光致Fenton氧化-混凝耦合工艺的镍皂废水有机物去除特性

doi:10.19965/j.cnki.iwt.2025-0081

摘要/Abstract

摘要：

以镍皂废水中的有机物为目标污染物，构建光致Fenton氧化-混凝耦合工艺，旨在提高有机物的去除效率并克服传统Fenton工艺的局限性，结合铁盐的混凝效应与配体到金属的电荷转移（LMCT）过程，实现对有机污染物的高效持续去除。考察了该工艺对有机物的去除效能及其影响因素，通过计算过氧化氢（H₂O₂）分解利用率明确了4种H₂O₂活化途径占比，采用电子顺磁共振（EPR）与化学探针技术对各体系内的自由基进行鉴定与量化，最后对该工艺下形成的上清液和絮体分别进行X射线光电子能谱（XPS）表征。结果表明，铁盐投加量为10 mmol/L，H₂O₂投加量为80 mmol/L，初始pH为3时，该工艺60 min内对镍皂废水的COD去除率达到75.9%，H₂O₂的利用率高达99%，显著优于传统Fenton工艺的去除效果。同时，该工艺能够通过可见光诱导的LMCT循环高效地将Fe³⁺还原至Fe²⁺，从而持续活化H₂O₂生成大量羟基自由基（·OH）并通过铁盐的混凝作用进一步去除氧化中间产物。通过对比过二硫酸盐（PDS）和过一硫酸盐（PMS）对该工艺COD去除率的影响进一步证实了光致Fenton氧化-混凝耦合工艺具有较为宽泛的适用性，表明该工艺在处理高COD、高盐度有机废水方面具有潜力，为工业废水的有效处理提供了新的技术途径。

关键词: 镍皂废水, 配体-金属电荷转移, 光致Fenton氧化-混凝耦合工艺, Fe³⁺还原, 自由基

Abstract:

A nickel soap wastewater-based photocatalytic Fenton oxidation-coagulation coupling process was developed to enhance the removal efficiency of organic pollutants and overcome the limitations of conventional Fenton processes. The process was combined the coagulation effect of iron salts with the ligand-to-metal charge transfer(LMCT) process to achieve efficient and continuous removal of organic contaminants. The removal efficiency and influencing factors of the process were investigated, and the H₂O₂ decomposition utilization rate was calculated to determine the proportion of four H₂O₂ activation pathways. Electron paramagnetic resonance(EPR) and chemical probe techniques were employed to identify and quantify the free radicals in each system. Finally, the supernatant and flocs formed in the process were characterized by X-ray photoelectron spectroscopy(XPS). The results showed that with iron salt dosage of 10 mmol/L, H₂O₂ dosage of 80 mmol/L, and initial pH of 3, the process achieved COD removal rate of 75.9% within 60 minutes, with H₂O₂ utilization rate as high as 99%, significantly outperforming the removal efficiency of conventional Fenton process. Additionally, the process efficiently reduced Fe³⁺ to Fe²⁺ through the LMCT cycle induced by visible light, continuously activating H₂O₂ to generate a large number of hydroxyl radicals(·OH), which further removed oxidation intermediates through the coagulation effect of iron salts. A comparison with peroxymonosulfate(PMS) and persulfate(PDS) revealed that the photocatalytic Fenton oxidation-coagulation coupling process had a broad applicability, demonstrating its potential in treating high COD and high salinity organic wastewater, which provided a new technical approach for the effective treatment of industrial wastewater.

Key words: nickel soap wastewater, ligand to metal charge transfer, photo-assisted Fenton oxidation-coagulation coupled process, Fe³⁺ reduction, free radicals

中图分类号:

X703.1

綦玥彤, 许路, 卫小嘉, 金鑫, 白雪, 石烜, 黄悦, 金鹏康. 光致Fenton氧化-混凝耦合工艺的镍皂废水有机物去除特性[J]. 工业水处理, 2025, 45(12): 55-64.

Yuetong QI, Lu XU, Xiaojia Wei, Xin JIN, Xue BAI, Xuan SHI, Yue HUANG, Pengkang JIN. Characteristics of organic contaminant removal from nickel soap wastewater via a photocatalytic Fenton oxidation-coagulation coupling process[J]. Industrial Water Treatment, 2025, 45(12): 55-64.

https://www.iwt.cn/CN/Y2025/V45/I12/55

图/表 14

表1 镍皂废水水质特征

Table 1 Water quality of nickel soap wastewater

pH	油/（mg·L^-1）	COD/（mg·L^-1）	TDS/（mg·L^-1）
4.7±0.2	5.05	3 700±100	171 100±1 500

图1 耦合工艺处理镍皂废水实验装置

Fig.1 Experimental setup for nickel soap wastewater treatment by coupling process

图2 原位耦合工艺和Fenton工艺催化性能对比

Fig.2 Comparison of catalytic performance between in situ coupling process and Fenton process

图3 不同反应体系COD去除效果对比

Fig.3 Comparison of COD removal effect of different reaction systems

图4 Fe³⁺投加量对COD去除率（a）与H₂O₂利用率（b）的影响

Fig.4 Effect of Fe³⁺ dosage on COD removal（a） and H₂O₂ utilization rate（b）

图5 H₂O₂投加量对COD去除率（a）和H₂O₂利用率（b）的影响

Fig.5 Effect of H₂O₂ dosage on COD removal（a） and H₂O₂ utilization rate（b）

图6 初始pH对COD去除率（a）与H₂O₂利用率（b）的影响

Fig.6 Effects of initial pH on COD removal（a） and H₂O₂ utilization rate（b）

图7 HSSW-Fe³⁺-H₂O₂-Vis体系H₂O₂活化途径分析

Fig.7 Analysis of H₂O₂ activation pathway in HSSW-Fe³⁺-H₂O₂-Vis system

图8 不同反应体系DMPO的EPR特征峰谱图

Fig.8 EPR characteristic peak spectra of DMPO for different reaction systems

图9 不同反应体系中·OH稳态浓度对比

Fig.9 Comparison of steady-state concentrations of ·OH in different reaction systems

图10 镍皂废水中C 1s的XPS分峰拟合曲线

Fig.10 XPS peak fitting curves of C 1s in nickel soap wastewater

图11 HSSW-Fe³⁺-H₂O₂-Vis体系反应过程中上清液和絮体中碳形态占比变化

Fig.11 Changes in the proportion of carbon forms in the supernatant and floc during the reaction of HSSW-Fe³⁺-H₂O₂-Vis system

图12 光致Fenton氧化-混凝原位耦合工艺协同反应机制

Fig.12 Synergistic reaction mechanism of photo-Fenton oxidation-coagulation in-situ coupling process

图13 不同氧化剂对反应体系COD去除率的影响

Fig.13 Effect of different oxidizing agents on COD removal in the reaction system

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