三维电极-电Fenton耦合法处理乳化含油废水

doi:10.19965/j.cnki.iwt.2024-0038

摘要/Abstract

摘要：

机加工产生的乳化含油废水中有机物成分复杂，可生化性差，采用纳米零价铁、活性炭及玻璃珠混合颗粒作为粒子电极，构建三维电极-电Fenton耦合工艺体系对其进行处理。考察阴极板材料、粒子电极投加比、电压、pH、极板间距、曝气量等因素对乳化含油废水总油、COD去除效果的影响。结果表明，pH、极板间距、曝气量、电压是主要影响因子，影响程度排序为pH>极板间距>曝气量>电压。采用三维电极-电Fenton体系处理COD 1 030 mg/L、总油质量浓度约为150 mg/L的乳化含油废水，在电压为25 V，活性炭、纳米零价铁、玻璃珠投加量分别为60、20、20 g/L，pH=3，极板间距6 cm，曝气量为1.0 L/min，电解液Na₂SO₄质量浓度4 g/L条件下污染物去除效果较佳，COD和总油去除率最高分别可达89.95%和93.97%。GC-MS图谱分析表明，三维电极-电Fenton耦合工艺可将乳化含油废水中的长链、短链石油烃等氧化、破链、分解成为分子较小的有机物，甚至矿化为二氧化碳和水。技术经济分析表明，该工艺具有一定的成本优势，有推广应用前景。

关键词: 三维电极, 电Fenton, 含油废水, 粒子电极

Abstract:

The emulsified oily wastewater generated from machining processes has complex organic components and poor biodegradability. Nanoscale zero-valent iron, activated carbon, and glass beaded mixed particles were used as particle electrodes to construct a three-dimensional electrode-electro-Fenton coupling system to effectively treat the wastewater. The effects of cathode plate material, particle electrode ratio, voltage, pH, electrode spacing, aeration rate, and other factors on the removal efficiencies of total oil and COD in emulsified oily wastewater were researched. The results showed that pH, electrode spacing, aeration rate, and voltage were the main effect factors, with the order of pH>electrode spacing>aeration rate>voltage. The three-dimensional electrode-electro-Fenton system was used to treat emulsified oily wastewater with COD of 1 030 mg/L and total oil of about 150 mg/L. Under the conditions of voltage of 25 V, activated carbon, nanoscale zero-valent iron, and glass bead dosages of 60, 20, and 20 g/L, pH=3, electrode plate spacing of 6 cm, aeration rate of 1.0 L/min, and electrolyte Na₂SO₄ concentration of 4 g/L, the pollutant removal effect was optimal, with COD and total oil removal rates reaching up to 89.95% and 93.97%, respectively. GC-MS analysis showed that the three-dimensional electrode-electro-Fenton system could oxidize, break, and decompose long-chain and short-chain petroleum hydrocarbons in emulsified oily wastewater into smaller organic compounds, and they were even mineralized into carbon dioxide and water. Technical and economic analysis showed that this process had certain cost advantages and had prospects for promotion and application.

Key words: three-dimensional electrode, electro-Fenton, oily wastewater, particle electrode

中图分类号:

X703.1

张华, 户传龙, 吴迪, 杨文新, 薛佳, 张文艺. 三维电极-电Fenton耦合法处理乳化含油废水[J]. 工业水处理, 2025, 45(2): 118-125.

Hua ZHANG, Chuanlong HU, Di WU, Wenxin YANG, Jia XUE, Wenyi ZHANG. Experimental study on three-dimensional electrode-electrode-Fenton coupling for emulsified oily wastewater treatment[J]. Industrial Water Treatment, 2025, 45(2): 118-125.

https://www.iwt.cn/CN/Y2025/V45/I2/118

图/表 10

图1 实验装置示意

Fig.1 Schematic diagram of experimental setup

图2 阴极材料对含油废水处理效果的影响

Fig.2 The influence of cathode material on the treatment effect of oily wastewater

图3 活性炭与nZVI粒子投加质量比对含油废水处理效果的影响

Fig.3 The influence of the mass ratio of activated carbon to nZVI particles on the treatment effect of oily wastewater

图4 低阻抗粒子与玻璃珠质量比对含油废水处理效果的影响

Fig.4 The influence of the mass ratio of low-impedance particles to glass beads on the treatment effect of oily wastewater

图5 电压对含油废水处理效果的影响

Fig.5 The influence of voltage on the treatment effect of oily wastewater

图6 曝气量对含油废水处理效果的影响

Fig.6 The influence of aeration volume on the treatment effect of oily wastewater

图7 初始pH对含油废水处理效果的影响

Fig.7 The influence of initial pH on the treatment effect of oily wastewater

图8 极板间距对含油废水处理效果的影响

Fig.8 The influence of plate spacing on the treatment effect of oily wastewater

表1 正交实验结果

Table 1 Orthogonal test results

序号	A（电压）/V	B（曝气量）/ （L·min^-1）	C（pH）	D（极板间距）/cm	COD去除率（α）/%	总油去除率（β）/%
1	20	0.5	1	4	56.41	60.04
2	20	1.0	3	6	85.34	90.29
3	20	1.5	5	8	50.27	55.94
4	25	0.5	3	8	75.85	79.60
5	25	1.0	5	4	66.28	69.74
6	25	1.5	1	6	72.98	78.01
7	30	0.5	5	6	68.81	74.24
8	30	1.0	1	8	73.76	77.96
9	30	1.5	3	4	74.39	78.02
k_α ₁	64.007	67.023	67.717	65.693
k_α ₂	71.703	75.127	78.527	75.710
k_α ₃	72.320	65.880	61.787	66.627
R_α	8.313	9.247	16.740	10.017
k_β ₁	68.757	71.293	72.003	69.267
k_β ₂	75.783	79.330	82.637	80.847
k_β ₃	76.740	70.657	66.640	71.167
R_β	7.983	8.673	15.997	11.580
主次顺序	C>D>B>A

图9 含油废水处理前后GC-MS图谱

Fig.9 GC-MS map before and after oily wastewater treatment

参考文献 14

1	曹梦竺，闫艳. 机械制造加工中乳化液含油废水的处理［J］. 河南科技，2021，40（31）：139-141.
	CAO Mengzhu， YAN Yan. Treatment of emulsion wastewater containing oil in machinery manufacturing process［J］. Henan Science and Technology，2021，40（31）：139-141.
2	HU Yang， YU Fuzhi， BAI Zhongteng，et al. Preparation of Fe-loaded needle coke particle electrodes and utilisation in three-dimensional electro-Fenton oxidation of coking wastewater［J］. Chemosphere，2022，308：136544. doi:10.1016/j.chemosphere.2022.136544
3	JUNG K W， HWANG M J， PARK D S，et al. Performance evaluation and optimization of a fluidized three-dimensional electrode reactor combining pre-exposed granular activated carbon as a moving particle electrode for greywater treatment［J］. Separation and Purification Technology，2015，156：414-423. doi:10.1016/j.seppur.2015.10.030
4	程佳鑫，李荣兴，杨海涛，等. 三维电催化氧化处理难生化降解有机废水研究进展［J］. 环境化学，2022，41（1）：288-304. doi:10.7524/j.issn.0254-6108.2020082804
	CHENG Jiaxin， LI Rongxing， YANG Haitao，et al. Review of three-dimensional electrodes for bio-refractory organic wastewater treatment［J］. Environmental Chemistry，2022，41（1）：288-304. doi:10.7524/j.issn.0254-6108.2020082804
5	于凤娇，朱佳，黄潇，等. 三维电芬顿催化降解四溴双酚A（TBBPA）效能研究［J］. 水处理技术，2022，48（5）：108-113.
	YU Fengjiao， ZHU Jia， HUANG Xiao，et al. Study on the catalytic degradation of tetrabromobisphenol A（TBBPA） by three-dimensional electro-Fenton process［J］. Technology of Water Treatment，2022，48（5）：108-113.
6	WANG Zhaoyang， QI Jingyao， FENG Yan，et al. Fabrication and electrocatalytic performance of a novel particle electrode［J］. Catalysis Communications，2014，46：165-168. doi:10.1016/j.catcom.2013.12.015
7	VOIRY D， CHHOWALLA M， GOGOTSI Y，et al. Best practices for reporting electrocatalytic performance of nanomaterials［J］. ACS Nano，2018，12（10）：9635-9638. doi:10.1021/acsnano.8b07700
8	王寒梅. 零价铁耦合芬顿氧化法深度处理含油废水研究［D］. 绵阳：西南科技大学，2022. doi:10.1021/acsestwater.2c00040
	WANG Hanmei. Advanced treatment of oil-bearing wastewater by zerovalent iron coupled Fenton oxidation. Mianyang：Southwest University of Science and Technology，2022. doi:10.1021/acsestwater.2c00040
9	刘济嘉. 三维电极-电芬顿耦合法处理石油采出水的试验研究［D］. 沈阳：沈阳建筑大学，2016.
	LIU Jijia. Experimental study on treatment of petroleum produced water by three-dimensional electrode-electro-Fenton coupling method［D］. Shenyang：Shenyang Jianzhu University，2016.
10	徐斌，张书陵，高月香，等. 石墨烯三维电极-电Fenton系统降解甲基橙［J］. 中国环境科学，2020，40（10）：4385-4394.
	XU Bin， ZHANG Shuling， GAO Yuexiang，et al. Degradation of methyl orange by graphene three-dimensional electrode-electro Fenton system［J］. China Environmental Science，2020，40（10）：4385-4394.
11	李亚峰，张策，单连斌，等. 三维电极电Fenton法对苯酚废水处理效果实验研究［J］. 环境工程，2020，38（9）：1-5.
	LI Yafeng， ZHANG Ce， SHAN Lianbin，et al. Experimental study on treatment of phenol wastewater by three-dimensional electrode Fenton method［J］. Environmental Engineering，2020，38（9）：1-5.
12	GAO Xinyu， ZHANG Chunying， WANG Yanqiu，et al. Treatment of membrane concentrated landfill leachate by a heterogeneous electro-Fenton process with an iron-loaded needle coke cathode［J］. Journal of Environmental Chemical Engineering，2022，10（5）：108287. doi:10.1016/j.jece.2022.108287
13	吴娜娜，钱虹，郑璐，等. 三维电极-电Fenton法处理孔雀石绿染料废水研究［J］. 沈阳建筑大学学报（自然科学版），2018，34（1）：183-192.
	WU Nana， QIAN Hong， ZHENG Lu，et al. Experimental study on the treatment of malachite green dyeing wastewater by three-dimensional electrode-electro-Fenton process［J］. Journal of Shenyang Jianzhu University（Natural Science），2018，34（1）：183-192.
14	陈子杨，黄胜，余健. 三维电极-电Fenton处理毒死蜱废水研究［J］. 工业水处理，2022，42（4）：132-137.
	CHEN Ziyang， HUANG Sheng， YU Jian. Study on treatment of chlorpyrifos wastewater by three-dimensional electrode-electro-Fenton process［J］. Industrial Water Treatment，2022，42（4）：132-137.

[1]	杨伟球, 史广宇. 锂电池生产废水处理工程设计和运行实例[J]. 工业水处理, 2025, 45(3): 206-211.
[2]	陈越, 彭雪儿, 周琛阳, 李婧, 孟欣怡, 高丽丽. CuFeKao粒子电极三维非均相电Fenton体系降解亚甲基蓝[J]. 工业水处理, 2025, 45(2): 54-62.
[3]	傅翔宇, 李亚峰. 三维电极电Fenton处理阿奇霉素制药废水研究[J]. 工业水处理, 2024, 44(6): 158-164.
[4]	马宁, 李志鹏, 郭宏山, 张秀芳, 王雪清. 超疏水异质纤维聚结材料的构建及乳化油去除性能[J]. 工业水处理, 2024, 44(5): 171-176.
[5]	董泽平, 刘振阳, 赵昕琛, 何争光, 崔丰启. 高效三维电极电Fenton降解苯酚实验研究[J]. 工业水处理, 2024, 44(3): 89-96.
[6]	李倩, 陈吉祥, 杨轩, 彭程, 王天烽. 3株高效石油降解菌对SBR处理含油废水的强化作用[J]. 工业水处理, 2024, 44(11): 52-60.
[7]	李亚峰, 许嗣鼎, 高崇, 傅翔宇. 负载型三维电极-电Fenton法处理活性艳橙X-GN废水[J]. 工业水处理, 2024, 44(1): 80-87.
[8]	肖信锦, 黄金, 王慧娟, 孙雪菲, 邓扬悟. PVA型超亲水-水下超疏油过滤膜油水分离性能研究[J]. 工业水处理, 2023, 43(8): 123-127.
[9]	李兆阳, 姚庆林, 张浩, 李诚, 顾悦, 王少坡. 三维电极氧化处理污水厂二级出水中试研究[J]. 工业水处理, 2023, 43(8): 159-164.
[10]	钟志贤, 刘晓婷, 黄小雯, 宋勇. 气浮/三维电解/生物降解处理芯片封装测试废水研究[J]. 工业水处理, 2023, 43(6): 171-175.
[11]	杨洋, 马迁, 李增辉, 袁旭冬, 魏平方, 戴捷. N-Mn-TiO₂/AC粒子电极的制备及其降解性能研究[J]. 工业水处理, 2023, 43(11): 114-119.
[12]	陈子杨, 黄胜, 余健. 三维电极-电Fenton处理毒死蜱废水研究[J]. 工业水处理, 2022, 42(4): 132-137.
[13]	范聪颖, 江博, 杨宇航, 戴捷. 聚苯胺改性石墨毡阴极电Fenton降解效能研究[J]. 工业水处理, 2022, 42(4): 73-77.
[14]	张黎,王春昊,黄殿男,张磊. 改性TiO₂/GAC光电协同处理甲基橙废水[J]. 工业水处理, 2022, 42(12): 122-127.
[15]	乔明晨,陈兴权,乔春生. 电絮凝破乳处理机加工行业废切削液工程实例[J]. 工业水处理, 2021, 41(9): 147-151.

选择文件类型/文献管理软件名称

选择包含的内容