Preparation method of hydroximic acid modified resin and application of hydroximic acid modified resin in separating gallium from high-acid high-impurity gallium-containing solution

Abstract

The preparation method of the hydroximic acid modified resin comprises the following steps: mixing chloromethylated polystyrene resin, aminosalicylic acid and a polar solvent, and reacting to obtain aminosalicylic acid cross-linked resin; mixing the aminosalicylic acid cross-linked resin, methanol and an inert solvent, adding concentrated sulfuric acid as a catalyst, and carrying out esterification reaction; and adding a product obtained after the esterification reaction and hydroxylamine hydrochloride into methanol, then adding alkali liquor to carry out amination reaction, and washing and vacuum-drying an obtained product to obtain the hydroximic acid modified resin which can be used for separating gallium from the high-acid high-impurity gallium-containing solution. The hydroximic acid modified polystyrene resin prepared by the method of the invention can co-adsorb low-concentration gallium and part of iron in the high-acid and high-impurity gallium-containing solution, basically does not adsorb other ions, and the hydroximic acid modified polystyrene resin realizes step-by-step desorption through sulfuric acid and hydrochloric acid, so as to realize selective separation and extraction of gallium; and the resin has no influence on an original system, can be recycled, so that the cost is greatly reduced, and a technical support is provided for selectively separating the gallium from the high-acid and high-impurity solution.

Description

technical field [0001] The invention belongs to the field of gallium adsorption, and in particular relates to a preparation method of a hydroxamic acid modified resin and a method for separating low-concentration gallium from a high-acid and high-impurity gallium-containing solution. Background technique [0002] Gallium is a scattered metal and is widely used in wireless communications, LED lighting, solar cells and other fields. It is known as "the new food of the semiconductor industry" and has been listed as a strategic reserve metal by many countries. Almost all applications of gallium are closely related to green energy and cutting-edge technology, and people's demand for gallium will continue to grow for a long time to come. [0003] Gallium is mainly associated with bauxite and lead-zinc ore, so primary gallium is generally obtained from aluminum smelting and zinc smelting industries, and 80% of zinc production in the world is produced by hydrometallurgy. Gallium is...

AI Technical Summary

Problems solved by technology

The electrolytic extraction of gallium is generally used in an alkaline system, which cannot effectively separate gallium in a high-acid and high-impurity system; although solvent extraction can selectively separate gallium, it requires a large amount of extractant, and the cost is high and the cycle is long , such as the patent application whose publication number is CN111254295A discloses a method and application of extracting and separating gallium from the sulfuric acid leaching solution of zinc replacement slag, which adopts P204-N235-sulfonated kerosene to carry out cooperative extraction of gallium in the sulfuric acid system, but it still There are co-extraction problems of iron, copper, zinc and other ions, and the need for multi-stage countercurrent extraction greatly reduces the comprehensive recovery of gallium

The adsorption method can achieve high-efficiency separation and extraction of low-concentration gallium, and is environmentally friendly and recyclable. However, the current research is mainly aimed at the adsorption and separation of gallium in the alkaline system of the aluminum smelting industry, which is costly and has poor cycle performance. There are few reports on the adsorption of gallium in acidic systems. The patent application with publication number CN106732411A discloses the preparation of an acrylic functionalized graphene oxide adsorbent and its application in the adsorption of gallium, but the pH range of its adsorption of gallium is only 2 ~3, the adsorption time is also longer, and the adsorption rate of gallium is only 60%

The patent application with the publication number CN104018012A discloses a method for extracting gallium from aluminum chloride solution. This patent realizes the co-adsorption of gallium and iron through a section of anion resin exchange, and needs to add a reducing agent to the eluent to remove Fe 3+ reduced to Fe 2+ , and then realize the adsorption and separation of gallium through two-stage anion resin exchange, the process is longer and the introduction of reducing agent will have an adverse effect on the adsorption effect of gallium

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