A gallium extraction reagent FP191, a preparation method and application thereof

Abstract

This invention discloses a gallium extraction reagent FP191, its preparation method, and its applications. The gallium extraction reagent FP191 is prepared from N,N-di(1-methylheptyl)acetamide, methyltrioctylammonium chloride, and trioctyl tertiary amine. This invention employs a composite extractant system as the core technology, achieving efficient separation and enrichment of gallium by systematically controlling key process parameters during the extraction process. The ultimate goal is to construct an environmentally friendly, economically feasible, and industrially applicable method for efficiently separating and enriching gallium from solutions containing low concentrations of gallium.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical technology, specifically relating to a gallium extraction reagent FP191, its preparation method, and its application. Background Technology

[0002] Gallium is a scarce and dispersed strategic metal with excellent semiconductor and optoelectronic properties. It is a core material for third-generation semiconductors, and its supply and application are directly linked to key sectors such as high-end manufacturing, information and communication, and national defense. It is a crucial strategic resource for ensuring the development of industries such as chips, 5G, and new energy, possessing extremely high economic and strategic value. China has the world's largest gallium reserves. Although not lacking in reserves, gallium does not have independent deposits and mainly occurs in association with minerals such as aluminum, zinc, and germanium. With current technology, the overall gallium recovery rate is only 30% to 50%, meaning that only a very small portion of the reserves can be recovered. Therefore, developing a method for efficiently separating and enriching gallium from solutions containing low concentrations of gallium remains a challenging problem to be solved. Summary of the Invention

[0003] The first objective of this invention is to provide a gallium extraction reagent FP191; the second objective is to provide a method for preparing the gallium extraction reagent FP191; and the third objective is to provide applications of the gallium extraction reagent FP191.

[0004] The first objective of this invention is achieved by the fact that the gallium extraction reagent FP191 is prepared from the raw materials N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine.

[0005] The second objective of this invention is achieved by reacting the raw materials N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine in the formulation ratio under an oxygen pressure atmosphere to obtain the target gallium extraction reagent FP191.

[0006] Specifically, N,N-di(1-methylheptyl)acetamide, methyltrioctylammonium chloride, and trioctyl tertiary amine are reacted at an oxygen pressure of 0.5-1.0 kPa and a temperature of 50-100℃ for 2-3 hours. After the reaction stops, the mixture is separated by filtration to obtain the gallium composite extractant FP191. The molar ratio of N,N-di(1-methylheptyl)acetamide, methyltrioctylammonium chloride, and trioctyl tertiary amine is 1-5:1-10:20-100. This reagent exhibits stable gallium extraction performance under high acid and high temperature conditions.

[0007] The technical principle of the gallium extraction reagent FP191 is as follows: In highly acidic, chlorine-containing systems, gallium mainly exists as a chloride complex anion, and its complexation reaction can be represented as follows: Ga 3+ (aq) + 4Cl- (aq) [GaCl4] - (aq) The quaternary ammonium salt component and the protonated tertiary amine component in FP191 can act as active organic ammonium salt components, undergoing anion exchange and ion association with gallium chloride complexed anions, thereby transferring gallium from the aqueous phase to the organic phase. The extraction process can be summarized as follows: RNH + Cl - (org) + [GaCl4] - (aq) RNH + [GaCl4] - (org) + Cl - (aq) In the formula, RNH + Cl - The active organic ammonium salt components in FP191 that have anion exchange capacity include quaternary ammonium salt components and protonated tertiary amine salts formed under acidic conditions.

[0008] The extraction mechanism of gallium by FP191 is as follows: In a highly acidic medium, gallium first forms a stable gallium chloride complex anion with chloride ions, which is then extracted into the organic phase by the quaternary ammonium salt and protonated tertiary amine in FP191 through anion exchange and ion association. N,N-di(1-methylheptyl)acetamide enhances the stability of the gallium extract in the organic phase through carbonyl coordination, solvation, and hydrophobic stabilization. These three components together constitute a synergistic extraction system, thereby improving the extraction capacity, selectivity, and phase stability of FP191 for gallium under high acid and high temperature conditions.

[0009] The third objective of this invention is achieved by the application of the gallium extraction reagent FP191 in the gallium extraction process of gallium-containing copper fume leaching solution.

[0010] Specifically, accurately measure 20-40% (v / v) of FP191 composite extractant and 60-80% of sulfonated kerosene, mix thoroughly, and extract from copper flue dust leaching solution containing 0.3-0.5 g / L of gallium. The ratio of O / A is 1:3-10, the stirring speed is 50-200 r / min, the reaction temperature is 20-40℃, and the extraction time is 5-10 min. After the reaction stops, the organic phase and aqueous phase are separated. The resulting raffinate contains Ga... 3+ The content is only 0.003~0.005g / L, and the gallium extraction rate reaches 98.3~99.4%.

[0011] This invention employs a composite extractant system as its core technology, achieving efficient separation and enrichment of gallium by systematically controlling key process parameters during the extraction process. The ultimate goal is to develop an environmentally friendly, economically feasible, and industrially applicable method for efficiently separating and enriching gallium from solutions containing low concentrations of gallium. Detailed Implementation

[0012] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0013] The gallium extraction reagent FP191 described in this invention is prepared from raw materials N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine.

[0014] The molar ratio of N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine is (1~5):(1~10):(20~100).

[0015] The method for preparing gallium extraction reagent FP191 according to the present invention involves reacting the raw materials N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine in an oxygen pressure atmosphere to obtain the target gallium extraction reagent FP191.

[0016] The oxygen pressure of the reaction is 0.5~1.0 kPa.

[0017] The reaction temperature is 50~100℃.

[0018] The reaction time is 2-3 hours.

[0019] The application of the gallium extraction reagent FP191 described in this invention is its application in the gallium extraction process of gallium-containing copper fume leaching solution.

[0020] The gallium-containing copper fume leaching process includes pretreatment and extraction steps, specifically including: A. Pretreatment: Sulfonated kerosene is added to gallium extraction reagent FP191 and mixed evenly to obtain extractant a; B. Extraction: Extractant a is added to the gallium-containing copper fume leachate to be treated for extraction to obtain organic phase b and aqueous phase c. Organic phase b is gallium-containing solution and aqueous phase c is raffinate.

[0021] The volume ratio of the gallium extraction reagent FP191 to sulfonated kerosene is (20~40):(60~80).

[0022] In step B, the extraction ratio O / A is 1:3~10, the stirring speed is 50~200 r / min, the reaction temperature is 20~40℃, and the extraction time is 5~10 min.

[0023] The present invention will be further described below with reference to specific embodiments: Example 1

[0024] The target gallium extraction reagent FP191 was obtained by reacting N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine in a molar ratio of 1:1:20 at an oxygen pressure of 0.5 kPa and a temperature of 50-80 °C for 3 h.

[0025] Example 2

[0026] The raw materials N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine in a molar ratio of 5:10:100 were reacted at an oxygen pressure of 1.0 kPa and a temperature of 80~100 °C for 2 h to obtain the target gallium extraction reagent FP191.

[0027] Example 3

[0028] The target gallium extraction reagent FP191 was obtained by reacting N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine in a molar ratio of 4:5:60 at an oxygen pressure of 0.8 kPa and a temperature of 60-80 °C for 2.5 h.

[0029] Comparative Example 1 Chinese patent CN120272720A discloses a method for stepwise extraction of gallium and iron from NdFeB waste acid leaching solution based on solvent extraction. The raw material is NdFeB waste that has undergone oxidative roasting and then leached with hydrochloric acid under certain conditions. The hydrochloric acid concentration in the leaching solution is adjusted to approximately 1-3 mol / L. The method also discloses the extraction of gallium and iron from NdFeB waste acid leaching solution. 3+ With a content of 0.2-0.3 g / L, a mixed solvent of 2-3% trioctyldecyl tertiary amine, 10-15% isodecanol, and sulfonated kerosene as a diluent was used. Under extraction conditions of an organic phase:water phase ratio of 1:1, an extraction temperature of 25℃, and an extraction time of 5 min, the acid leaching solution underwent eight stages of extraction and phase separation to obtain a gallium-containing organic phase and a first raffinate. The raffinate contained Ga... 3+ The content is only 0.005-0.01 g / L, and the gallium extraction rate reaches 95-98.3%.

[0030] Example 4

[0031] Accurately measure 20% (v / v) of the FP191 composite extractant prepared in Example 3 and 80% of sulfonated kerosene, mix thoroughly, and extract from a copper fume leaching solution containing 0.46 g / L of gallium. The ratio of O / A is 1:3, the stirring speed is 200 r / min, the reaction temperature is 20-30℃, and the extraction time is 10 min. After the reaction stops, the organic phase and aqueous phase are separated. The resulting raffinate contains Ga... 3+ The content was only 0.0047 g / L, and the gallium extraction rate reached 99.01%.

[0032] Example 5

[0033] Accurately measure 40% (v / v) of the FP191 composite extractant prepared in Example 1 and 60% of sulfonated kerosene, mix thoroughly, and extract from a copper flue dust leachate containing 0.34 g / L of gallium. The ratio of O / A is 1:10, the stirring speed is 50 r / min, the reaction temperature is 30-40℃, and the extraction time is 5 min. After the reaction stops, the organic phase and the aqueous phase are separated. The resulting raffinate contains Ga... 3+ The content was only 0.0035 g / L, and the gallium extraction rate reached 98.97%.

[0034] Example 6

[0035] Accurately measure 30% (v / v) of the FP191 composite extractant prepared in Example 2 and 70% of sulfonated kerosene, mix thoroughly, and extract from a copper fume leaching solution containing 0.43 g / L of gallium. The ratio of O / A is 1:3~10, the stirring speed is 100 r / min, the reaction temperature is 25~35℃, and the extraction time is 8 min. After the reaction stops, the organic phase and the aqueous phase are separated. The resulting raffinate contains Ga... 3+ The content was only 0.0039 g / L, and the gallium extraction rate reached 99.31%.

Claims

1. A gallium extraction reagent FP191, characterized in that, The gallium extraction reagent FP191 is prepared from the raw materials N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine.

2. The gallium extraction reagent FP191 according to claim 1, characterized in that, The molar ratio of N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine is (1~5):(1~10):(20~100).

3. A method for preparing the gallium extraction reagent FP191 according to claim 1 or 2, characterized in that, The target gallium extraction reagent FP191 is obtained by reacting the raw materials N,N-bis(1-methylheptyl)acetamide, methyltrioctylammonium chloride and trioctyl tertiary amine in an oxygen pressure atmosphere.

4. The preparation method according to claim 3, characterized in that, The oxygen pressure of the reaction is 0.5~1.0 kPa.

5. The preparation method according to claim 3, characterized in that, The reaction temperature is 50~100℃.

6. The preparation method according to claim 3, characterized in that, The reaction time is 2-3 hours.

7. The application of the gallium extraction reagent FP191 according to claim 1 or 2, characterized in that, The application of the gallium extraction reagent FP191 in the gallium extraction process of gallium-containing copper fume leaching solution.

8. The application according to claim 7, characterized in that, The gallium-containing copper fume leaching process includes pretreatment and extraction steps, specifically including: A. Pretreatment: Sulfonated kerosene is added to gallium extraction reagent FP191 and mixed evenly to obtain extractant a; B. Extraction: Extractant a is added to the gallium-containing copper fume leachate to be treated for extraction to obtain organic phase b and aqueous phase c. Organic phase b is gallium-containing solution and aqueous phase c is raffinate.

9. The application according to claim 8, characterized in that, The volume ratio of the gallium extraction reagent FP191 to sulfonated kerosene is (20~40):(60~80).

10. The application according to claim 8, characterized in that, In step B, the extraction ratio O / A is 1:3~10, the stirring speed is 50~200 r / min, the reaction temperature is 20~40℃, and the extraction time is 5~10 min.