掺硼金刚石电极电化学处理二甲基亚砜工业废水

doi:10.19965/j.cnki.iwt.2025-0312

摘要/Abstract

摘要：

掺硼金刚石（Boron-doped diamond，BDD）作为高性能的电化学阳极材料，在废水中难降解有机物的矿化处理领域有广泛的应用。以BDD为阳极材料，探究电化学处理未加盐/加盐二甲基亚砜（DMSO）工业废水的效能与污染物去除机制。结果表明，未添加盐时，BDD阳极能够有效去除DMSO和COD，在电流密度3.33~23.33 mA/cm²下反应120 min，去除率分别超过90.43%和62.35%。反应过程中仅检测到微量的活性自由基，DMSO和COD的去除以直接氧化为主。外加氯化钠和硫酸钠均可提高DMSO工业废水的电导率，并可促进活性氧自由基的生成，加速电化学氧化反应速率。投加氯化钠后，在电流密度40 mA/cm²和55 mA/cm²下反应20 min即可完全去除DMSO。自由基猝灭实验证实，BDD阳极对加盐DMSO工业废水中DMSO和COD的去除机制仍以阳极氧化为主，自由基氧化为辅。对比不加盐/加盐DMSO工业废水，适量添加电解质（尤其是氯化钠）可大幅缩短反应时间，降低能耗，为电化学法高效节能处理DMSO工业废水提供理论参考。

关键词: 硅基掺硼金刚石, 二甲基亚砜, 工业废水, 电化学氧化

Abstract:

Boron-doped diamond (BDD), as a high-performance electrochemical anode material, has been extensively applied in the mineralization treatment of refractory organic compounds in wastewater. This study investigated the efficacy and mechanisms of pollutant removal during the electrochemical treatment of dimethyl sulfoxide (DMSO) industrial wastewater by using a BDD anode, under both salt-free and saline conditions. The results demonstrated that the BDD anode effectively removed both DMSO and chemical oxygen demand(COD) without the addition of salts. Across a current density range of 3.33-23.33 mA/cm², effective removal of DMSO (≥90.43%) and COD (≥62.35%) was achieved within 120 min. The detection of merely trace radical species confirmed that direct oxidation was the predominant removal mechanism. Both NaCl and Na₂SO₄ additions increased the wastewater conductivity and facilitated reactive oxygen species (ROS) formation, thereby enhancing the electrochemical oxidation kinetics. Complete DMSO removal was achieved within 20 min at 40 mA/cm²and 55 mA/cm² after NaCl introduction. Quenching experiments demonstrated that anodic oxidation was still the principal mechanism for DMSO and COD removal from saline wastewater using the BDD anode, while radical oxidation played a minor role. In contrast to the salt-free system, the judicious addition of electrolytes (NaCl) markedly enhanced process efficiency by reducing both reaction time and energy input, thereby paving the way for more economical electrochemical treatment of DMSO wastewater.

Key words: silicon-based boron-doped diamond, dimethyl sulfoxide, industrial wastewater, electrochemical oxidation

中图分类号:

X703

武英, 徐黄欢, 龙盈桥, 王雨石, 魏秋平, 蔡群欢, 薛罡. 掺硼金刚石电极电化学处理二甲基亚砜工业废水[J]. 工业水处理, 2026, 46(3): 57-64.

Ying WU, Huanghuan XU, Yingqiao LONG, Yushi WANG, Qiuping WEI, Qunhuan CAI, Gang XUE. Electrochemical treatment of dimethyl sulfoxide industrial wastewater by boron doped diamond electrode[J]. Industrial Water Treatment, 2026, 46(3): 57-64.

https://www.iwt.cn/CN/Y2026/V46/I3/57

图/表 8

图1 电化学实验装置

Fig.1 Electrochemical experimental apparatus

图2 电流密度对DMSO废水处理效果的影响

Fig.2 Effect of current density on the treatment efficiency of DMSO-containing wastewater

图3 外加氯化钠（a~c）及硫酸钠（d~f）条件下电流密度对DMSO废水处理效果的影响

Fig.3 Effect of current density on the treatment efficiency of DMSO-containing wastewater after sodium chloride addition（a-c） and sodium sulfate addition（d-f）

图4 相同浓度下不同电解质对DMSO降解效能的影响

Fig.4 Effects of different electrolytes at the same concentration on degradation efficiency of DMSO

图5 猝灭剂对加盐组中DMSO去除率的影响及加盐组中·OH的浓度

Fig.5 Effects of quenchers on the DMSO removal rates in salt-added group and ·OH concentration in salt-added groups

图6 DMSO降解过程功率的变化

Fig.6 Changes of power in DMSO degradation process

表1 BDD处理DMSO工业废水实验结果

Table 1 Experimental results of DMSO industrial wastewater treated by BDD

电流密度/（mA·cm^-2）	电压	电流/A	反应时间/min	COD去除率/%	DMSO去除率/%	阶段耗电量/（W·h·L^-1）	能耗/（kW·h·m^-3）
23.33	可变	3.50	120.00	94.01	100.00	71.36	71.36
16.67	可变	2.50	120.00	76.46	100.00	49.92	49.92
10.00	可变	1.50	120.00	66.84	98.23	25.01	25.01
3.33	可变	0.50	120.00	62.35	90.43	6.82	6.82

表2 BDD处理加盐DMSO工业废水实验结果

Table 2 Experimental results of salted DMSO industrial wastewater treated by BDD

电解质	电流密度/（mA·cm^-2）	电压/V	电流/A	反应时间/min	COD 去除率/%	DMSO去除率/%	阶段耗电量/（W·h·L^-1）	能耗/（kW·h·m^-3）
氯化钠	40	9.86~10.06	6.0	10	28.52	73.26	9.99	9.99
				20	36.73	100	19.86	19.86
				30	43.37	100	29.70	29.70
氯化钠	55	10.16~12.17	8.25	10	35.35	86.99	15.96	15.96
				20	51.98	100	30.93	30.93
				30	54.15	100	45.15	45.15
硫酸钠	40	9.21~11.5	6.0	10	7.45	34.40	11.15	11.15
				20	21.12	56.11	21.47	21.47
				30	33.93	69.04	30.96	30.96
硫酸钠	55	10.72~14.18	8.25	10	12.61	37.40	18.37	18.37
				20	24.62	61.27	34.93	34.93
				30	39.91	79.03	50.51	50.51

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