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鋅冶煉過程中提取鎵的技術研究及其進展

Research and prospect of gallium recovery technology in zinc smelting

  • 摘要: 針對鎵從鋅冶煉過程中回收占比低的問題,總結分析了鋅冶煉過程中鎵回收技術研究進展. 在鼓風爐煉鋅(ISP)工藝中,鎵主要富集在鼓風爐爐渣里,其質量分數通常在0.025%~0.031%,從鼓風爐爐渣中回收鎵主要有還原蒸發法、高溫氯化揮發法、硫酸浸出法、堿熔–浸出法、還原熔煉–電解法和還原熔煉–熔融造渣法等方法,但這些工藝普遍流程長,回收率低,加工成本偏高,部分工藝環境污染大,難以工業化應用. 傳統的濕法煉鋅工藝中,大于93.5%的鎵富集在浸出渣中,浸出渣處理以火法還原揮發工藝為主,在回轉窯揮發浸出渣工藝中90%的鎵保留在窯渣中,導致鎵的回收流程長且回收率低,濕法處理浸出渣存在鎵和鐵分離的難題,至今未得到有效解決. 氧壓浸出煉鋅工藝中,鎵主要富集在鋅粉置換渣里,鋅粉置換渣采用酸性浸出和萃取工藝分離富集鎵,最終制備金屬鎵,鎵的綜合回收率達到71%. 通過對火法和濕法煉鋅中鎵回收工藝進行分析,對鎵回收工藝中存在的關鍵問題和分離技術進行了總結,提出萃取分離、乳狀液膜和樹脂吸附有望成為鋅冶煉過程中回收鎵的綠色高效短流程關鍵技術.

     

    Abstract: Gallium is an important dispersive metal with widespread applications in high-tech fields such as semiconductor materials, optoelectronics, and radio technology. Recently, the market demand for gallium metal has grown, given the continuous progress of science and technology. Gallium is primarily recovered as a by-product of aluminum and zinc metallurgy, accounting for approximately 90% and 10% of the total gallium production. The relatively low production share derived from zinc metallurgy is because of the high recovery difficulty. In this study, various technological routes for gallium extraction from zinc metallurgy are summarized with detailed analyses based on technological and economic perspectives. During closed blast furnace zinc smelting, >95% of Ga is enriched in water-quenched slag with an average mass fraction of 0.025%–0.031%. Several methods for extracting Ga from the slag are proposed, including reduction evaporation, chlorination volatilization, sulfuric acid leaching, caustic fusion–leaching, reduction smelting–electrolysis, and reduction smelting–slagging . However, these methods are difficult to obtain industrial applications due to long flow, low recovery, high cost, or severe pollution. During the conventional roasting–leaching–purification–electrowinning process, >93.5% of Ga remains in the leaching residue, closely associated with a ZnFe2O4 phase. Next, the reduction volatilization or hot acid leaching is employed to treat the residue. Only 10% of Ga volatilizes into the crude zinc oxide dust, whereas the other Ga remains in the kiln slag, causing huge Ga loss. Ga and Fe are dissolved into the solution through hot acid leaching, and the Ga and Fe separation is a large technological problem. Compared to roasting–leaching, pressure leaching is considered more suitable for treating the Ga-rich zinc concentrate due to the absence of a roasting procedure. Ga can be leached directly into the solution with a high reaction temperature and strong oxidization atmosphere. Before Fe removal, Ga is successfully enriched in the refining residue, with an average mass grade of >0.25%, through preneutralization and zinc powder replacement. Next, the Ga-enriching residue can be further treated by H2SO4 leaching and subsequent solvent extraction. Finally, Ga with 99% purity is produced using neutralization–sedimentation, alkaline dissolution, and electrowinning. The total recovery for Ga production from zinc concentrate to gallium product is >70%. Based on this technological route, an annual production of 15 t Ga is established in the Danxia smelter. In this research, the gallium distribution behavior among the multiphase during various procedures such as roasting, leaching, replacement, and sedimentation is clarified carefully, and a reasonable technological route for enriching Ga from zinc metallurgy is proposed. Moreover, the methods for separation and enrichment of Ga from the leaching solution are summarized. The development of solvent extraction, emulsion film, and resin adsorption should be the key progress for green and efficient Ga recovery from zinc metallurgy.

     

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