Separation and purification method of iron-containing copper-cobalt-germanium material

Abstract

The present application relates to the technical field of hydrometallurgy, in particular to a separation and purification method of iron, copper, cobalt and germanium-containing material.The present application provides a separation and purification method of iron, copper, cobalt and germanium-containing material.The method provided by the present application can effectively separate germanium and other valuable metal components in the copper, cobalt and germanium-containing material, and the other valuable metal components can also be sequentially separated and purified, the separation is relatively complete, and the process is simple.The present application solves the problems of the current germanium concentrate production process, such as complex process flow, high cost, serious pollution and the like, provides a simple process, which can realize the separation of germanium, copper, iron and cobalt, and obtains germanium concentrate rich in germanium, has good separation effect, low cost, environmental friendliness, good economic and social benefits, and is suitable for industrial production.Experiments show that the present application successfully separates germanium, iron, cobalt and copper in the iron, copper, cobalt and germanium-containing material, the recovery rate of germanium reaches more than 95%, and the by-products such as iron, cobalt and copper are also successfully separated and purified.

Description

A method for separating and purifying iron-copper-cobalt-germanium-containing materials Technical Field

[0001] This invention relates to the field of hydrometallurgical technology, specifically a method for separating and purifying iron-containing copper, cobalt, and germanium materials. Background Technology

[0002] Germanium is a rare dispersed metal with dual properties of metal and nonmetal. It has a wide range of applications and can be used to make various transistors, rectifiers and other devices. Germanium compounds are used to manufacture fluorescent panels and various high refractive index glasses.

[0003] Currently, germanium concentrate is produced using pyrometallurgical, hydrometallurgical, and combined processes, selected based on the different raw materials. Pyrometallurgical enrichment is used to extract germanium from coal, while hydrometallurgical enrichment is used to recover germanium during heavy non-ferrous metal smelting. Germanium-containing waste generated in semiconductor device production is pretreated and directly added to the germanium metal production process. Germanium metal production mainly includes chemical treatment and refining, reduction to produce germanium metal, and physical purification. First, the germanium concentrate is chlorinated with concentrated hydrochloric acid to produce germanium tetrachloride. Then, the main impurity, arsenic, is removed by hydrochloric acid solvent extraction. After two distillations in a quartz column, it is washed with high-purity hydrochloric acid to obtain high-purity germanium tetrachloride. Germanium tetrachloride is then hydrolyzed with high-purity water to obtain high-purity germanium dioxide. Some impurities may enter the mother liquor, so the hydrolysis process is also a purification process. Pure germanium dioxide is dried and calcined, then reduced with hydrogen at 650℃~680℃ in a quartz tube of a reduction furnace to obtain metallic germanium.

[0004] However, current methods are complex and the separation and purification are not thorough enough. Leaching-precipitation is currently the most commonly used process for recovering germanium in industry. It is a mature process that can be adapted to industrialization, but its disadvantages are that it causes significant environmental pollution and is not suitable for materials with low germanium content or a high number of impurities. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a method for separating and purifying iron-containing copper, cobalt and germanium materials. The method provided by the present invention can effectively separate germanium and other valuable metal components in copper, cobalt and germanium materials, and the other valuable metal components can also be separated and purified in sequence. The separation is relatively thorough and the process is simple.

[0006] This invention provides a method for separating and purifying iron-, copper-, cobalt-, and germanium-containing materials, which is carried out according to the following steps:

[0007] S1) After acid leaching of iron-containing copper-cobalt-germanium materials, the solid material is washed with water to obtain a washing solution.

[0008] S2) The complexing agent, organic phase, back-extraction solution and the washing solution described in step S1) are mixed and extracted to obtain raffinate and back-extraction solution;

[0009] S3) Following the processing order of iron precipitation, copper precipitation, and cobalt precipitation, iron by-products, copper by-products, and cobalt by-products are sequentially extracted from the raffinate described in step S2).

[0010] The iron-copper-cobalt-germanium material described in this invention is a germanium concentrate obtained from a resource company in Yunnan Province. The germanium concentrate is a compound containing germanium, copper, cobalt, iron, and other components. The method described in this invention uses a wet process to sequentially purify and separate the valuable metals of the germanium concentrate, obtaining germanium, copper, and cobalt products. This reduces the difficulty of subsequent processing of the recovered germanium metal and improves product quality. This method is simple, requires little equipment investment, is pollution-free, and has good economic benefits, effectively separating impurities from germanium. The composition of the iron-copper-cobalt-germanium material described in this invention includes: 0.25wt%–0.35wt% germanium; 35wt%–50wt% copper; 3wt%–5wt% cobalt; 5wt%–15wt% iron; 0wt%–4wt% arsenic; 0wt%–3wt% nickel; 0wt%–2wt% lead; 0wt%–0.5wt% silicon; and the balance being water. In one embodiment, the composition of the iron-copper-cobalt-germanium material includes: 0.25wt%–0.35wt% germanium, 35wt%–50wt% copper, 3wt%–5wt% cobalt, 5wt%–15wt% iron, 2wt%–4wt% arsenic, 0.5wt%–3wt% nickel, 1wt%–2wt% lead, and 0.2wt%–0.5wt% silicon; the balance being water. In another embodiment, the composition of the iron-copper-cobalt-germanium material includes: 0.33wt% germanium, 42.74wt% copper, 4.21wt% cobalt, 10.23wt% iron, 2.17wt% arsenic, 1.82wt% nickel, 1.49wt% lead, and 0.28wt% silicon; the balance being 36.73wt% water.

[0011] The inventors of this application have creatively discovered that, due to the complexity of the composition of iron-containing copper, cobalt, and germanium materials, each step of this invention is a whole, rather than a single processing method for a single material. The core point is that the separation steps of each valuable metal need to be strictly carried out in the above order, namely: after the iron-containing copper, cobalt, and germanium materials are acid leached, copper is initially separated from other valuable metals; germanium in the leachate is separated from copper, cobalt, and iron elements after germanium extraction and germanium precipitation; and then, by adjusting the pH value of the solution, iron, copper, and cobalt in the solution can be analyzed in sequence, thereby achieving the purpose of separating and purifying each element of the material. Therefore, the separation sequence and pH control of each solution in the purification process of the method described in this invention are particularly critical. For example, the steps of iron precipitation, copper precipitation, and cobalt precipitation cannot be reversed because the pH adjusted for copper precipitation and cobalt precipitation is higher than that for iron precipitation, and the pH for cobalt precipitation is higher than that for copper precipitation. If copper or cobalt is precipitated first, iron will also precipitate, resulting in iron slag mixed in with copper or cobalt slag. If the pH is too high during iron precipitation, some copper will precipitate out. Similarly, if the pH is not properly controlled during copper precipitation, cobalt metal will precipitate together with copper, thus failing to achieve the purpose of separation and purification.

[0012] This invention first involves acid leaching of iron-containing copper-cobalt-germanium materials. Specifically, the iron-containing copper-cobalt-germanium materials are first leached in an acidic solution; the acidic solution is selected from sulfuric acid. This invention does not impose any particular restrictions on the order in which the iron-containing copper-cobalt-germanium materials and the acidic solution are added; the iron-containing copper-cobalt-germanium materials can be added to the acidic solution, or the acidic solution can be added to the iron-containing copper-cobalt-germanium materials.

[0013] This invention may generate hydrogen gas during the acid addition process. The amount of hydrogen gas generated is high at the beginning of the addition of concentrated sulfuric acid, gradually decreasing later. Therefore, the sulfuric acid addition rate must be different at the beginning and end. For the first 0.5 hours, sulfuric acid should be added at a rate of 100 L / h to 200 L / h, and then at a rate of 500 L / h to 1000 L / h, which can be adjusted appropriately within this range. In some embodiments of this invention, after acid leaching of iron-containing copper, cobalt, and germanium materials, the solid material is taken and water is added to make the total volume 27 to 28 m³. 3 Sulfuric acid is then added, with the addition rate being 100-200 L / h for the first 0.5 hours and then 500-1000 L / h thereafter. In one embodiment, the acid leaching treatment is carried out at a pH of 0.3-0.6. In another embodiment, the acid leaching treatment temperature is 85°C-90°C, and the acid leaching time is 3-4 hours.

[0014] Before acid leaching, the iron-containing copper-cobalt-germanium material can be ground. In some embodiments of the invention, the iron-containing copper-cobalt-germanium material is fed into a ball mill via a screw conveyor for grinding. The feed rate of the screw conveyor is controlled at 1000–2000 kg / h, and water is introduced during grinding at a flow rate of 3–6 m³ / h. 3 / h, when the total weight of the input materials reaches 4500-4800 kg wet weight (calculated based on a water content of 36.73 wt%) and the total water flow reaches 12-15 m³ / h. 3 Stop grinding and use a mortar pump to pressurize at 3-6m intervals. 3 The material will be acid-leached at a rate of / h.

[0015] This invention involves acid leaching of iron-containing copper, cobalt, and germanium materials, followed by water washing of the solid material to obtain a washing solution. Specifically, the solid material is washed with water, filtered, and then a washing solution and a washing residue are obtained; the washing residue is a copper by-product. In some embodiments of this invention, the water washing process is carried out at 50–60°C for 3–4 hours.

[0016] In this invention, after obtaining the washing solution, a complexing agent, an organic phase, a back-extraction solution, and the washing solution are mixed and extracted to obtain a raffinate and a post-extraction solution. Specifically, this invention mixes the complexing agent and the washing solution, then adds the organic phase and the back-extraction solution to it for extraction to obtain a raffinate and a post-extraction solution. In one embodiment, the inflow rate of the complexing agent, organic phase, back-extraction solution, and washing solution is 1200–1750 L / h. In one embodiment, the extraction temperature is not higher than 45°C. In one embodiment, the extraction is carried out at a pH of 0.6–0.8. In one embodiment, the amount of the complexing agent is three times the weight of germanium metal in the washing solution. In one embodiment, the complexing agent is selected from at least one of tartaric acid and oxalic acid; the organic phase is selected from at least one of N235 and N263; and the back-extraction solution is selected from at least one of sodium hydroxide and potassium hydroxide.

[0017] Before performing the above-mentioned extraction process, the present invention further includes adjusting the electrode potential of the washing solution after obtaining it. In some embodiments of the present invention, when the electrode potential of the washing solution is ≤360mV, 3kg of iron powder is added to the washing solution; when the electrode potential of the washing solution is >360mV, iron powder is added to the washing solution to make the electrode potential of the washing solution <360mV.

[0018] This invention obtains a germanium product by subjecting the back-extraction solution described in step S2) to germanium precipitation. Specifically, the germanium precipitation treatment in step S2) includes: reacting the back-extraction solution and a germanium precipitant at a pH of 8-9 to obtain the germanium product. In some embodiments of this invention, the germanium precipitant is added to the back-extraction solution, the pH is adjusted to 8-9, and the mixture is stirred to carry out the germanium precipitation reaction to obtain the germanium product. In some embodiments of this invention, the germanium precipitant in step S2) is selected from at least one of ferric chloride and tannin. In one embodiment, the germanium precipitation treatment time is 1 hour to 5 hours, preferably 1 hour.

[0019] In some embodiments of the present invention, the back-extraction solution and ferric chloride solution described in step S2) are mixed for germanium precipitation to obtain a germanium product; the total iron mass in the ferric chloride solution is 4 to 8 times the germanium mass in the back-extraction solution. In one embodiment, the ratio of the back-extraction solution to the ferric chloride solution is 300 kg to 500 kg: 200 L.

[0020] This invention extracts iron, copper, and cobalt byproducts sequentially from the raffinate in step S2) according to the processing order of iron precipitation, copper precipitation, and cobalt precipitation. First, the raffinate in step S2) undergoes iron precipitation treatment. Specifically, the iron precipitation treatment includes: reacting the raffinate in step S2) with an iron precipitant at a pH of 1.5–1.8 to obtain iron byproducts and a post-precipitation liquid. In some embodiments of this invention, the pH of the raffinate is adjusted to 1.5–1.8, an iron precipitant is added to the raffinate, and an iron precipitation reaction is carried out to obtain iron byproducts and a post-precipitation liquid. In one embodiment, the pH of the raffinate is adjusted to 1.5–1.8 at a temperature of 60°C–65°C, preferably to 1.6–1.8. The temperature is then raised to 85–90°C, and an iron precipitant is added to the raffinate to induce an iron precipitation reaction. When the iron content in the raffinate is less than 4 g / L, the addition of the iron precipitant is stopped, and the iron precipitation reaction continues at the same temperature. The mixture is then filtered to obtain an iron by-product and a liquid after iron precipitation. In one embodiment, the iron precipitant is selected from at least one of sodium chlorate or sodium carbonate. In another embodiment, the iron precipitant is selected from sodium chlorate and sodium carbonate, wherein the amount of sodium chloride added is 0.3–0.4 times the weight of the iron in the raffinate, the sodium chloride is added at a rate of 10–50 kg / h, and the concentration of sodium carbonate is 150–250 g / L.

[0021] This invention, after subjecting the raffinate obtained in step S2) to an iron precipitation reaction and filtering, further includes washing the resulting filter residue with water to obtain an iron by-product. Specifically, the filter residue is washed with water until the cobalt content in the filter residue is less than 2000 ppm to obtain the iron by-product. In some embodiments of this invention, the ratio of the amount of filter residue to the amount of water added is 1:6-7, based on a water content of 20 wt%. In one embodiment, the water washing is carried out at a temperature of 50°C-60°C for 3-4 hours. In another embodiment, 12-15 ml of water is added to the filter residue obtained after filtration. 3 Add 3 to 4 tons of wet iron and vanadium slag, based on a moisture content of 20% and a solid-liquid ratio of 1:6 to 7, and wash it with water.

[0022] This invention involves treating the raffinate from step S2) to obtain an iron by-product and a post-iron precipitation solution, followed by copper precipitation treatment of the post-iron precipitation solution. Specifically, the post-iron precipitation solution is subjected to a copper precipitation reaction at a pH of 5.0–5.3 to obtain a copper by-product and an iron precipitation solution. In one embodiment, the copper precipitation reaction takes 1–2 hours. In some embodiments of this invention, after the copper precipitation reaction of the post-iron precipitation solution, the solution is filtered to obtain a copper precipitation reaction residue and an iron precipitation solution. The copper precipitation reaction residue is then washed with water to obtain a copper by-product. In one embodiment, the ratio of the copper precipitation reaction residue to water, based on a water content of 40 wt%, is 1:6–7. In one embodiment, the water washing is performed at a temperature of 50°C–60°C for 3–4 hours.

[0023] This invention involves treating the iron-laden liquid with copper precipitation to obtain copper by-products and iron-laden liquid, followed by cobalt precipitation treatment of the iron-laden liquid. Specifically, the iron-laden liquid is subjected to a cobalt precipitation reaction at a pH of 10.0–10.5 to obtain cobalt by-products. In one embodiment, an alkaline solution is added to the iron-laden liquid at a rate of 500–1500 L / h; in another embodiment, the cobalt precipitation reaction takes 1–2 hours.

[0024] This invention provides a method for separating and purifying iron-containing copper-cobalt-germanium materials. The method effectively separates germanium from other valuable metal components in these materials, allowing for the sequential separation and purification of the remaining valuable metals. The separation is thorough and the process is simple. This invention solves the problems of complex processes, high chemical reagent consumption, high costs, and the generation of large amounts of toxic and harmful gases in current germanium concentrate production processes. It provides a simple refining process that separates germanium from copper, iron, and cobalt, yielding germanium-enriched concentrate. This process is low-cost, energy-efficient, and achieves good separation results. The entire production process requires minimal equipment investment, generates no waste gas, allows for the reuse of most wastewater, and is pollution-free, offering significant economic and social benefits and making it suitable for industrial production. Experiments show that this invention successfully separates germanium, iron, cobalt, and copper from iron-containing copper-cobalt-germanium materials, achieving a germanium recovery rate of over 95%. Iron, cobalt, and copper byproducts are also successfully separated and purified. Attached Figure Description

[0025] Figure 1 is a process flow diagram of the separation and purification method for iron-containing copper, cobalt, and germanium materials according to the present invention. Detailed Implementation

[0026] This invention discloses a method for separating and purifying iron-containing copper, cobalt, and germanium materials. Those skilled in the art can refer to this document and appropriately modify the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The method and application of this invention have been described through preferred embodiments. Those skilled in the art can clearly modify or appropriately change and combine the method and application described herein without departing from the content, spirit, and scope of this invention to implement and apply the technology of this invention.

[0027] The present invention will be further described below with reference to the embodiments:

[0028] Example 1

[0029] An industrial process is used to process an iron-copper-cobalt-germanium material with the following composition: germanium content 0.33%, copper content 42.74%, cobalt content 4.21%, iron content 10.23%, arsenic content 2.17%, nickel content 1.82%, lead content 1.49%, silicon content 0.28%, and moisture content 36.73%. Germanium is extracted from the iron-copper-cobalt-germanium material. In this case, a batch processing volume of 4777 kg was used. The main equipment used included a ball mill, filter press, stirring tank, and extractor. Before feeding, all equipment, material pipelines, and ventilation systems were strictly checked for proper functioning. The separation and purification process flow of this invention is shown in Figure 1. Figure 1 is a process flow diagram of the separation and purification method for iron-copper-cobalt-germanium material according to this invention. The specific steps are as follows:

[0030] 1. Ball Mill Feeding: After confirming that the equipment is in normal working order, feed the iron-containing copper, cobalt, and germanium material into the ball mill via a screw conveyor. Control the screw conveyor feed rate to 1500 kg / h (wet weight). Simultaneously, open the ball mill's tap water inlet valve and adjust the water flow rate to 4 m³ / h. 3 / h, when the total weight of the input materials reaches 4800kg wet weight and the total water inflow reaches 14m³ 3 Turn off the ball mill. After ball milling, pump the slurry using a mortar pump at a speed of 4.0 m / s. 3 / h, pumped into the leaching tank.

[0031] 2. Acid leaching heating: Check whether the leaching tank, ball mill, and its exhaust, stirring, and related pipeline valves are normal. Turn on the stirring and exhaust of the leaching tank, and add tap water to the leaching tank to make the final total volume of the tank 27m³. 3 With stirring and ventilation enabled, concentrated sulfuric acid was added. For the first 0.5 hours, the sulfuric acid was added to the leaching tank at a rate of 150 L / h. After 0.5 hours, the rate was increased to 750 L / h. The total amount of sulfuric acid added was equal to the feed amount * 0.5 + 50 (in L). The pH was controlled between 0.3 and 0.6 at the reaction endpoint. After adding the concentrated sulfuric acid, the tank temperature was raised to 85°C, and the reaction was stirred and maintained at a constant temperature for 4 hours.

[0032] 3. Acid leaching residue washing: Check the washing tank, belt conveyor, agitator, and related pipeline valves for proper functioning. Turn on the agitator and ventilation in the leaching tank, and add 10m³ of tap water to the leaching tank. 3 Then, add two batches of leaching residue, about 3200 kg, and start heating at the same time. After the materials are added, keep the temperature at 55℃ and stir for 4 hours. After the temperature is maintained, filter by pressing. After washing with water, filter by pressing again. The filtrate is reused in the acid leaching process. The filter residue is bagged, the copper content is tested, and it is temporarily stored as a copper by-product.

[0033] 4. Pretreatment before germanium extraction: Start stirring and take a sample to measure the electrode potential. If the electrode potential is ≤360mV, add 3kg of iron powder. If the electrode potential is >360mV, add an appropriate amount of iron powder for reduction to control the electrode potential <360mV. Then add tartaric acid at 3 times the weight of germanium metal, 32kg per batch. Take a sample to measure the pH value of the solution. Control the pH value to 0.7 with liquid alkali. After adding the liquid alkali, continue stirring for 10 minutes until stable, then confirm the pH value. After adjusting the pH value, stop stirring to prevent oxidation.

[0034] 5. Germanium Extraction: The extraction temperature should not exceed 45℃ (pre-extraction treatment does not require heating). Check and confirm that the pipeline connections and valve openings are correct. Turn on the stirring motor of the extraction system, and then simultaneously turn on all feed pumps. The feed liquid flow rate is 1200L / h. The organic phase flow rate is adjusted according to the feed liquid flow rate at an oil-to-water ratio of 1:1. The back-extraction solution is adjusted to 1 / 10 of the feed liquid flow rate, and the actual reading is 1 / 5 of the feed liquid flow rate. The water washing solution flow rate is 400L / h. The water washing solution is not recycled but reused in the leaching step. Prepare a 120g / L NaOH solution as the back-extraction solution. It should be prepared in a timely manner to ensure normal extraction. After back-extraction, the solution is pumped to the germanium precipitation tank for germanium precipitation. The residual extract is transferred to the copper precipitation process.

[0035] 6. Germanium precipitation: Check the germanium precipitation tank, its ventilation, agitation, and related pipeline valves to ensure they are functioning properly. Turn on the agitation in the germanium precipitation tank. For each tank (approximately 25m³),... 3 Add 400 kg of deep-precipitated germanium material to the solution, then add 200 L of ferric chloride solution. Calculate the total mass of iron and germanium, with the iron mass being 6 times the germanium mass. Then add sulfuric acid to adjust the pH to 8.8, continue stirring for 1 hour, take a sample for testing of germanium and arsenic until the germanium content is <10 ppm, thus completing the germanium precipitation. Perform pressure filtration, pack the filter residue and send it to the primary chlorination distillation, and then discharge it to the wastewater treatment workshop.

[0036] 7. Iron precipitation: Close the outlet valve of the iron removal stirring tank, check the equipment for damage, start the agitator, add the raffinate, and heat with steam to 65℃. At a constant temperature of 65℃, add liquid alkali to adjust the pH to 1.6, then continue heating to 85℃. Calculate the amount of sodium chlorate to add based on the iron content in the solution. The amount of sodium chlorate should be 0.4 times the weight of the iron, added at a rate of 20 kg / h. Simultaneously, add 200 g / L liquid sodium carbonate to maintain the pH at 1.7. Strictly control the pH at 1.7 during the iron precipitation oxidation process. Measure the pH every 30 minutes during the addition of sodium chlorate or sodium carbonate solution; the pH should not exceed 1.8. Take a sample from each tank during the iron precipitation oxidation process to test the iron content. When the iron content is less than 4 g / L, stop adding sodium chlorate and continue the reaction at the specified temperature for 4 hours.

[0037] 8. Iron slag washing: Inspect the washing tank and belt conveyor equipment to ensure they are operating properly. With the agitator and exhaust fan on, add 14m³ of water. 3 Four tons of wet iron-vanadium slag, with a moisture content of 20%, were added to the filter residue at a solid-liquid ratio of 1:6 via a belt conveyor while the heating process was initiated. After the materials were added, the temperature was maintained at 55°C, and the mixture was stirred and reacted for 4 hours. The filter residue was then tested for cobalt content. If the cobalt content was greater than 2000 ppm, it needed to be washed again to reduce the cobalt content to less than 2000 ppm. Once qualified, the filter residue was bagged and classified as an iron by-product.

[0038] 9. Copper plating: Check the reaction tank, its ventilation, stirring and supporting pipeline valves to ensure they are normal. Turn on the stirring and check that the ventilation system is normal. With the stirring and ventilation turned on, start adding liquid alkali at a rate of 1200L / h. Control the pH at the end point to be 5.2. After adding the liquid alkali, stir the reaction for 2 hours. If the pH value is 5.2 again, then filter by pressure.

[0039] 10. Copper slag washing: Inspect the washing tank and belt conveyor to ensure they are operating properly. With the agitator and exhaust fan on, add 14m³ of water. 3 Add a small amount of sulfuric acid with an acidity of 0.5%. The copper slag contains 40% moisture. Add 4 tons of wet copper slag at a solid-liquid ratio of 1:6 and feed it via belt conveyor. At the same time, start heating. After the materials are added, keep the temperature at 55°C and stir the reaction for 4 hours. After the heat preservation is completed, filter the mixture.

[0040] 11. Cobalt precipitation: Check whether the agitator and exhaust system of the cobalt precipitation tank are normal. With the agitator and exhaust system turned on, start adding liquid alkali at a rate of 1200L / h. Control the pH at the end point to be 10.5. After adding the liquid alkali, stir and react for 2 hours. If the pH value is 10.5 again, then filter by pressure.

[0041] The analysis results obtained by processing copper-cobalt-germanium-containing materials using the above process are shown in Table 1.

[0042] Table 1

[0043] Germanium concentration in the solution before precipitation (ppm) / Germanium concentration in the solution after precipitation (ppm) 186 162 104 39 37 251 surface

[0044] As shown in Table 1, the method of the present invention controls the process conditions at each stage of the production process, first using leaching precipitation to remove impurities, and then using extraction to purify germanium, so that the germanium recovery rate can reach more than 95%, achieving the purpose of recovering and enriching germanium, which not only does not pollute the environment but also improves the germanium recovery rate.

[0045] The analysis results for each by-product are shown in Table 2:

[0046] Table 2

[0047] Element Detection: Ge / % Cu / % Co / % Fe / % As / % Ni / % Moisture / % Iron By-products: 0.03 1.91 0.17 29.16 8.71 0.06 33.25 Cobalt By-products: 0.02 7.53 25.55 0.13 / 8.17 71.62 Copper By-products: 0.07 50.05 0.51 3.86 0.91 0.21 41.17 Acid Leaching By-products: 0.03 48.71 0.35 4.72 0.74 0.14 28.97 surface

[0048] The results in Table 2 above further confirm that the germanium in the raw materials was recovered very thoroughly, and that the separation of iron, copper, cobalt, nickel, etc. has achieved the purpose of purification. The produced germanium products can be used for further purification in downstream processes.

[0049] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for separating and purifying iron-, copper-, cobalt-, and germanium-containing materials, characterized in that, The process is as follows: S1) After acid leaching of the iron-containing copper, cobalt, and germanium material, the solid material is washed with water to obtain a washing solution; the acid leaching is carried out at a pH of 0.3 to 0.6; S2) The complexing agent and the washing solution obtained in step S1) are mixed, and an organic phase and a back-extraction solution are added to the mixture for extraction to obtain a raffinate and a back-extraction solution; the organic phase is N263; the complexing agent is at least one of tartaric acid and oxalic acid; the back-extraction solution is at least one of sodium hydroxide and potassium hydroxide; the extraction is carried out at a pH of 0.6 to 0.8; S3) Iron by-products, copper by-products, and cobalt by-products are extracted sequentially from the raffinate in step S2) according to the processing order of iron precipitation, copper precipitation, and cobalt precipitation.

2. The method according to claim 1, characterized in that, The germanium product is obtained by subjecting the back-extraction liquid described in step S2) to germanium precipitation treatment.

3. The method according to claim 2, characterized in that, The germanium precipitation process described in step S2) specifically includes: performing a germanium precipitation reaction between the back-extraction liquid and the germanium precipitant at a pH of 8-9.

4. The method according to claim 3, characterized in that, The iron precipitation treatment in step S3) specifically includes: carrying out an iron precipitation reaction between the raffinate and the iron precipitant in step S2) at a pH of 1.5 to 1.8 to obtain iron by-products and iron precipitation liquid.

5. The method according to claim 4, characterized in that, The copper precipitation process described in step S3) specifically includes: subjecting the iron precipitation liquid to a copper precipitation reaction at a pH of 5.0~5.3 to obtain copper by-products and iron precipitation liquid.

6. The method according to claim 5, characterized in that, The cobalt precipitation process described in step S3) specifically includes: subjecting the iron precipitate to a cobalt precipitation reaction at a pH of 10.0~10.5 to obtain a cobalt byproduct.

7. The method according to claim 6, characterized in that, The acid leaching treatment in step S1) is carried out in sulfuric acid; the germanium precipitant in step S2) is selected from at least one of ferric chloride and tannin; the iron precipitant in step S3) is at least one of sodium chlorate or sodium carbonate.

8. The method according to any one of claims 1 to 7, characterized in that, The composition of the iron-copper-cobalt-germanium material includes: 0.25 wt% to 0.35 wt% germanium; 35 wt% to 50 wt% copper; 3 wt% to 5 wt% cobalt; 5 wt% to 15 wt% iron; 0 wt% to 4 wt% arsenic; 0 wt% to 3 wt% nickel; 0 wt% to 2 wt% lead; 0 wt% to 0.5 wt% silicon; and the balance being water.

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