基于掺硼金刚石电极的工业废水处理研究进展

doi:10.16085/j.issn.1000-6613.2023-0269

摘要/Abstract

摘要：

工业废水普遍具有可生化性差、污染物种类多、有机物含量高、难降解等特点，常规处理手段难使其达标排放。以电化学高级氧化工艺为代表的污水深度处理工艺处理污水效果显著，是近年来环境工作者的研究热点之一。掺硼金刚石（boron-doped diamond，BDD）电极理化性质优异，是目前电化学高级氧化处理废水最为理想高效的阳极材料，但关于大尺寸BDD电极的应用及处理真实工业废水的研究情况尚未及时总结归纳。本文以基于BDD电极的电化学高级氧化工艺过程为对象，对该过程涉及到的废水特点、工艺原理、BDD电极特点及制备方法、处理案例和工艺参数优化等方面的研究进展进行综述，重点聚焦不同污染体系下的大型实验室装置、中试装置和处理真实工业废水案例，总结了BDD电极材料开发情况和不同类型工艺的技术特点，探讨了工艺优化方面的研究进展和目前限制该技术大规模工业化应用的主要原因。最后对基于BDD电极的电化学高级氧化工艺应用前景和重点发展方向作出了展望。

关键词: 电化学, 废水, 氧化, 掺硼金刚石, 工艺优化

Abstract:

Industrial wastewater is generally characterized by poor biochemical properties, with many kinds of pollutants, high organic content and difficulty in degradation, etc. It is difficult to meet the discharge standards with conventional treatment methods. The deep treatment process of wastewater represented by the electrochemical advanced oxidation process can effectively treat industrial wastewater, which is one of the research hotspot for environmentalists in recent years. Boron-doped diamond (BDD) electrode has excellent physicochemical properties and is the most ideal and efficient anode material for the electrochemical oxidation treatment of wastewater. However, the research on the application of BDD electrodes in large size and the treatment of real industrial wastewater has not been summarized in time. This paper firstly reviewed the research progress on industrial wastewater characteristics, process principles, BDD electrode characteristics and preparation methods, treatment cases and optimization of process parameters involved in this process based on the electrochemical advanced oxidation process with BDD electrodes, and focused on large laboratory installations, pilot plants, and real industrial wastewater under different pollution systems. In the following, the development of BDD electrode materials and the technical characteristics of different types of processes were summarized. At the same time, the research progress of process optimization and the main reasons that currently limited the large-scale industrial application of this technology were also discussed. Finally, this paper concluded with an outlook on the industrial application prospects and main development directions of the electrochemical advanced oxidation process based on BDD electrodes.

Key words: electrochemistry, wastewater, oxidation, boron-doped diamond, process optimization

中图分类号:

王博, 张长安, 赵利民, 袁俊, 宋永一. 基于掺硼金刚石电极的工业废水处理研究进展[J]. 化工进展, 2024, 43(1): 501-513.

WANG Bo, ZHANG Chang’an, ZHAO Limin, YUAN Jun, SONG Yongyi. Industrial wastewater treatment technology based on boron-doped diamond electrodes:A review[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 501-513.

图/表 9

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阳极材料	析氧过电位/V（vs.SHE）
石墨	1.7
Pt	1.6~1.9
RuO₂	1.4~1.7
IrO₂	1.5~1.8
Ebonex^® (Ti₄O₇)	1.7~1.8
PbO₂	1.8~2.0
SnO₂	1.9~2.2
BDD	2.2~2.6

阳极材料	析氧过电位/V（vs.SHE）
石墨	1.7
Pt	1.6~1.9
RuO₂	1.4~1.7
IrO₂	1.5~1.8
Ebonex^® (Ti₄O₇)	1.7~1.8
PbO₂	1.8~2.0
SnO₂	1.9~2.2
BDD	2.2~2.6

参数	NeoCoat	湖南新锋	参数	NeoCoat	湖南新锋
基底	硅、金属（铌、钽、钨）	硅、铌、钽、泡沫金属	基体厚度/mm	1~2	—
电极形状	矩形、网状、定制形状	矩形、圆盘、网格、泡沫、定制形状	晶体尺寸/μm	—	1~10
尺寸/mm	矩形（100×100）矩形（100×100）定制形状（最大400×1200）	矩形（1×1~350×350）圆盘（ϕ1~350）颗粒（2×10^-4~30）	BDD涂层厚度/μm	—	5~50
尺寸/mm	矩形（100×100）矩形（100×100）定制形状（最大400×1200）	矩形（1×1~350×350）圆盘（ϕ1~350）颗粒（2×10^-4~30）	膜厚度均匀性	±5%(100mm)	—
析氧过电位/V	—	2.4~2.7	膜厚度均匀性	±5%(100mm)	—
析氧过电位/V	—	2.4~2.7	掺硼水平/μg·g^-1	500~10000	5000~50000
应用条件	阴极/阳极/双极	阴极/阳极/双极	掺硼水平/μg·g^-1	500~10000	5000~50000
应用条件	阴极/阳极/双极	阴极/阳极/双极	电阻率/mΩ·cm	1~100	0.01~10
涂层面	单面/双面	单面/双面	电阻率/mΩ·cm	1~100	0.01~10

参数	NeoCoat	湖南新锋	参数	NeoCoat	湖南新锋
基底	硅、金属（铌、钽、钨）	硅、铌、钽、泡沫金属	基体厚度/mm	1~2	—
电极形状	矩形、网状、定制形状	矩形、圆盘、网格、泡沫、定制形状	晶体尺寸/μm	—	1~10
尺寸/mm	矩形（100×100）矩形（100×100）定制形状（最大400×1200）	矩形（1×1~350×350）圆盘（ϕ1~350）颗粒（2×10^-4~30）	BDD涂层厚度/μm	—	5~50
尺寸/mm	矩形（100×100）矩形（100×100）定制形状（最大400×1200）	矩形（1×1~350×350）圆盘（ϕ1~350）颗粒（2×10^-4~30）	膜厚度均匀性	±5%(100mm)	—
析氧过电位/V	—	2.4~2.7	膜厚度均匀性	±5%(100mm)	—
析氧过电位/V	—	2.4~2.7	掺硼水平/μg·g^-1	500~10000	5000~50000
应用条件	阴极/阳极/双极	阴极/阳极/双极	掺硼水平/μg·g^-1	500~10000	5000~50000
应用条件	阴极/阳极/双极	阴极/阳极/双极	电阻率/mΩ·cm	1~100	0.01~10
涂层面	单面/双面	单面/双面	电阻率/mΩ·cm	1~100	0.01~10

合成方法	原理	优势	劣势	最大电极尺寸	应用情况
热丝法（HFCVD）	利用金属丝（Ta、W）通电产生热量，激发气源形成等离子体，并在基底表面沉积成膜	工艺、设备简单，投资低，参数范围宽，通过合理的灯丝排布可实现大面积BDD电极制备^[33]	成膜均匀性较差，易受灯丝气化污染，沉积速率低（1~10μm/h），对氧化性气体敏感	400mm×1200mm	技术成熟，应用广泛。瑞士NeoCoat公司，德国DiaChem公司均有成熟产品，我国湖南新锋科技有限公司、北京沃尔德金刚石工具有限公司以及中南大学、吉林大学等均有广泛研究和成熟产品
微波等离子体法（MPCVD）	利用微波辉光放电等离子体激发气源，在基底表面沉积成膜	成膜均匀，质量高，沉积温度低^[34]	设备昂贵，有效沉积面积难扩大	ϕ350mm	技术成熟，但应用较少，德国Iplas公司具有专利产品（CYRANNUS^®）,国内武汉工程大学、北京科技大学、西南科技大学等均有相关研究
直流等离子体喷射法（DCPJCVD）	利用直流放电击穿流经阴阳极之间的气体形成电弧，气体被急剧加热后从等离子体炬喷口迅速喷出并在基底表面沉积成膜	金刚石沉积速率快^[35]	设备昂贵，投资高，工艺控制困难，易对基底造成热损伤	—	多以实验室研究为主，尚无成熟产品