Method for improving grade of germanium deposition material through germanium deposition of extraction liquid

Abstract

The invention discloses a method for improving the grade of a germanium-deposited material by depositing germanium in extract liquor, which comprises the following steps: (1) pre-neutralization operation: adding a neutralizer into the extract liquor containing germanium, carrying out neutralization reaction, and carrying out filter pressing after the reaction is completed to obtain a clear solution; (2) germanium deposition operation: adding a germanium deposition agent into the pre-neutralized clear solution, and carrying out germanium deposition reaction; and (3) filter pressing operation: filtering the mixed solution after the germanium precipitation reaction, and washing filter residues to obtain a high-grade germanium precipitation material. The method effectively solves the problems of low germanium precipitation material grade and serious impurity entrainment in the germanium precipitation process of the extract liquor, significantly improves the germanium grade of the germanium precipitation material by optimizing pre-neutralization clarification, accurately controlling the dosage of the germanium precipitation agent and adopting a sectional washing process, further efficiently recovers germanium metal, and reduces the production cost. The resource comprehensive utilization rate and the economic benefit are improved.

Description

Technical Field

[0001] This invention relates to the field of metallurgical technology, and more specifically to a method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract. Background Technology

[0002] In the hydrometallurgical processes of lead and zinc or indium smelting, germanium-containing raffinates are generated. Currently, the germanium grade of the precipitated material obtained from these solutions is generally low, typically only around 1.5%. Although such low-grade materials are marketable, their economic value is limited, and the costs associated with subsequent transportation, processing, or sales are high. Effectively improving the germanium grade of the precipitated material would not only significantly enhance the recovery efficiency of germanium metal but also reduce the processing load and costs of subsequent refining processes, which is of great significance for improving the comprehensive utilization of resources and enhancing corporate economic benefits. Existing technologies lack a simple and efficient method for system optimization of the germanium precipitation process in the raffinate to directly obtain high-grade germanium precipitates.

[0003] Currently, the germanium content of the precipitated material obtained from the recovery of germanium from the raffinate solution is generally low, typically only around 1.5%. Although such low-grade materials are available for sale, their economic value is limited, and the costs in subsequent transportation, processing, or sales are high.

[0004] Therefore, how to develop a method to effectively improve the grade of germanium precipitated in the extract has become a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, the present invention provides a method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract. The present invention effectively solves the problems of low grade and severe impurity entrainment in the germanium-precipitated material during the extraction process. By optimizing pre-neutralization and clarification, precisely controlling the dosage of the germanium-precipitating agent, and adopting a segmented washing process, the germanium grade of the precipitated material is significantly improved, further enabling efficient recovery of germanium metal and improving resource utilization and economic benefits.

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

[0007] A method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract includes the following steps: (1) Pre-neutralization operation: Add a neutralizing agent to the extract containing germanium to carry out the neutralization reaction. After the reaction is completed, filter the solution by pressure, and focus on ensuring the clarity of the solution obtained by pressure filtration. (2) Germanium precipitation process: Add a germanium precipitating agent to the pre-neutralized clear solution to carry out the germanium precipitation reaction. The key is to accurately control the amount of germanium precipitating agent used. (3) Filtration operation: The mixture after the germanium precipitation reaction is filtered and the filter residue is washed to obtain high-grade germanium precipitation material.

[0008] This invention effectively solves the problems of low grade and high impurity content in the materials obtained from germanium precipitation from extracts in existing technologies. By enhancing the clarification effect of the pre-neutralization solution, impurities entering the precipitation system are reduced from the source; by optimizing the dosage of germanium precipitating agent, high recovery rate is ensured while avoiding grade dilution caused by excessive precipitation; and an innovative two-stage washing process of "acid washing + water washing" is adopted to effectively remove impurities and residual reagents entrained in the precipitate, thereby achieving a significant improvement in the grade of the germanium precipitated material.

[0009] Preferably, in step (1), the neutralizing agent is zinc calcinate. Zinc calcinate can not only effectively neutralize free acid in the solution, but some of its components may also promote the coagulation and sedimentation of impurities, which is beneficial for subsequent filtration and clarification.

[0010] Clarification of the filter press solution refers to obtaining a solution that is visually clear and transparent, free of obvious residue or impurities, through a filter press operation. Sufficient clarification of the solution is a crucial prerequisite for ensuring the efficiency of the subsequent germanium precipitation reaction and reducing the co-precipitation of impurities.

[0011] Preferably, in step (2), the germanium precipitant is taratanine. Taratanine can form a stable complex precipitate with germanium and has good selectivity.

[0012] The dosage of the germanium precipitation agent should be appropriate, typically added at 20-40 times the mass of germanium metal in the solution. The precise criterion for determining the final dosage is whether the germanium content in the solution after precipitation reaches the minimum requirement of the process. Adding too much will lead to an increase in the volume of the precipitate, carrying more impurities, which will reduce the material grade and increase unnecessary auxiliary material costs; adding too little will result in incomplete precipitation and a decrease in germanium metal recovery rate.

[0013] Preferably, in step (3), the filter press operation is specifically a three-stage process: The first step is a primary acid wash: the mixture after the germanium precipitation reaction is pumped to an acid wash filter press for pressure filtration and separation, and the resulting filtrate overflows into the combined post-liquid storage tank; the filter residue (i.e. the initial germanium precipitate) enters the slurry tank and is slurry washed with concentrated sulfuric acid in order to dissolve certain acid-soluble impurities and unreacted germanium precipitating agents carried in the filter residue. The second step is a primary water wash: the material after the primary acid washing and pulping is pumped to a water washing filter press for filtration, and the resulting filtrate overflows into a combined post-liquid storage tank; the filter residue enters the pulping tank again and is pulped and washed with production water to remove residual acid and soluble salts; The third step is the slag discharge of germanium-precipitated material: the material after the first washing and slurrying is sent to the diaphragm filter press for final filtration and dewatering through a conveying pump. The resulting filtrate overflows into the comprehensive post-liquid storage tank, and the filter cake is the purified high-grade germanium-precipitated material.

[0014] As can be seen from the above technical solution, compared with the prior art, the present invention has the following technical effects: Process Innovation: This invention combines pre-neutralization and clarification control, precise regulation of germanium precipitation agent dosage, and a specific two-stage washing process to form a systematic quality improvement process. The process steps are clear, highly operable, and easily implemented and applied to existing production facilities.

[0015] Innovative Processing Effect: Applying the method of this invention, the germanium grade of germanium-precipitated materials can be significantly increased from approximately 1.5% to 3.0%, effectively enriching germanium metal. While improving the main metal recovery rate, it also reduces the impurity content in the product, enhances the direct economic value of the material, and creates favorable conditions for subsequent deep extraction of germanium, thus improving the overall resource utilization rate and process economic benefits. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0017] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0018] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1 This embodiment provides a method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract, including the following steps: (1) Pre-neutralization process: Add zinc calcinate to the extract containing germanium to carry out the neutralization reaction. After the reaction is completed, filter under pressure to obtain a solution that is visually clear and transparent with no obvious residue or impurities. (2) Germanium precipitation: Add taratin to the pre-neutralized clear solution to carry out the germanium precipitation reaction. The key is to accurately control the amount of germanium precipitating agent. (3) Filtration operation: The mixture after the germanium precipitation reaction is sent to the acid washing filter press for filtration separation by a transfer pump. The resulting filtrate overflows into the comprehensive liquid storage tank; the filter residue (i.e. the initial germanium precipitate) enters the slurry tank and is slurry washed with concentrated sulfuric acid. The material after the first pickling and pulping is sent to a water washing filter press for filtration by a conveying pump. The resulting filtrate overflows into the combined post-liquid storage tank. The filter residue enters the pulping tank again and is pulped and washed with production water. The material after washing and pulping is pumped to a diaphragm filter press for final filtration and dewatering. The resulting filtrate overflows into a combined post-liquid storage tank, and the filter cake is the purified high-grade germanium precipitate.

[0020] Comparative Example 1 (Comparative example for clarification of pre-neutralization solution) 1. Clarification of the pre-neutralization solution Pre-neutralization operation: 200ml of raffinate 3 It contains 165 mg / L germanium. After adding 20 tons of zinc calcinate, the pre-neutralized raffinate contains 9.5 g / L acid, 85 g / L zinc, and 1.3 g / L ferric iron.

[0021] The filter solution was clear and free of obvious impurities. The germanium precipitation solution contained 5 mg / L of germanium, and the germanium content in the precipitated material was 2.16%.

[0022] 2. The pre-neutralization solution was turbid. Pre-neutralization operation: 200ml of raffinate 3 It contains 160 mg / L germanium. After adding 20 tons of zinc calcinate, the pre-neutralized raffinate contains 9.6 g / L acid, 86 g / L zinc, and 1.2 g / L ferric iron.

[0023] The filter press solution was turbid. After the germanium precipitation process, the solution contained 15 mg / L of germanium, and the germanium content in the precipitated material was 0.80%.

[0024] The comparison shows that the clarification effect of the pre-neutralization solution has a significant impact on the grade of the germanium precipitate. In conclusion, the clarification of the pre-neutralization solution is the optimal one.

[0025] Comparative Example 2 (Comparative example regarding the amount of germanium precipitating agent used in germanium precipitation operations) 1. Add germanium precipitating agent at a ratio of 36 times the germanium metal content of the solution. Germanium precipitation process: 200 ml of raffinate pre-neutralization solution 3 The sample contained 105 mg / L of germanium. 0.75 tons of taratin were added (36 times the amount of germanium metal added during pre-neutralization of the raffinate). Under the conditions of temperature of 55-65℃, time of 1-2 hours, and uniform stirring, the germanium-precipitated liquid contained 8 mg / L of germanium, and the germanium-precipitated material contained 1.65% germanium.

[0026] 2. Add the germanium precipitating agent at a ratio of 43 times the germanium metal content of the solution. Germanium precipitation process: 200 ml of raffinate pre-neutralization solution 3The sample contained 105 mg / L of germanium. 0.90 tons of taratin were added (43 times the amount of germanium metal added in the pre-neutralization of the raffinate). Under the conditions of temperature of 55-65℃, time of 1-2 hours, and uniform stirring, the germanium-precipitated liquid contained 0.5 mg / L of germanium, and the germanium-precipitated material contained 1.38% germanium.

[0027] The comparison shows that the amount of germanium precipitating agent used in germanium precipitation has a significant impact on the grade of germanium precipitated material. In summary, precise addition of germanium precipitating agent is the optimal method in germanium precipitation. The precise criterion for the final addition amount is that the germanium content in the solution after germanium precipitation is 5-10 mg / L.

[0028] Comparative Example 3 (Comparative example using a two-stage washing method in the filter press operation) 1. Filter press operation without washing Germanium precipitation process: 200 ml of raffinate pre-neutralization solution 3 The sample contained 105 mg / L of germanium. 0.75 tons of taratin were added (36 times the amount of germanium metal added during pre-neutralization of the raffinate). Under the conditions of temperature of 55-65℃, time of 1-2 hours, and uniform stirring, the germanium-precipitated liquid contained 8 mg / L of germanium, and the germanium-precipitated material contained 1.65% germanium.

[0029] 2. Two-stage washing in filter press operation Germanium precipitation process: 200 ml of raffinate pre-neutralization solution 3 The sample contained 105 mg / L of germanium. 0.75 tons of taratin were added (36 times the amount of germanium metal added during pre-neutralization of the raffinate). Under the conditions of temperature of 55-65℃, time of 1-2 hours, and uniform stirring, the germanium-precipitated liquid contained 8 mg / L of germanium, and the germanium-precipitated material contained 1.65% germanium.

[0030] Filtration process: After the germanium-precipitated material is acid-washed once with concentrated sulfuric acid, the germanium content of the slag material is increased to 2.31%. After washing once with production water, the germanium content of the slag material is increased to 3.08%. The high-germanium material is produced by the filtration process.

[0031] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from other embodiments. Similar or identical parts between embodiments can be referred to interchangeably. For the apparatus disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the description is relatively simple; relevant parts can be referred to the method section.

[0032] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract, characterized in that, Includes the following steps: (1) Pre-neutralization process: Add a neutralizing agent to the extract containing germanium to carry out the neutralization reaction. After the reaction is completed, filter under pressure to obtain a clear solution; (2) Germanium precipitation process: Add a germanium precipitating agent to the pre-neutralized clear solution to carry out the germanium precipitation reaction; (3) Filtration operation: The mixture after the germanium precipitation reaction is filtered and the filter residue is washed to obtain high-grade germanium precipitation material.

2. The method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract according to claim 1, characterized in that, The neutralizing agent mentioned in step (1) is zinc calcinate.

3. The method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract according to claim 1, characterized in that, The clarified solution mentioned in step (1) is a solution that is visually clear and transparent, without obvious residue or impurities.

4. The method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract according to claim 1, characterized in that, The germanium precipitant mentioned in step (2) is taratanine.

5. The method for improving the grade of germanium-precipitated material by precipitating germanium with an extract according to claim 4, characterized in that, The amount of germanium precipitant added in step (2) is 20 to 40 times the mass of germanium metal in the clarified solution.

6. The method for improving the grade of germanium-precipitated materials by precipitating germanium in an extract according to claim 1, characterized in that, Step (3) of the filter press operation is specifically divided into three stages: The first step is a single acid wash: the mixture after the germanium precipitation reaction is pumped to an acid wash filter press for filter separation, and the resulting filtrate overflows into a combined post-liquid storage tank; the filter residue enters a slurry tank and is slurry washed with concentrated sulfuric acid; The second step is a primary water wash: the material after the primary acid washing and pulping is sent to a water washing filter press for filtration by a conveying pump, and the resulting filtrate overflows into a comprehensive post-liquid storage tank; the filter residue enters the pulping tank again and is pulped and washed using production water. The third step is the slag discharge of germanium-precipitated material: the material after the first washing and slurrying is sent to the diaphragm filter press for final filtration and dewatering through a conveying pump. The resulting filtrate overflows into the comprehensive post-liquid storage tank, and the filter cake is the purified high-grade germanium-precipitated material.

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