic separation is used. The working magnetic field strength is 10 × 10⁻⁶. 5 A / m. After magnetic separation, the gallium content can reach 140 g / t. This step can basically remove elemental iron and some magnetic materials to obtain gallium-rich material.

[0069] Gallium-rich material, after removing elemental iron, was mixed with a 6 mol / L hydrochloric acid solution. The liquid-to-solid ratio was controlled at 15:1. After the addition was complete, the mixture was heated to 30°C and allowed to stand for leaching for 10 hours to obtain a gallium leaching solution. After leaching, the gallium leaching rate reached 95%. After leaching, the residue was separated from the leaching solution by pressure filtration.

[0070] After leaching, pure iron powder with a purity of 99% or higher is added to the gallium leaching solution. Stirring and heating are performed simultaneously with the addition of the iron powder at a temperature of 80°C. The amount of iron powder added is 120% of the molar mass of trivalent iron in the gallium leaching solution.

[0071] The reduced gallium leaching solution needs to be extracted immediately. In the extraction process, the volume ratio of the organic phase to the aqueous phase is 1:7. The effective extractants in the organic phase are TOPO and neodecanoic acid, and the diluent can be industrial kerosene. The proportion (volume ratio) of the effective extractants in the organic phase is 1:1, accounting for 30% of the total organic phase volume, and the amount of diluent added accounts for 70% of the organic phase volume. The extraction method is a centrifugal extractor. The extraction process can be a single stage, allowing 99% of the gallium to enter the organic phase through extraction. After extraction, the raffinate can be used to produce products such as ferric chloride and ferrous chloride.

[0072] The gallium-containing organic phase was then back-extracted, with the pH of the back-extraction aqueous phase controlled at 10. The gallium recovery rate after back-extraction reached 97%. The solution in the back-extraction aqueous phase was a mixture of sodium bicarbonate and pure water, and the back-extraction process consisted of 5 stages. The gallium after back-extraction existed as gallium hydroxide, with a gallium content of 50 wt%. The obtained gallium-rich raw material could be dissolved in alkali and then electrolyzed to finally obtain metallic gallium conforming to GB / T 1475-2022.

[0073] Example 3

[0074] The gallium extraction raw material involved in this embodiment—converter ash—has a main component content of 10% Fe, 80% Fe2O3, and 9% MnO, with the remainder being a mixture of Na2O, MgO, CaCO3, Al2O3, TiO2, V2O5, Cr2O3, ZnO, PbO, CuO, NiO, chlorides, and sulfides, totaling 1%. The gallium content of the converter ash is 200 g / t.

[0075] The converter ash particles are all below 3mm and have a moisture content of 5%. The ball mill is the separation device in this embodiment. An appropriate amount of water is added for wet grinding, which takes 10 minutes to completely separate the iron balls.

[0076] The dissociated particles are pretreated by magnetic separation to improve gallium enrichment. In this embodiment, wet magnetic separation is used, with a working magnetic field strength of 0.6 × 10⁻⁶. 5 A / m. After magnetic separation, the gallium content of the gallium-rich material can reach 700 g / t. This step essentially removes elemental iron, yielding the gallium-rich material.

[0077] Gallium-rich material (after removing elemental iron) was mixed with a 2 mol / L hydrochloric acid solution. The liquid-to-solid ratio was controlled at 30:1. After the addition was complete, the mixture was heated to 90°C and leached for 10 hours. During leaching, the solution could be agitated to obtain a gallium leachate. After leaching, the gallium leaching rate reached 90%. After leaching, the residue was separated from the leachate by vacuum filtration.

[0078] After leaching, reduced iron powder is added to the gallium leaching solution, and the mixture is stirred during dissolution while being heated to 5°C. The amount of reduced iron powder added is 120% of the molar mass of trivalent iron in the gallium leaching solution.

[0079] The reduced gallium leaching solution needs to be extracted immediately. In the extraction process, the volume ratio of the organic phase to the aqueous phase is 1:10. The effective extractants in the organic phase are neodecanoic acid, TBP, P2O4, and N235, and the diluent is sulfonated kerosene. The ratio (volume ratio) of the effective extractants in the organic phase is 1:2:1:1, but it accounts for 55% of the total organic phase volume. The amount of diluent added accounts for 40% of the organic phase volume. The extraction device is a centrifugal extractor. The extraction process is three-stage, and more than 99% of the gallium can be extracted into the organic phase. After extraction, the raffinate can be used to produce products such as ferric chloride and ferrous chloride.

[0080] The gallium-containing organic phase was then back-extracted, with the pH of the back-extraction aqueous phase controlled at 6. The gallium recovery rate after back-extraction precipitate reached over 98%. The solution in the back-extraction aqueous phase was pure water. The back-extraction process consisted of 5 stages. The gallium after back-extraction existed in the form of gallium hydroxide, with a gallium content of 54 wt%. The obtained gallium-rich raw material could be dissolved in alkali and then electrolyzed to finally obtain metallic gallium conforming to GB / T 1475-2022.

[0081] Example 4

[0082] The gallium extraction raw material involved in this embodiment—converter ash—has the following main components by mass: 30% Fe, 50% Fe2O3, 5% SiO2, and 12% MnO. The remainder is a mixture of Na2O, MgO, CaCO3, Al2O3, TiO2, V2O5, Cr2O3, ZnO, PbO, CuO, NiO, chlorides, and sulfides, totaling 3%. The gallium content of the converter ash is 300 g / t.

[0083] The converter ash particles are all below 3mm. The ball mill is the separation device in this embodiment. Direct dry grinding is carried out for 10 minutes to completely separate the iron balls.

[0084] After dissociation, the particles undergo magnetic separation pretreatment to improve gallium enrichment. In this embodiment, wet magnetic separation is used, with a working magnetic field strength of 40 × 10⁻⁶. 5 A / m. After magnetic separation, the gallium content of the gallium-rich material can reach 500 g / t. This step essentially removes elemental iron, yielding the gallium-rich material.

[0085] Gallium-rich material (after removing elemental iron) was mixed with an 8 mol / L hydrochloric acid solution. The liquid-to-solid ratio was controlled at 2:1. After the addition was complete, the mixture was heated to 30°C and leached for 0.5 hours. The solution could be stirred during leaching to obtain a gallium leaching solution. After leaching, the gallium leaching rate reached 99%. After leaching, the residue was separated from the leaching solution by centrifugation.

[0086] After leaching is complete, the gallium leaching solution is heated to 80°C, and then a mixture of carbon monoxide and hydrogen in any proportion is introduced. The amount of this mixture introduced is 150% of the molar mass of trivalent iron in the gallium leaching solution.

[0087] The reduced gallium leaching solution needs to be extracted immediately. In the extraction process, the volume ratio of the organic phase to the aqueous phase is 2:1. The extractants in the organic phase are TBP, TOPO, and P507, and the diluent is industrial kerosene. The effective extractant ratio (volume ratio) in the organic phase is 2:2:1, but it accounts for 40% of the total organic phase volume. The diluent accounts for 60% of the organic phase volume. The extraction device is an extraction tower. The extraction process is a single-stage process, and over 98% of the gallium can be extracted into the organic phase. After extraction, the raffinate can be used to produce products such as ferric chloride and ferrous chloride.

[0088] The gallium-containing organic phase was then back-extracted, with the pH of the back-extraction aqueous phase controlled at 9. The gallium recovery rate after back-extraction precipitate reached over 99%. The solution in the back-extraction aqueous phase consisted of sodium hydroxide and pure water. The back-extraction process was a single-stage process. The gallium after back-extraction existed in the form of gallium hydroxide, with a gallium content of 40 wt%. The obtained gallium-rich raw material could be dissolved in alkali and then electrolyzed to finally obtain metallic gallium conforming to GB / T1475-2022.

[0089] It should be noted that the components or steps in the above embodiments can be interchanged, substituted, added, or deleted. Therefore, the combinations formed by these reasonable permutations and transformations should also fall within the protection scope of this invention, and the protection scope of this invention should not be limited to the above embodiments.

[0090] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention (including the claims) is limited to these examples. Within the framework of the invention, technical features of the above embodiments or different embodiments can be combined, and many other variations of the different aspects of the invention as described above exist, which are not provided in the details for the sake of brevity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the invention should be included within the protection scope of the invention.

Claims

1. A method for enriching gallium using converter ash, characterized in that, Includes the following steps: S1: Remove iron particles from converter ash to obtain gallium-rich material. The mass content of each component in the converter ash is as follows: 10-30% Fe, 50-80% Fe2O3, 0-5% SiO2, 1-9% MnO, and the remainder is any combination of Na2O, MgO, CaCO3, Al2O3, TiO2, V2O5, Cr2O3, ZnO, PbO, CuO, NiO, chloride, and sulfide, with a total content of less than 20%. The content of elemental gallium in the converter ash is 100-500 g / t. S2: Leach the gallium-rich material from step S1 with a leaching agent to obtain a gallium leaching solution; S3: Reduce the gallium leaching solution from step S2 using a reducing agent to obtain a reduced gallium leaching solution; S4: Extract the reduced gallium leaching solution from step S3 to obtain a gallium-containing organic phase; S5: Back-extract the gallium-containing organic phase from step S4 to obtain a gallium-containing aqueous phase; S6: The gallium-containing aqueous phase in step S5 is processed to obtain a gallium-containing precipitate. After the gallium-containing precipitate is dissolved in alkali, it is electrolyzed to obtain metallic gallium.

2. The method according to claim 1, characterized in that, Step S1 includes the following steps: S1-1: Remove the oxides on the surface of the iron particles by dry grinding or wet grinding to completely dissociate the iron beads. The dissociation process takes 5-30 minutes. S1-2: Iron particles are removed by dry or wet magnetic separation, wherein the working magnetic field strength of the magnetic separator is (0.6-40)×10 5 A / m.

3. The method according to claim 1, characterized in that, In step S2, the gallium-rich material is mixed with the leaching agent, wherein, The leaching agent is a 2-8 mol / L hydrochloric acid solution, the mass ratio of the leaching agent to the gallium-rich material is (2-30):1, the leaching temperature is 30-90℃, and the leaching time is 0.5-10h.

4. The method according to claim 1, characterized in that, In step S3, the reducing agent is one or more of carbon monoxide, hydrogen, vitamin C, and pure iron powder.

5. The method according to claim 4, characterized in that, The purity of pure iron powder is >99%.

6. The method according to claim 1, characterized in that, In the extraction process of step S4, the volume ratio of the organic phase to the aqueous phase is 1:(0.5-10). The organic phase includes an extractant and a diluent. The volume of the extractant accounts for less than 60% of the volume of the organic phase, and the amount of the diluent added accounts for at least 40% of the volume of the organic phase.

7. The method according to claim 6, characterized in that, The extractant is one or more of TBP, P204, N235, P507, TOPO, and neodecanoic acid, and different extractants are combined in any proportion. The diluent is sulfonated kerosene or industrial kerosene.

8. The method according to claim 1, characterized in that, In step S5, the pH of the back-extraction aqueous phase is 5-10, wherein, The solution in the aqueous phase of the back-extraction is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and pure water in any proportion.

9. The method according to claim 8, characterized in that, In step S5, the gallium-containing precipitate is gallium hydroxide.

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