电活性膜去除氯酚污染物——面向工程应用的放大策略
Electrochemical Removal of Chlorophenol Pollutants by Reactive Electrode Membranes: Scale-up Strategy for Engineered Applications
氯酚(CP)是一类重要的难降解污染物,对人类和其他生物具有高度毒性。电活性膜(REM)通过穿流式操作,能够强化对流传质,在电化学去除难降解污染物过程中彰显出巨大潜力。然而相关研究通常报道的是实验室规模,无法直接保证REM反应器在工程化放大中的成功运行。本研究证明了由亚氧化钛陶瓷阳极和不锈钢阴极配置的同轴管式电极(TCE)可用于大规模的CP 去除。理论和试验结果均表明,TCE构型不仅使电极表面处处正交于电场线,而且具有与电极长度成反比的欧姆电阻。此外,TCE构型可根据废水流动方向将从阳极流向阴极(AC模式)调整为从阴极流向阳极(CA模式),为CP的选择性降解创造了可控条件。单程穿流实验结果证实在CA模式下,2,4-二氯苯酚(2,4-DCP)的去除动力学常数较AC模式高一个数量级,2,4-DCP 和化学需氧量(COD)去除率分别为98%和72.5%。理论计算和实验结果表明,CA模式具有较低的反应活化能和自由能。在不增加欧姆电阻或降低活性面积的情况下,TCE构型适用于组件化策略来放大电化学反应器规模。使用三个TCE组件时,2,4-DCP的去除率达到99.4%,能耗为1.5 kW h m−3。本研究为REM反应器提出了一种合理的电极构型设计,为电化学去除氯酚类污染物在跨越面向工程放大的'死亡之谷'提供有效策略。
Chlorophenols (CPs) are significant refractory pollutants that are highly toxic to humans and other organisms. Reactive electrode membranes (REMs) show considerable potential in the electrochemical removal of refractory pollutants by allowing flow-through operations with convection-enhanced mass transfer. However, relevant studies are commonly performed on the laboratory scale, and there is no straightforward method that guarantees success in scaling up engineered REM reactors. In this study, we demonstrated that a tubular concentric electrode (TCE) configuration with a titanium suboxide ceramic anode and a stainless-steel cathode is suitable for large-scale CPs removal. Both theoretical and experimental results showed that the TCE configuration not only allows the electrode surface to be orthogonal to electric field lines everywhere, but also has an ohmic resistance that is inversely proportional to the length of the electrode. In addition, the TCE configuration can be operated in either the anode-to-cathode (AC) or the cathode-to-anode (CA) mode based on the flow direction, creating adjustable conditions for selective degradation of CPs. This was confirmed by 98% removal of 2,4-dichlorophenol (2,4-DCP) and 72.5% removal of chemical oxygen demand (COD) in the CA mode, in which the kinetic constant was one order of magnitude higher than that for the AC mode under flow-through single-pass operations. This can be explained by the lower activation energy and free energy in the CA mode, as revealed by theoretical calculations and experimental measurements. The TCE configuration is also suitable for a numbering-up strategy to scale up the electrochemical reactor without increasing the ohmic resistance or decreasing the specific electrode area, achieving 99.4% removal of 2,4-DCP with an energy consumption of 1.5 kW·h·m−3 when three TCE modules were employed. This study presents a suitable electrode design configuration for the REM reactor, offering effective strategies to bridge the 'Valley of Death' encountered when scaling up the electrochemical removal of CP pollutants.
Chlorophenols / Reactive electrode membrane / Tubular concentric electrode / Scale-up
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