构建了导电陶瓷膜(CCM)为阴极、钛钌铱电极为阳极的一体化电化学耦合膜反应系统,开展了电场辅助膜分离处理含油废水实验及膜污染减缓机制研究.结果表明,以喷雾热解-原位沉淀法制备的CCM电极表面稳定附着了Sb-SnO2导电涂层,膜表面平均粗糙度约为324nm,比改性前降低了32%.在-1.0V电化学条件下,CCM电极阻抗值约38 Ω·cm2,腐蚀电位为-0.36V,具备良好的电极稳定性和抗腐蚀性.在处理含油废水实验中,当施加电场强度为0.6~9.8V/cm时,CCM膜通量衰减幅度均表现出随电场强度增加膜通量衰减幅度逐步减缓的趋势.当电场强度达到4.2V/cm时,膜通量衰减速率逐步稳定,以水力反冲洗方式循环处理0.1g/L和0.5g/L的含油废水5次后,CCM膜通量较无电场条件可提高15%~17%,具备更长的膜应用周期.膜污染分析表征显示,CCM电极相比改性前具备更好的亲水性和表面电负性,在电场辅助膜分离过程中,与油滴(Zeta电位为-35.2~-16.7mV)会发生明显的斥力作用.膜污染堵塞模型揭示电场作用显著改善了膜污染的不可逆情况,可将膜污染过程由标准堵塞模型转化为完全堵塞模型,进一步证实了电场作用对减缓膜污染的支撑作用.
Abstract
An integrated electrochemical-coupled membrane reactor system was constructed, where a conductive ceramic membrane (CCM) cathode fabricated by spray pyrolysis-in situ precipitation and a Ti/RuO2-IrO2 anode were employed to investigate the mitigation mechanism of membrane fouling during electric field-assisted oil-containing wastewater treatment. It was demonstrated that a stable Sb-SnO2 conductive coating was successfully deposited on the CCM electrode surface through the spray pyrolysis-in-situ precipitation method, exhibiting an average roughness of approximately 324nm, which represented a 32% reduction compared to the pre-modified state. Under an electrochemical potential of -1.0V, the CCM electrode was characterized by an impedance value of 38 Ω·cm² and a corrosion potential of -0.36V, indicating excellent electrode stability and corrosion resistance. In oily wastewater treatment experiments, when the applied electric field intensity was varied between 0.6~9.8V/cm, the flux decline rate of the CCM membrane was observed to progressively decrease with increasing electric field intensity. The flux decay rate was found to stabilize when the electric field intensity reached 4.2V/cm. After five cycles of hydraulic backwashing, the CCM membrane flux was measured to be 15%~17% higher for both 0.1g/L and 0.5g/L oily wastewater concentrations compared to non-electrified conditions, demonstrating extended membrane service life. Membrane fouling characterization revealed that the modified CCM exhibited enhanced hydrophilicity and surface electronegativity, which generated strong repulsive forces against oil droplets (Zeta potential: -35.2 to~16.7mV) during electric field-assisted separation. Analysis of the membrane fouling mechanism indicated that the electric field application significantly improved the irreversibility of membrane fouling, with the fouling process being transformed from a standard clogging model to a complete clogging model. These findings further confirmed the critical role of electric fields in mitigating membrane fouling progression.
关键词
导电陶瓷膜 /
含油废水 /
电化学 /
膜污染
Key words
conductive ceramic membrane /
oily wastewater /
electrochemistry /
membrane fouling
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基金
国家能源集团科技项目(GJNY-21-129)
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