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超声辅助酸浸强化废铅锡合金中铅与锡的分离:选择性溶解及声化学机理

Intensifying separation of Pb and Sn from waste Pb-Sn alloy by ultrasound-assisted acid leaching: Selective dissolution and sonochemistry mechanism.

作者信息

Liu Bingbing, Shi Chaoya, Huang Yanfang, Han Guihong, Sun Hu, Zhang Li

机构信息

Henan Critical Metals Institute, Zhengzhou University, Zhengzhou 450001, Henan, PR China; School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, PR China.

Henan Critical Metals Institute, Zhengzhou University, Zhengzhou 450001, Henan, PR China; School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, PR China.

出版信息

Ultrason Sonochem. 2024 Jan;102:106758. doi: 10.1016/j.ultsonch.2024.106758. Epub 2024 Jan 9.

Abstract

Clean and efficient extraction and separation of precious metals from discarded Pb-Sn alloy is critical to the sustainable utilization of solid waste resources. Dense oxide layer and compact alloy texture in the waste Pb-Sn alloy pose challenges to the effective leaching process. Ultrasonic waves are demonstrated to improve separation efficiency via the favorable physical and chemical effects in solution system. In this study, ultrasound-assisted leaching technology is attempted to rapidly and selectively extract Pb from the waste Pb-Sn alloy, and gives emphasis on ultrasonic electrochemical behaviors. The Eh-pH diagrams of Sn-HO and Pb-HO systems were firstly analyzed to lay the selective dissolution foundation. It's indicated that oxidizing HNO lixiviant is suitable to realize the selective separation of Pb. Both Sn and Pb can be dissolved to ionic Sn and Pb in the HNO solution. However, Sn rapidly oxidizes to Sn and Sn further hydrolyzes to insoluble SnO, which will agglomerate on unreacted materials to limit internal metal leaching in conventional leaching process. Due to the vibratory stripping of oxide layer by physical effect of ultrasound, the conventional acid leaching time for Pb extraction can be halved with the ultrasound assistance. About 99.12 % Pb and only 0.1 % Sn are dissolved in ultrasound-assisted leaching under the following optimal parameters: 0.5 mol/L HNO, leaching temperature of 80 °C, time of 30 min, liquid-to-solid ratio of 20 mL/g, and ultrasound intensity of 0.52 W/cm. Leaching kinetics of Pb, phase transition, microstructure evolution, Pb-Sn galvanic corrosion and dissolution polarization curve were studied to determine the ultrasonic enhanced dissolution mechanism. Notably, Pb and Sn form a microcorrosion galvanic cell in which Sn acts as a cathode and is protected while the Pb undergoes intensifying corrosion as the anode giving rise to the higher Pb dissolution efficiency. Eventually, it's suggested that Pb can be rapidly extracted and separated from the waste Pb-Sn alloy during the ultrasound-assisted HNO leaching process via the ultrasound physical and chemical effects, especially the sonochemistry aspect of intensified spot corrosion and galvanic corrosion. The proposed ultrasonic electrochemical corrosion in this work were applicable to the extraction of valuable metals from various waste alloys through leaching method.

摘要

从废弃铅锡合金中清洁高效地提取和分离贵金属对于固体废物资源的可持续利用至关重要。废弃铅锡合金中的致密氧化层和致密的合金结构对有效的浸出过程构成挑战。超声波通过溶液体系中良好的物理和化学作用被证明可以提高分离效率。在本研究中,尝试采用超声辅助浸出技术从废弃铅锡合金中快速选择性地提取铅,并重点研究超声电化学行为。首先分析了Sn-HO和Pb-HO体系的Eh-pH图,为选择性溶解奠定基础。结果表明,氧化型硝酸浸出剂适合实现铅的选择性分离。在硝酸溶液中,锡和铅都能溶解为离子态的锡和铅。然而,锡迅速氧化为Sn,Sn进一步水解为不溶性的SnO,这会在未反应的物料上团聚,从而限制传统浸出过程中内部金属浸出。由于超声波的物理作用使氧化层发生振动剥离,在超声辅助下,提取铅的传统酸浸时间可减半。在以下最佳参数下:0.5mol/L硝酸、浸出温度80℃、时间30分钟、液固比20mL/g、超声强度0.52W/cm,超声辅助浸出中约99.12%的铅被溶解,而锡仅溶解0.1%。研究了铅的浸出动力学、相变、微观结构演变、铅锡电偶腐蚀和溶解极化曲线,以确定超声增强溶解机制。值得注意的是,铅和锡形成了一个微腐蚀原电池,其中锡作为阴极受到保护,而铅作为阳极腐蚀加剧,导致铅的溶解效率更高。最终表明,在超声辅助硝酸浸出过程中,通过超声的物理和化学作用,特别是强化点蚀和电偶腐蚀的声化学方面,可以从废弃铅锡合金中快速提取和分离铅。本工作中提出的超声电化学腐蚀适用于通过浸出法从各种废合金中提取有价金属。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d19f/10825661/9381e8294194/gr1.jpg

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