Method for extracting gallium and germanium from alkyl hydroximic acid extraction resin

Abstract

The invention provides a method for extracting gallium and germanium from alkyl hydroximic acid extraction resin, and relates to the technical field of metal recovery. The preparation method comprises the following specific steps: putting HZ818 macroporous resin into a beaker, adding a mixed extraction solvent of C7-9 alkyl hydroximic acid and absolute ethyl alcohol, heating to 60 DEG C, stirring for 4 hours, filtering, washing and drying to obtain alkyl hydroximic acid extraction resin; the method comprises the following steps: loading alkyl hydroximic acid extraction resin into an ion exchange column, and introducing a zinc hydrometallurgy leaching solution containing low-concentration gallium and germanium to adsorb gallium and germanium; eluting the extraction resin adsorbing gallium and germanium with a sulfuric acid solution and an NH4F solution in sequence to obtain a gallium-rich solution and a germanium-rich solution respectively. The method is easy to operate, the gallium and germanium separation effect is good, the gallium and germanium adsorption rates can reach 84% or above and 95% or above respectively, and meanwhile the gallium and germanium desorption rates exceed 95%.

Description

Technical Field

[0001] The invention relates to the technical field of metal recovery, and in particular to a method for extracting gallium and germanium by using an alkyl hydroxamic acid leaching resin. Background Art

[0002] Gallium and germanium, as important rare metals, are widely used in semiconductor materials, new energy and other fields; however, the abundance of gallium and germanium in the earth's crust is very low, only one in 150,000; generally there are no independent deposits, but most of them exist in association with other main metal deposits. Therefore, how to extract gallium and germanium efficiently and environmentally friendly is also of great significance.

[0003] At present, the extraction technologies of gallium and germanium are divided into pyrolysis and wet processing. However, due to the low efficiency of the pyrolysis process and its great adverse impact on the environment, it has gradually been replaced by wet processing. The main wet extraction technologies include: extraction, ion exchange, microemulsion liquid membrane, etc.

[0004] The liquid membrane method has problems such as complicated emulsification and demulsification processes and unstable liquid membranes. Although the extraction method is simple to operate and can achieve a high recovery rate, the extractant YW100 commonly used in industrial production has a high water solubility, which will cause environmental damage and increase production costs. The resin used in the ion exchange method has poor adsorption effect on gallium and germanium in complex acidic systems.

[0005] The leaching resin adsorption method combines the advantages of solvent extraction and ion exchange. It not only achieves the high selectivity of solvent extraction, but also avoids the problems of extractant loss and poor resin adsorption effect. It is an effective separation method. Summary of the invention

[0006] In view of the above problems, the present invention provides a method for extracting gallium germanium by using an alkyl hydroxamic acid leaching resin. The method has a simple process and the resin has good selectivity and separation effect for gallium germanium.

[0007] To solve the above problems, the technical solution adopted by the present invention is:

[0008] A method for extracting gallium and germanium with an alkyl hydroxamic acid leaching resin comprises the following steps: S1, preparing the alkyl hydroxamic acid leaching resin: washing the macroporous resin with anhydrous ethanol and filtering and drying; placing the pretreated macroporous resin in a beaker, adding C 7～9A mixed extraction solvent of alkyl hydroxamic acid and anhydrous ethanol is stirred at 40-60°C for more than 4 hours, then the solid and liquid are separated, and the resin is washed with deionized water to clean the extraction solvent on the resin surface and the gap between particles. The resin is then placed in a vacuum drying oven and dried to constant weight at 60°C to prepare an alkyl hydroxamic acid leaching resin; S2, adsorption: the alkyl hydroxamic acid leaching resin is loaded into an ion exchange column, and a wet zinc smelting leaching solution containing low concentrations of gallium and germanium is introduced into the resin column at a certain flow rate to adsorb gallium and germanium; S3, elution: a sulfuric acid solution is introduced into the leaching resin adsorbing gallium and germanium for elution to obtain a gallium-rich solution, and then NH 4 F solution is then eluted to obtain a germanium-rich solution.

[0009] Preferably, the macroporous resin is HZ818.

[0010] Preferably, in step S1, the impregnating agent contains C 7～9 The concentration of alkyl hydroxamic acid is 50-60%.

[0011] Preferably, in step S2, the hydrometallurgical zinc leaching solution containing low concentrations of gallium and germanium is adjusted to a pH value of 1.4 to 1.6 using sodium hydroxide and then subjected to resin adsorption.

[0012] Preferably, the resin column is pretreated by the following process: eluting the resin column with a 3 mol / L sulfuric acid solution, and then washing the resin column with deionized water until the pH value of the effluent remains stable.

[0013] Preferably, the concentration of the sulfuric acid solution used for elution in step S3 is 2.5 to 4 mol / L, NH 4 The concentration of F solution is 1~2 mol / L.

[0014] The beneficial effects of the present invention are:

[0015] Compared with the prior art, the process of the present invention is simple, and the prepared alkyl hydroxamic acid leaching resin has good selectivity for gallium germanium, can effectively adsorb and extract gallium germanium from an acidic solution containing low-concentration gallium germanium, has a high gallium germanium recovery rate, and has a small amount of impurity ions. The gallium and germanium adsorption rates can reach 84.24% and 96.73% respectively, and the gallium and germanium desorption rates can reach 95.49% and 97.31% respectively; at the same time, the leaching resin after adsorbing gallium germanium can be eluted and recovered gallium germanium by different eluents, which is convenient for subsequent further recovery and purification. DETAILED DESCRIPTION

[0016] The present invention is further described below in conjunction with embodiments.

[0017] The invention discloses a method for extracting gallium and germanium by using an alkyl hydroxamic acid leaching resin. The specific steps are as follows: placing HZ818 macroporous resin in a beaker, adding C 7～9A mixed extraction solvent of alkyl hydroxamic acid and anhydrous ethanol is heated to 60°C and stirred for 4 hours, and then filtered, washed and dried to obtain an alkyl hydroxamic acid extraction resin.

[0018] The alkyl hydroxamic acid leaching resin is loaded into an ion exchange column, and a wet zinc smelting leaching solution containing low concentrations of gallium and germanium is introduced to adsorb gallium and germanium. The leaching resin adsorbing gallium and germanium is successively treated with sulfuric acid solution and NH 4 The invention is simple to operate, has good gallium-germanium separation effect, gallium and germanium adsorption rates can reach 84% and 95% or more respectively, and gallium and germanium desorption rates exceed 95%.

[0019] A method for extracting gallium and germanium using an alkyl hydroxamic acid leaching resin comprises the following steps:

[0020] Step 1: Preparation of alkyl hydroxamic acid leaching resin: Wash the macroporous resin with anhydrous ethanol and filter and dry; Place the pretreated macroporous resin in a beaker and add C 7～9 A mixed extraction solvent of alkyl hydroxamic acid and anhydrous ethanol is stirred at 40-60°C for more than 4 hours, then the solid-liquid separation is carried out, and the extraction solvent on the resin surface and the gap between particles is cleaned with deionized water. The resin is then placed in a vacuum drying oven and dried to constant weight at 60°C to prepare an alkyl hydroxamic acid extraction resin.

[0021] Step 2: Adsorption: The alkyl hydroxamic acid leaching resin is loaded into an ion exchange column, and a wet zinc smelting leaching solution containing low concentrations of gallium and germanium is introduced into the resin column at a certain flow rate to adsorb gallium and germanium.

[0022] Step 3: Elution: Sulfuric acid solution is passed into the leaching resin adsorbing gallium germanium to obtain a gallium-rich solution, and then NH 4 F solution is then eluted to obtain a germanium-rich solution.

[0023] Specifically, the gallium and germanium contents of the wet zinc smelting leaching solution containing low concentrations of gallium and germanium are: Ga 20-30 mg / L, Ge 60-80 mg / L.

[0024] Specifically, the macroporous resin is preferably HZ818. The color of HZ818 macroporous adsorption resin is milky white or light yellow, which facilitates the processing operation and makes it easier to observe when separating and purifying colored organic compounds. HZ818 has stable physical and chemical properties and is insoluble in any acid, alkali and organic solvent, which is convenient for the selection of adsorbents and desorbents. It can be used below 150°C and is suitable for a variety of treatment processes under high temperature environments. HZ818 macroporous adsorption resin has the effects of concentrating, enriching and separating organic matter and is not affected by the presence of inorganic salts. Its application range is wider.

[0025] Specifically, the impregnating agent C 7～9 The concentration of alkyl hydroxamic acid is 50-60%. Within this concentration range, the resin has a higher impregnation rate and the gallium-germanium adsorption is the highest. If the concentration is too low, the impregnation rate of the extractant is low, while if the concentration is too high, the resin pores may be filled with too much extractant, affecting the adsorption effect.

[0026] Specifically, the pH value of the wet zinc smelting leaching solution containing low concentrations of gallium and germanium is adjusted to 1.4-1.6 using sodium hydroxide and then subjected to resin adsorption. At this pH value, the resin has the best adsorption effect on gallium and germanium. Too low a pH value of the solution will lead to a decrease in the gallium adsorption rate, while too high a pH value may cause hydrolysis of gallium and germanium.

[0027] Specifically, the resin column is pretreated by the following process: eluting the resin column with a 3 mol / L sulfuric acid solution, and then washing the resin column with deionized water until the pH value of the effluent remains stable.

[0028] Preferably, the concentration of the sulfuric acid solution used for elution is 2.5 to 4 mol / L, NH 4 The concentration of F solution is 1-2 mol / L. For the wet zinc smelting leaching solution system used, if the concentration of the eluent is lower than this range, the desorption effect of gallium and germanium will be poor, and too high a concentration will cause waste.

[0029] Beneficial effects of the present invention:

[0030] (1) The process of the present invention is simple, and the prepared alkyl hydroxamic acid leaching resin has good selectivity for gallium germanium and can effectively adsorb and extract gallium germanium from an acidic solution containing low concentration of gallium germanium. The gallium germanium recovery rate is high and the impurity ions are small. The gallium and germanium adsorption rates can reach 84.24% and 96.73% respectively, and the gallium and germanium desorption rates can reach 95.49% and 97.31% respectively.

[0031] (2) After adsorbing gallium and germanium, the leaching resin can be eluted and recovered by different eluents to facilitate further recovery and purification.

[0032] The present invention will be further described below by way of examples, however the scope of the present invention is not limited to the following examples.

[0033] Embodiment 1:

[0034] Preparation of alkyl hydroxamic acid leaching resin: Wash HZ818 macroporous resin with anhydrous ethanol and filter and dry. Place the pretreated macroporous resin in a beaker and add C 7～9A mixed extraction solvent of alkyl hydroxamic acid and anhydrous ethanol, with a C7-9 alkyl hydroxamic acid concentration of 50%, is stirred at 60°C for 4 hours, then solid-liquid separation is performed, and the resin is washed with deionized water to clean the extraction solvent on the resin surface and the gap between particles. The resin is then placed in a vacuum drying oven and dried to constant weight at 60°C to prepare an alkyl hydroxamic acid extraction resin.

[0035] Adsorption and elution: The gallium and germanium content of the wet zinc smelting leachate containing low concentrations of gallium and germanium is: Ga27.72mg / L, Ge68.43mg / L, and the pH value is adjusted to 1.5. The alkyl hydroxamic acid leaching resin is loaded into the ion exchange column, and the resin column is eluted with a 3mol / L sulfuric acid solution, followed by washing with deionized water, and then 4BV of the wet zinc smelting leachate containing low concentrations of gallium and germanium is passed into the resin column at a flow rate of 2BV / H to adsorb gallium and germanium. After the resin column is rinsed with deionized water, 4BV of a 3mol / L sulfuric acid solution is passed into it for elution to obtain a gallium-rich solution, which is then rinsed with deionized water and 3BV of 1mol / L NH 4 The adsorption rate and elution rate are shown in Table 1.

[0036] Table 1

[0037] Ga Ge Adsorption rate / % 79.24 92.21 Elution rate / % 91.52 96.79

[0038] Embodiment 2:

[0039] Preparation of alkyl hydroxamic acid leaching resin: Wash HZ818 macroporous resin with anhydrous ethanol and filter and dry. Place the pretreated macroporous resin in a beaker and add C 7～9 A mixed extraction solvent of alkyl hydroxamic acid and anhydrous ethanol, C 7～9 The concentration of alkyl hydroxamic acid is 50%, stirred at 60°C for 4 hours, then solid-liquid separation, and washed with deionized water to clean the extraction solvent on the resin surface and the gap between particles, and then placed in a vacuum drying oven at 60°C and dried to constant weight to prepare alkyl hydroxamic acid leaching resin.

[0040] Adsorption and elution: The gallium and germanium content of the wet zinc smelting leachate containing low concentrations of gallium and germanium is: Ga22.60mg / L, Ge76.61mg / L, and the pH value is adjusted to 1.5. The alkyl hydroxamic acid leaching resin is loaded into the ion exchange column, and the resin column is eluted with a 3mol / L sulfuric acid solution, followed by deionized water. Then, 2BV of the wet zinc smelting leachate containing low concentrations of gallium and germanium is passed into the resin column at a flow rate of 2BV / H to adsorb gallium and germanium. After the resin column is eluted with deionized water, 4BV of a 3mol / L sulfuric acid solution is passed into it for elution to obtain a gallium-rich solution, which is then rinsed with deionized water and 3BV of a 1mol / L NH4F solution is passed through it for elution to obtain a germanium-rich solution. The adsorption rate and elution rate are shown in Table 2.

[0041] Table 2

[0042] Ga Ge Adsorption rate / % 84.24 96.73 Elution rate / % 95.49 97.31

[0043] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for extracting gallium and germanium using an alkyl hydroxamic acid leaching resin, characterized in that: The steps include: S1. Preparation of alkyl hydroxamic acid leaching resin: wash the macroporous resin with anhydrous ethanol and filter and dry; place the pretreated macroporous resin in a beaker and add C 7～9 A mixed extraction solvent of alkyl hydroxamic acid and anhydrous ethanol is stirred at 40-60°C for more than 4 hours, and then the solid and liquid are separated and washed with deionized water to clean the extraction solvent on the resin surface and the gap between particles. The resin is then placed in a vacuum drying oven and dried at 60°C to constant weight to prepare an alkyl hydroxamic acid extraction resin; S2, adsorption: the alkyl hydroxamic acid leaching resin is loaded into an ion exchange column, and a wet zinc smelting leaching solution containing low concentrations of gallium and germanium is introduced into the resin column at a certain flow rate to adsorb gallium and germanium; S3, elution: passing a sulfuric acid solution into the leaching resin adsorbing gallium and germanium to elute to obtain a gallium-rich solution, and then passing an NH4F solution to elute to obtain a germanium-rich solution.

2. The method for extracting gallium and germanium using an alkyl hydroxamic acid leaching resin according to claim 1, characterized in that: The macroporous resin is preferably HZ818.

3. The method for extracting gallium and germanium using an alkyl hydroxamic acid leaching resin according to claim 1, characterized in that: In step S1, C 7～9 The concentration of alkyl hydroxamic acid is 50-60%.

4. The method for extracting gallium and germanium using an alkyl hydroxamic acid leaching resin according to claim 1, characterized in that: In step S2, the pH value of the hydrometallurgical zinc leaching solution containing low concentrations of gallium and germanium is adjusted to 1.4-1.6 using sodium hydroxide and then subjected to resin adsorption.

5. The method for extracting gallium and germanium using an alkyl hydroxamic acid leaching resin according to claim 1, characterized in that: The resin column was pretreated by the following process: eluting the resin column with a 3 mol / L sulfuric acid solution, and then washing the resin column with deionized water until the pH value of the effluent remained stable.

6. The method for extracting gallium and germanium using an alkyl hydroxamic acid leaching resin according to claim 1, characterized in that: The concentration of the sulfuric acid solution used for elution in step S3 is 2.5-4 mol / L, and the concentration of the NH4F solution is 1-2 mol / L.