阴极阳极协同电催化降解高硫酸盐废水中活性染料

doi:10.19965/j.cnki.iwt.2023-0294

摘要/Abstract

摘要：

采用辊压法制备炭黑/聚四氟乙烯（C/PTFE）气体扩散电极，并对其微观结构进行表征。构建以掺硼金刚石（BDD）为阳极，C/PTFE气体扩散电极为阴极的电催化氧化体系，阳极硫酸盐活化技术与阴极原位合成H₂O₂技术协同处理高硫酸盐废水中的活性艳蓝X-BR。结果表明，制备的C/PTFE电极作阴极时，电催化氧化体系中活性艳蓝X-BR去除效果优于铂（Pt）阴极体系和不锈钢（SS）阴极体系。通过猝灭实验发现，BDD/（C/PTFE）电化学体系中产生的SO₄ ^·-和·OH等高活性物质间相互转化，为电化学体系提供了可持续氧化能力，二者对于体系中活性艳蓝X-BR去除贡献度分别为54.51%和25.75%。建立了电化学氧化体系中TOC去除率及单位能耗二次项模型，通过响应曲面法优化降解含活性艳蓝X-BR废水的运行参数。优化条件下（初始pH=5.0，电流密度=120 mA/cm²， $C N a 2 S O 4$ =0.25 mol/L，C _{活性艳蓝X-BR}=1 000 mg/L），电解120 min，废水TOC去除率为63.86%，体系单位质量TOC能耗为256.02 kW·h/kg，继续电解至240 min，可将水中的活性艳蓝X-BR完全矿化，为双电极协同电催化氧化处理高硫酸盐有机废水提供理论支持。

关键词: 电催化氧化, BDD阳极, C/PTFE气体扩散阴极, 电活化硫酸盐, Doehlert响应曲面设计

Abstract:

A carbon black/polytetrafluoroethylene(C/PTFE) gas diffuser electrode was prepared by the roller compaction method and its micro-structure was characterized. An electrocatalytic oxidation system using a boron-doped diamond as anode and a C/PTFE gas diffuser electrode as cathode was constructed. The reactive brilliant blue X-BR in high sulfate wastewater was treated cooperatively by combining sulfate activation technology at anode with in-situ synthesis of H₂O₂ technology at cathode. The results showed that when the prepared C/PTFE electrode was used as the cathode, the removal effect of active brilliant blue X-BR in electro-activated sulfate system was better than that in platinum(Pt) cathode system and stainless steel(SS) system. According to the quenching experiment, the interaction between the highly active substances such as SO₄ ^·- and ·OH produced by the electrochemical system of BDD/(C/PTFE) provided the bulk sustainable oxidation capacity for the degradation of reactive brilliant blue X-BR, and the contribution of these two substances to the removal of active brilliant blue X-BR were 54.51% and 25.75%, respectively. A quadratic model of TOC removal rate and unit energy consumption in electrochemical oxidation system was established. The operational parameters of reactive brilliant blue X-BR degradation were optimized by experimental design matrix. Under optimized conditions (initial pH=5.0, current density=120 mA/cm², $C N a 2 S O 4$ =0.25 mol/L,C _{active brilliant blue X-BR}=1 000 mg/L), and electrolysis for 120 min, the removal rate of TOC in wastewater was 63.86% and the unit energy consumption of the system was 256.02 kW·h/kg. The reactive brilliant blue X-BR in water could be completely mineralized by continued electrolysis to 240 min. The results provide theoretical support for the dual-electrode collaborative electrocatalytic oxidation treatment of high sulfate organic wastewater.

Key words: electrocatalytic oxidation, BDD anode, C/PTFE gas diffusion cathode, electroactivated sulfate, Doehlert experimental design matrix

中图分类号:

TQ426
X703

刘楚楚, 金春姬, 孙楠, 高孟春. 阴极阳极协同电催化降解高硫酸盐废水中活性染料[J]. 工业水处理, 2024, 44(4): 127-137.

Chuchu LIU, Chunji JIN, Nan SUN, Mengchun GAO. Electrocatalytic degradation of reactive dyes in high sulfate wastewater by synergistic effect of anode and cathode[J]. Industrial Water Treatment, 2024, 44(4): 127-137.

https://www.iwt.cn/CN/Y2024/V44/I4/127

图/表 8

图1 电催化氧化体系装置示意

Fig.1 Schematic diagram of electric catalytic oxidation system device

图2 C/PTFE 复合电极材料的SEM

Fig.2 SEM of C/PTFE composite electrode material

图3 不同阴极体系中活性艳蓝X-BR的质量浓度变化及TOC的去除率

Fig.3 Concentration changes of reactive brilliant blue X-BR and removal rates of TOC in different cathode systems

图4 BDD/（C/PTFE）与BDD/SS电催化氧化体系ESR能谱

Fig.4 ESR spectrum of electro-activated sulfate system of BDD/（C/PTFE） and BDD/SS

图5 不同自由基猝灭剂下活性艳蓝X-BR去除率的变化

Fig.5 Removal rate changes of reactive brilliant blue X-BR under different free radical scavengers

表1 Doehlert实验设计的编码和操作水平及实验结果

Table 1 Coding and operating level of Doehlert experimental design and experiment results

序号	X ₁	X ₂/（mA·cm^-2）	X ₃/（mol·L^-1）	X ₄/（mg·L^-1）	TOC去除率/%	单位质量TOC能耗/（kW·h·kg^-1）
1	0.5（9）	0.866（160）	0（0.21）	0（800）	57.64	461.00
2	-0.5（5）	0.866	0	0	56.10	460.25
3	0（7）	0.577（140）	-0.817（0.01）	0	38.65	676.33
4	-0.5	0.289（120）	0.817（0.41）	0	58.17	333.51
5	0	0（100）	0（0.21）	0	62.93	320.99
6	-0.5	-0.866（40）	0	0	31.93	450.99
7	-0.5	-0.289（80）	-0.817	0	37.54	510.39
8	0.5	-0.289	-0.817	0	35.73	536.24
9	0	0.577	-0.204（0.16）	-0.791（400）	43.67	781.70
10	0.5	0.289	0.204（0.26）	0.791（1 200）	55.82	284.25
11	-0.5	0.289	0.204	0.791	58.71	207.43
12	0	0	0.613（0.36）	-0.791	46.29	789.57
13	-0.5	-0.289	-0.204	-0.791	37.00	1 027.03
14	1（11）	0	0	0	58.71	341.94
15	-1（3）	0	0	0	61.35	348.68
16	0.5	-0.289	-0.204	-0.791	36.79	1 022.02
17	0.5	-0.866	0	0	30.55	467.10
18	0	-0.577（60）	0.204	0.791	43.24	298.93
19	0	0	-0.613（0.06）	0.791	47.76	320.10
20	0.5	0.289	0.817	0	60.34	323.69
21	0	-0.577	0.817	0	36.34	467.80

图6 两因素交互作用对TOC去除率影响的三维曲面和等高线

Fig.6 Three-dimensional surface and contour map of the influence of the interaction of two factors on the TOC removal rate

图7 两因素交互作用对单位能耗影响的三维曲面和等高线

Fig.7 Three-dimensional surface and contour map of the influence of the interaction of two factors on the unit energy consumption

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