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新型次氯酸钙/二价铁预处理超滤膜工艺用于藻类污染水体的净化。

Novel calcium hypochlorite/ferrous iron as an ultrafiltration membrane pretreatment process for purifying algae-laden water.

机构信息

School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan, 250101, PR China; Resources and Environment Innovation Institute, Shandong Jianzhu University, Jinan, 250101, PR China.

School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan, 250101, PR China.

出版信息

Environ Res. 2024 Jan 1;240(Pt 1):117572. doi: 10.1016/j.envres.2023.117572. Epub 2023 Nov 7.

Abstract

Algal fouling has become one of the most critical factors hindering the large-scale development of membrane processes in algae-laden water treatment. Herein, novel calcium hypochlorite (Ca(ClO))/ferrous iron (Fe(II)) process was proposed as an ultrafiltration (UF) membrane pretreatment technology, and its effects on membrane fouling and water properties were systematically studied. Results showed that the terminal specific fluxes were significantly elevated to 0.925 and 0.933, with the maximum removal ratios of reversible resistance reaching 99.65% and 96.99% for algae-laden water and extracellular organic matter (EOM), respectively. The formation of cake filtration was dramatically delayed, accompanied by a significant reduction of the adhesion free energy, and the contaminants attached to the membrane surface were effectively decomposed. With respect to water quality, the removal ratios of OD and turbidity achieved 81.25-95.31% and 90.16-97.72%, individually. The maximum removal rates of DOC, UV and fluorescent organics in influent water reached 46.14%, 55.17% and 75.77%, respectively. Furthermore, the generated reactive species (e.g., •OH, Cl•, Cl• and ClO•) could efficiently degrade EOM, which appreciably reduced the electrostatic repulsion between the algal foulants while ensuring the integrity of algal cells. At the Ca(ClO)/Fe(II) dosage of 0.04/0.24 mM, the zeta potential changed from -32.9 mV to -10.8 mV, and a large range of aggregates was formed. The macromolecules in the algal solution were significantly removed, and the proportion of micromolecular organics was increased to some extent. Coagulation of in-situ formed Fe(III) dominated the membrane fouling mitigation, and the reactive species also contributed to the improvement of filtration performance. Overall, Ca(ClO)/Fe(II) pretreatment has an exceptional prospect for efficient degradation of algal pollutants and enhancement of UF capability.

摘要

藻类污染已成为阻碍富含藻类水中膜处理大规模发展的最关键因素之一。在此,提出了一种新型的次氯酸钙(Ca(ClO))/二价铁(Fe(II))工艺作为超滤(UF)膜预处理技术,并系统研究了其对膜污染和水质的影响。结果表明,终端比通量显著提高至 0.925 和 0.933,藻类和胞外有机物(EOM)的可逆阻力去除率最大值分别达到 99.65%和 96.99%。滤饼过滤的形成明显延迟,同时自由能的附着显著降低,附着在膜表面的污染物被有效分解。就水质而言,OD 和浊度的去除率分别达到 81.25-95.31%和 90.16-97.72%。进水 DOC、UV 和荧光有机物的最大去除率分别达到 46.14%、55.17%和 75.77%。此外,生成的活性物质(如•OH、Cl•、Cl•和 ClO•)可有效降解 EOM,在保证藻细胞完整性的同时,显著降低藻污染物之间的静电斥力。在 Ca(ClO)/Fe(II)剂量为 0.04/0.24 mM 时,zeta 电位从-32.9 mV 变为-10.8 mV,形成了较大范围的聚集物。藻类溶液中的大分子物质明显被去除,小分子有机物的比例在一定程度上有所增加。原位形成的 Fe(III)的混凝作用主导了膜污染的缓解,活性物质也有助于改善过滤性能。总体而言,Ca(ClO)/Fe(II)预处理在有效降解藻类污染物和提高 UF 能力方面具有显著的前景。

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