A method for separating and enriching gallium germanium from a low-concentration gallium germanium solution

Abstract

The application provides a method for separating and enriching gallium germanium in a low-concentration gallium germanium-containing solution and relates to the technical field of resource comprehensive recycling. The method comprises the following steps: firstly, preparing a new extraction organic phase, mixing the new extraction organic phase with the gallium germanium-containing solution, extracting, and separating the phases after extraction to obtain a germanium-rich organic phase and a germanium-lean aqueous phase; then, adding a neutralizing agent to the germanium-lean aqueous phase to pre-neutralize and adjust the acid, adding a reducing agent, separating the liquid and solid after the reaction is completed, and obtaining a pretreated liquid; finally, mixing the germanium-rich organic phase with the pretreated liquid, extracting, and separating the phases to obtain a gallium- and germanium-rich organic phase and a gallium-lean raffinate. The method can effectively separate gallium and germanium from impurity elements such as zinc, iron, cadmium, copper, cobalt and nickel in the gallium germanium-containing solution, realizes efficient enrichment and recovery of gallium germanium, has the advantages of simple operation, simultaneous separation of gallium and germanium, effective control of the concentration of organic matter in the raffinate and significant inhibition of iron co-extraction.

Description

Technical Field

[0001] This invention relates to the field of comprehensive resource recycling technology, and in particular to a method for separating and enriching gallium and germanium from a low-concentration gallium-germanium solution. Background Technology

[0002] Gallium and germanium are both strategically important rare metals, widely used in key fields such as infrared optics, fiber optic communication, high-frequency electronics, semiconductor devices, aerospace, and defense. Due to their unique physicochemical properties, they have become indispensable core materials for modern optoelectronics and high-end equipment manufacturing. Germanium, with its excellent infrared transmittance, high carrier mobility, and superior optical properties, plays an irreplaceable role in devices such as infrared thermal imaging lenses, 5G / 6G fiber optic communication, high-speed transistors, and multi-junction photovoltaic cells. Gallium and its compounds, with their excellent semiconductor properties, occupy a key position in third-generation semiconductors, radio frequency devices, chips, and advanced electronic packaging, jointly supporting the high-quality development of next-generation information technology and defense technology. Therefore, the separation and recovery of gallium and germanium is of significant strategic importance.

[0003] Gallium and germanium are dispersed in nature, rarely forming independent deposits, and mainly occurring as associated minerals in zinc sulfide ores, lignite, and bauxite. Gallium-germanium-containing solutions produced during zinc smelting are currently an important source of raw materials for gallium and germanium extraction. The YW100 (oxime acid)-P204 extraction system is a process that has been industrially applied, offering advantages such as good selectivity and high gallium-germanium recovery rates. However, the extractant YW100 has high water solubility, resulting in significant losses during the extraction cycle; moreover, this system exhibits significant iron co-extraction during extraction, which is detrimental to subsequent deep separation of gallium and germanium; furthermore, the extractant dissolved in the aqueous phase entering the main metal production system can adversely affect the main process, becoming a key technical challenge that urgently needs to be addressed in the industry.

[0004] Therefore, based on the idea of ​​controlling the dissolution of YW100 extractant, inhibiting iron co-extraction, and ensuring gallium-germanium extraction efficiency, this invention designs and develops a new method for the economical and effective separation and enrichment of gallium-germanium from low-concentration gallium-germanium solutions. Summary of the Invention

[0005] To address the problems of high water solubility and significant loss of the extractant in the existing YW100 system extraction and separation process for gallium and germanium, the adverse effects of dissolved extractant entering the main smelting system on production, and significant iron co-extraction, this invention provides a method for separating and enriching gallium and germanium from a low-concentration gallium-germanium solution. This invention uses a primary amine as the core reagent to inhibit the dissolution of alkyl oxime acids, designs a novel oxime acid-primary amine-phosphate composite extraction system, and introduces a reduction pretreatment step to suppress iron co-extraction. Through the design of the extraction system, efficient separation and enrichment of gallium and germanium in sulfuric acid medium are achieved while controlling extractant dissolution and reducing extractant consumption. The technical solution is as follows:

[0006] A method for separating and enriching gallium and germanium from a low-concentration gallium-germanium solution, the method comprising: S1. Preparation of a new organic phase for extraction: The extractant, hydrolysis inhibitor, modifier and diluent are mixed evenly to obtain a new organic phase for extraction. S2, Extraction and separation of germanium: The newly prepared organic phase for extraction was mixed with a gallium-germanium-containing solution and extracted. After extraction, the phases were separated by standing to obtain a germanium-rich organic phase and a germanium-poor aqueous phase. S3, Iron co-extraction inhibition pretreatment: The germanium-poor aqueous phase obtained in S2 was pre-neutralized and acidified with a neutralizing agent, and then a reducing agent was added. After the reaction was completed, liquid and solid separation was performed to obtain the pretreated solution. S4. Extraction and separation of gallium: The germanium-rich organic phase obtained in S2 was mixed with the pretreatment solution obtained in S3 and extracted. After extraction, the mixture was allowed to stand and separate to obtain gallium-rich organic phase, germanium-rich organic phase and gallium-poor raffinate.

[0007] The extractant in S1 is alkyloxime acid, the hydrolysis inhibitor is secondary carbon amine or n-octylamine, the modifier is tributyl phosphate or trioctyl phosphate, and the diluent is kerosene or sulfonated kerosene.

[0008] The extractant has a volume concentration of 0.5% to 5% in the newly extracted organic phase, the hydrolysis inhibitor has a volume concentration of 1% to 20% in the newly extracted organic phase, and the modifier has a volume concentration of 5% to 10% in the newly extracted organic phase.

[0009] The sulfuric acid concentration in the gallium-germanium solution in S2 is 50~120g / L, and the gallium-germanium concentration is less than 200mg / L.

[0010] In S2, the newly extracted organic phase is mixed with a gallium-germanium-containing solution for extraction at room temperature for 5-10 minutes, with a phase ratio of 1.

[0011] The neutralizing agent in S3 is zinc calcined sand or zinc oxide. The germanium-poor aqueous phase is pre-neutralized with the neutralizing agent to adjust the pH to 0.5~1.0.

[0012] The reducing agent in S3 is zinc powder or iron powder, and the molar ratio is: reducing agent:Fe 3+ The metal ions were added in a 1:2 ratio, reacted at room temperature for 30 minutes, and the final pH was controlled to not exceed 1.5 to ensure complete reduction and prevent hydrolysis of the metal ions. Among them, Fe... 3+ For the original Fe in the solution 3+ .

[0013] In S4, the extraction temperature is room temperature, the extraction time is 5-10 min, the phase ratio is 1, and the pH at the extraction endpoint is controlled at 2.0-2.5.

[0014] The gallium- and germanium-rich organic phase obtained in S4 can be separated from the organic phase by referring to existing segmented back-extraction methods, such as first back-extracting germanium with ammonia or ammonium fluoride, and then back-extracting gallium with sulfuric acid.

[0015] The beneficial effects of the technical solutions provided in the embodiments of the present invention include at least the following: The above scheme can effectively reduce the dissolution of the extractant in the aqueous phase during the extraction process, inhibit the co-extraction of iron during the extraction process, and achieve efficient extraction and separation of gallium and germanium. It is an efficient and green method for the separation and enrichment of gallium and germanium. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying 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.

[0017] Figure 1 This is a flowchart of a method for separating and enriching gallium and germanium in a low-concentration gallium-germanium solution provided in an embodiment of the present invention. Detailed Implementation

[0018] The technical solution of the present invention will now be described with reference to the accompanying drawings.

[0019] In embodiments of the present invention, words such as "exemplarily," "for example," etc., are used to indicate that something is an example, illustration, or description. Any embodiment or design described as "exemplary" in the present invention should not be construed as being more preferred or advantageous than other embodiments or designs. Specifically, the use of the word "exemplary" is intended to present the concept in a concrete manner. Furthermore, in embodiments of the present invention, the meaning expressed by "and / or" can be both, or either one.

[0020] In this embodiment of the invention, sometimes a subscript such as W1 may be written in a non-subscript form such as W1. When the difference is not emphasized, the meaning they express is the same.

[0021] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.

[0022] This invention provides a method for separating and enriching gallium and germanium in a low-concentration gallium-germanium solution. For example... Figure 1 The flowchart shown illustrates a method for separating and enriching gallium and germanium from a low-concentration gallium-germanium solution. This method may include the following steps:

[0023] S1. Preparation of a new organic phase for extraction: The extractant, hydrolysis inhibitor, modifier and diluent are mixed evenly to obtain a new organic phase for extraction. S2, Extraction and separation of germanium: The newly prepared organic phase for extraction was mixed with a gallium-germanium-containing solution and extracted. After extraction, the phases were separated by standing to obtain a germanium-rich organic phase and a germanium-poor aqueous phase. S3, Iron co-extraction inhibition pretreatment: The germanium-poor aqueous phase obtained in S2 was pre-neutralized and acidified with a neutralizing agent, and then a reducing agent was added. After the reaction was completed, liquid and solid separation was performed to obtain the pretreated solution. S4. Extraction and separation of gallium: The germanium-rich organic phase obtained in S2 was mixed with the pretreatment solution obtained in S3 and extracted. After extraction, the mixture was allowed to stand and separate to obtain gallium-rich organic phase, germanium-rich organic phase and gallium-poor raffinate.

[0024] The following description, in conjunction with specific embodiments, illustrates this point.

[0025] Example 1 A method for separating and enriching gallium and germanium from low-concentration gallium-germanium solutions S1, a freshly extracted organic phase (0.5v% alkyloxime acid + 1v% secondary carbon primary amine + 5v% tributyl phosphate + sulfonated kerosene) was mixed with a gallium-germanium solution (Ge 0.1g / L, Ga 0.1g / L, Zn 20.12g / L, Fe 0.42g / L, Cd 3.16g / L, Cu 2.65g / L, Co 0.14g / L, Ni 0.1g / L, H2SO4 120g / L). Extraction was performed under the conditions of phase O / A=1, room temperature, and 10 min. After extraction, the phases were separated by standing to obtain a germanium-rich organic phase and a germanium-poor aqueous phase. After three stages of countercurrent extraction, the germanium extraction rate was 95.56%, and other metal ions were basically not extracted. The total organic carbon concentration of the raffinate was less than 100mg / L.

[0026] S2, using zinc calcined ore as a neutralizing agent, adjusts the pH of the germanium-poor aqueous phase obtained in S1 to 0.5. Zinc powder is used as a reducing agent, according to the following ratio (mol): Fe 3+ Add (mol) in a 1:2 ratio, react at room temperature for 30 min, and then rapidly separate the liquid and solid to obtain the pretreated solution.

[0027] In step S3, the germanium-rich organic phase extracted from germanium in step S1 was mixed with the pretreatment solution from step S2, and extraction was performed under conditions of O / A = 1, room temperature, and 10 min. After extraction, the phases were separated by standing to obtain a gallium-rich germanium organic phase and a gallium-poor aqueous phase. After four stages of countercurrent extraction, the gallium extraction rate reached 96.32%, the extraction rate of other metal ions was less than 1%, and the total organic carbon concentration of the raffinate was less than 80 mg / L.

[0028] Example 2 A method for separating and enriching gallium and germanium from low-concentration gallium-germanium solutions S1, a freshly extracted organic phase (3.0 v% alkyloxime acid + 5 v% secondary carbon primary amine + 10 v% tributyl phosphate + sulfonated kerosene) was mixed with a gallium-germanium solution (Ge 0.1 g / L, Ga 0.1 g / L, Zn 20.12 g / L, Fe 0.42 g / L, Cd 3.16 g / L, Cu 2.65 g / L, Co 0.14 g / L, Ni 0.1 g / L, H2SO4 120 g / L). Extraction was performed under the conditions of phase O / A=1, room temperature, and 10 min. After extraction, the phases were separated by standing to obtain a germanium-rich organic phase and a germanium-poor aqueous phase. After three stages of countercurrent extraction, the germanium extraction rate was 98.33%, the extraction rate of other metal ions was less than 2%, and the total organic carbon concentration of the raffinate was less than 110 mg / L.

[0029] S2, using zinc oxide as a neutralizing agent, requires adjusting the pH of the germanium-poor aqueous phase obtained in S1 to 0.5. Using iron powder as a reducing agent, the ratio of reducing agent (mol): Fe 3+ Add (mol) in a 1:2 ratio, react at room temperature for 30 min, and then rapidly separate the liquid and solid to obtain the pretreated solution.

[0030] In step S3, the germanium-rich organic phase extracted from S1 was mixed with the pretreatment solution from S2, and extraction was performed under conditions of O / A = 1, room temperature, and 10 min. After extraction, the phases were separated by standing to obtain a gallium-rich germanium organic phase and a gallium-poor aqueous phase. After four stages of countercurrent extraction, the gallium extraction rate reached 98.67%, the extraction rate of other metal ions was less than 1%, and the total organic carbon concentration of the raffinate was less than 95 mg / L.

[0031] Example 3 A method for separating and enriching gallium and germanium from low-concentration gallium-germanium solutions S1, a freshly extracted organic phase (5.0 v% alkyloxime acid + 10 v% secondary carbon primary amine + 10 v% trioctyl phosphate + sulfonated kerosene) was mixed with a gallium-germanium solution (Ge 0.1 g / L, Ga 0.1 g / L, Zn 20.12 g / L, Fe 0.42 g / L, Cd 3.16 g / L, Cu 2.65 g / L, Co 0.14 g / L, Ni 0.1 g / L, H2SO4 120 g / L). Extraction was performed under the conditions of phase O / A=1, room temperature, and 10 min. After extraction, the phases were separated by standing to obtain a germanium-rich organic phase and a germanium-poor aqueous phase. After three stages of countercurrent extraction, the germanium extraction rate was 99.14%, the extraction rate of other metal ions was less than 2%, and the total organic carbon concentration of the raffinate was less than 125 mg / L.

[0032] S2, using zinc oxide as a neutralizing agent, requires adjusting the pH of the germanium-poor aqueous phase obtained in S1 to 1.0. Using iron powder as a reducing agent, the ratio of reducing agent (mol): Fe 3+ Add (mol) in a 1:2 ratio, react at room temperature for 30 min, and then rapidly separate the liquid and solid to obtain the pretreated solution.

[0033] In step S3, the germanium-rich organic phase extracted from S1 was mixed with the pretreatment solution from S2, and extraction was performed under conditions of O / A = 1, room temperature, and 10 min. After extraction, the phases were separated by standing to obtain a gallium-rich germanium organic phase and a gallium-poor aqueous phase. After four stages of countercurrent extraction, the gallium extraction rate reached 99.53%, the extraction rate of other metal ions was less than 2%, and the total organic carbon concentration of the raffinate was less than 100 mg / L.

[0034] Example 4 A method for separating and enriching gallium and germanium from low-concentration gallium-germanium solutions S1, a freshly extracted organic phase (5.0 v% alkyloxime acid + 20 v% secondary carbon primary amine + 10 v% trioctyl phosphate + sulfonated kerosene) was mixed with a gallium-germanium solution (Ge 0.1 g / L, Ga 0.1 g / L, Zn 20.12 g / L, Fe 0.42 g / L, Cd 3.16 g / L, Cu 2.65 g / L, Co 0.14 g / L, Ni 0.1 g / L, H2SO4 50 g / L). Extraction was performed under the conditions of phase O / A=1, room temperature, and 5 min. After extraction, the phases were separated by standing to obtain a germanium-rich organic phase and a germanium-poor aqueous phase. After three stages of countercurrent extraction, the germanium extraction rate was 98.34%, the extraction rate of other metal ions was less than 3%, and the total organic carbon concentration of the raffinate was less than 120 mg / L.

[0035] S2, using zinc oxide as a neutralizing agent, requires adjusting the pH of the germanium-poor aqueous phase obtained in S1 to 1.0. Using zinc powder as a reducing agent, the ratio of reducing agent (mol): Fe 3+Add (mol) in a 1:2 ratio, react at room temperature for 30 min, and then rapidly separate the liquid and solid to obtain the pretreated solution.

[0036] In step S3, the germanium-rich organic phase extracted from S1 was mixed with the pretreatment solution from S2, and extraction was performed under conditions of O / A = 1, room temperature, and 5 min. After extraction, the phases were separated by standing to obtain a gallium-rich germanium organic phase and a gallium-poor aqueous phase. After four stages of countercurrent extraction, the gallium extraction rate reached 98.82%, the extraction rate of other metal ions was less than 1%, and the total organic carbon concentration of the raffinate was less than 100 mg / L.

[0037] Example 5 A method for separating and enriching gallium and germanium from low-concentration gallium-germanium solutions S1, a freshly extracted organic phase (5.0 v% alkyloxime acid + 10 v% n-octylamine + 10 v% trioctyl phosphate + kerosene) was mixed with a gallium-germanium solution (Ge 0.18 g / L, Ga 0.15 g / L, Zn 19.24 g / L, Fe 0.36 g / L, Cd 2.36 g / L, Cu 4.24 g / L, Co 0.12 g / L, Ni 0.11 g / L, H2SO4 100 g / L). Extraction was performed under the conditions of phase O / A=1, room temperature, and 10 min. After extraction, the phases were separated by standing to obtain a germanium-rich organic phase and a germanium-poor aqueous phase. After three stages of countercurrent extraction, the germanium extraction rate was 99.26%, the extraction rate of other metal ions was less than 2%, and the total organic carbon concentration of the raffinate was less than 125 mg / L.

[0038] S2, using zinc oxide as a neutralizing agent, requires adjusting the pH of the germanium-poor aqueous phase obtained in S1 to 1.0. Using zinc powder as a reducing agent, the ratio of reducing agent (mol): Fe 3+ Add (mol) in a 1:2 ratio, react at room temperature for 30 min, and then rapidly separate the liquid and solid to obtain the pretreated solution.

[0039] In step S3, the germanium-rich organic phase extracted from S1 was mixed with the pretreatment solution from S2, and extraction was performed under conditions of O / A = 1, room temperature, and 10 min. After extraction, the phases were separated by standing to obtain a gallium-rich germanium organic phase and a gallium-poor aqueous phase. After four stages of countercurrent extraction, the gallium extraction rate reached 98.71%, the extraction rate of other metal ions was less than 2%, and the total organic carbon concentration of the raffinate was less than 110 mg / L.

[0040] Comparative Example 1 Referring to Example 1, the difference is that in step S1, no hydrolysis inhibitor is added to the newly extracted organic phase, which consists of 0.5v% alkyloxime acid + 5v% tributyl phosphate + sulfonated kerosene. This results in the total organic carbon concentration in the germanium-poor aqueous phase exceeding 350 mg / L and the total organic carbon concentration in the gallium-poor aqueous phase exceeding 300 mg / L (far higher than in Example 1), which is not conducive to the solution being incorporated into the main metal recovery system.

[0041] Comparative Example 2 Referring to Example 4, the difference is that in step S1, no hydrolysis inhibitor is added to the newly extracted organic phase, which consists of 5.0 v% alkyloxime acid + 10 v% trioctyl phosphate + sulfonated kerosene. This results in the total organic carbon concentration in the germanium-poor aqueous phase exceeding 460 mg / L and the total organic carbon concentration in the gallium-poor aqueous phase exceeding 400 mg / L (far higher than in Example 4), which is not conducive to the solution being incorporated into the main metal recovery system.

[0042] Comparative Example 3 Referring to Example 2, the difference is that the pretreatment operation in step S2 was not performed, resulting in an iron extraction rate of over 85% in step S3 (far higher than in Example 2). Since gallium and iron were not separated during extraction, iron will enter the back-extraction solution during the subsequent back-extraction process, which is not conducive to the further separation and recovery of gallium.

[0043] Comparative Example 4 Referring to Example 2, the difference is that: during the pretreatment operation in step S2, the ratio of reducing agent (mol): Fe 3+ Adding (mol) in a 1:4 ratio resulted in an iron extraction rate exceeding 40% in step S3 (far higher than in Example 2), failing to achieve high selective separation of gallium and iron during extraction. This also led to iron entering the back-extraction solution during subsequent back-extraction, which was detrimental to the further recovery of gallium.

[0044] Comparative Example 5 Referring to Example 3, the difference is that: during the pretreatment operation in step S2, an excess of neutralizing agent was added to adjust the pH of the solution to 2.8, resulting in the formation of a large amount of flocculent reddish-brown precipitate, making subsequent operations impossible.

[0045] The comparison between the examples and the comparative examples shows that the comparative examples are significantly inferior to the examples in terms of controlling the organic carbon content in the raffinate and inhibiting iron co-extraction. This indicates that the extraction system and extraction process provided by the present invention are not simply combinations or conventional replacements of the extractant and process conditions, but rather achieve unexpected synergistic effects through targeted and rational design, reducing the water solubility loss of the extractant, inhibiting iron co-extraction, and simultaneously ensuring the efficient separation and enrichment of gallium and germanium.

[0046] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for separating and enriching gallium and germanium from a low-concentration gallium-germanium solution, characterized in that, The method includes: S1. Preparation of a new organic phase for extraction: The extractant, hydrolysis inhibitor, modifier and diluent are mixed evenly to obtain a new organic phase for extraction. S2, Extraction and separation of germanium: The newly prepared organic phase for extraction was mixed with a gallium-germanium-containing solution and extracted. After extraction, the phases were separated by standing to obtain a germanium-rich organic phase and a germanium-poor aqueous phase. S3, Iron co-extraction inhibition pretreatment: The germanium-poor aqueous phase obtained in S2 was pre-neutralized and acidified with a neutralizing agent, and then a reducing agent was added. After the reaction was completed, liquid and solid separation was performed to obtain the pretreated solution. S4. Extraction and separation of gallium: The germanium-rich organic phase obtained in S2 was mixed with the pretreatment solution obtained in S3 and extracted. After extraction, the mixture was allowed to stand and separate to obtain gallium-rich organic phase, germanium-rich organic phase and gallium-poor raffinate. The extractant in S1 is alkyloxime acid, the hydrolysis inhibitor is secondary carbon amine or n-octylamine, the modifier is tributyl phosphate or trioctyl phosphate, and the diluent is kerosene or sulfonated kerosene. The extractant has a volume concentration of 0.5% to 5% in the newly extracted organic phase, the hydrolysis inhibitor has a volume concentration of 1% to 20% in the newly extracted organic phase, and the modifier has a volume concentration of 5% to 10% in the newly extracted organic phase.

2. The method for separating and enriching gallium and germanium in a low-concentration gallium-germanium solution according to claim 1, characterized in that, The sulfuric acid concentration in the gallium-germanium solution in S2 is 50~120g / L, and the concentrations of gallium and germanium are both below 200mg / L.

3. The method for separating and enriching gallium and germanium in a low-concentration gallium-germanium solution according to claim 1, characterized in that, In S2, the newly extracted organic phase is mixed with a gallium-germanium-containing solution for extraction at room temperature for 5-10 minutes, with a phase ratio of 1.

4. The method for separating and enriching gallium and germanium in a low-concentration gallium-germanium solution according to claim 1, characterized in that, The neutralizing agent in S3 is zinc calcined sand or zinc oxide. The germanium-poor aqueous phase is pre-neutralized with the neutralizing agent to adjust the pH to 0.5~1.

0.

5. The method for separating and enriching gallium and germanium in a low-concentration gallium-germanium solution according to claim 1, characterized in that, The reducing agent in S3 is zinc powder or iron powder, and the molar ratio is: reducing agent:Fe 3+ The solution was added in a 1:2 ratio, the reaction temperature was room temperature, the reaction time was 30 minutes, and the final pH was controlled to not exceed 1.5 to ensure complete reduction and prevent hydrolysis of metal ions.

6. The method for separating and enriching gallium and germanium in a low-concentration gallium-germanium solution according to claim 1, characterized in that, In S4, the extraction temperature is room temperature, the extraction time is 5-10 min, the phase ratio is 1, and the pH at the extraction endpoint is controlled at 2.0-2.5.

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