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用于控制酸性矿山排水的 PropS-SH/Ce(dbp) 涂层在抑制黄铁矿氧化方面的性能和机理。

Performance and mechanisms of PropS-SH/Ce(dbp) coatings in the inhibition of pyrite oxidationtion for acid mine drainage control.

机构信息

Guangdong Provincial Key Lab of Green Chemical Product Technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, PR China.

Key Lab of Pollution Control and Ecosystem Restoration in Industry Cluster, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou, 510006, PR China.

出版信息

Environ Pollut. 2023 Apr 1;322:121162. doi: 10.1016/j.envpol.2023.121162. Epub 2023 Jan 27.

Abstract

Inhibition of tailings oxidation could availably control the generation of acid mine wastewater from its source. Organosilanes serving as a high-efficiency inhibitor of the oxidation of pyrite, bring some problems including safety hazards caused by large amounts of organic solvents, difficult high-temperature curing, poor long-term properties, and so on. In our work, the PropS-SH/Ce (dbp) (PS/Ce (dbp)) passivator with excellent passivation performance and self-healing properties was prepared by choosing 3-mercaptopropyltrimethoxysilane (PropS-SH) and dibutyl phosphate (Ce (dbp)) as the main passivating agent and the repair agent, respectively. We reduced the ratio of ethanol to water by adjusting the pH of the organosilane condensation and also achieved room-temperature curing by extending the curing time. Electrochemical and chemical leaching experiments results showed that the most appropriate addition of Ce (dbp) was 0.2 wt% for enhancing the passivation performance of the passivated coating. In a 6-month chemical leaching experiment, the PS/Ce (dbp)-0.2 passivation coating cured at room temperature showed a better passivation effect and maintained 90.55% and 78.54% of total Fe and SO passivation efficiencies. The passivation and self-healing mechanisms were investigated by FT-IR, XPS, Si NMR, and other characterization methods, which were as follows: silane formed a cross-linked mesh structure by Si-O-Si bonding, in which Ce (dbp) was physically filled. And the Si-OH on the surface of the passivation film formed Fe-O-Si bonds with the hydroxyl groups on the surface of the pyrite, thus attaching to the surface of the pyrite and isolating the oxidation medium. When the passivation coating was locally damaged, the oxidation reaction caused a change in pH, which accelerated the dissolution of Ce (dbp) in the passivation layer. Ce underwent a valence change and formed a CeO precipitate, while dbp could form a complex with Fe on the pyrite surface, both of which worked together to repair the broken passivation coating and prevent the oxidation reaction.

摘要

抑制尾矿氧化可以有效地从源头上控制酸性矿山废水的产生。有机硅烷作为一种高效的黄铁矿氧化抑制剂,带来了一些问题,包括大量有机溶剂带来的安全隐患、高温固化困难、长期性能差等。在我们的工作中,选择 3-巯丙基三甲氧基硅烷(PropS-SH)和磷酸二丁酯(Ce(dbp))作为主要的钝化剂和修复剂,制备了具有优异的钝化性能和自修复性能的 PropS-SH/Ce(dbp)(PS/Ce(dbp))钝化剂。我们通过调节有机硅烷缩合的 pH 值来降低乙醇与水的比例,并通过延长固化时间实现了室温固化。电化学和化学浸出实验结果表明,Ce(dbp)的最佳添加量为 0.2wt%,可提高钝化涂层的钝化性能。在 6 个月的化学浸出实验中,室温固化的 PS/Ce(dbp)-0.2 钝化涂层表现出更好的钝化效果,保持了 90.55%和 78.54%的总铁和 SO 的钝化效率。通过傅里叶变换红外光谱(FT-IR)、X 射线光电子能谱(XPS)、硅核磁共振(Si NMR)等表征方法研究了钝化和自修复机制,结果表明:硅烷通过 Si-O-Si 键形成交联的网状结构,其中 Ce(dbp)被物理填充。钝化膜表面的 Si-OH 与黄铁矿表面的羟基形成 Fe-O-Si 键,从而附着在黄铁矿表面并隔离氧化介质。当钝化涂层局部损坏时,氧化反应会导致 pH 值发生变化,从而加速钝化层中 Ce(dbp)的溶解。Ce 发生价态变化形成 CeO 沉淀,而 dbp 可以与黄铁矿表面的 Fe 形成配合物,两者共同修复破损的钝化涂层,阻止氧化反应。

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