华北电力大学马双忱教授：电吸附技术在电力行业废水处理中的应用

4 电吸附技术国内外发展

电吸附技术概念是由Blair和Murphy在1960年首次提出[55]。20世纪70年代，Johnson和Newman以多孔碳制作成吸附模型，得出决定电吸附吸附量的相关技术，包括电极表面积，施加的电压大小以及双电层电容等[56]。20世纪90年代中期，美国Lawrence Livermore 国家实验室将碳气凝胶将作为吸附电极应用于建立的电吸附模型中[57]。与初期缓慢的发展形成对比，近几十年电吸附技术飞速发展，在装置结构、离子交换膜、电极材料等方面取得巨大进步，电吸附受到广泛关注[58]。

最初电吸附装置进水方式是串联，供电方式是并联，导致通道里的管道呈蛇形分布，每对电极分开单独供电[57]。目前进水方式和供电方式相反，进水方式为并联，供电方式为串联，装置为直通式，水下进上出，串联供电，电能以离子形式储存在电吸附装置中，因此可将电吸附装置作为一个电容器，能量在内部回收，减少能量消耗。

20世纪90年代中期是电吸附技术产业化研究和使用的起步阶段。1996年，美国Lawrence Livermore 国家实验室研发了完整的电吸附系统，这是历史上第1套电吸附应用装置[57]。1999年，Biosource 公司开发出一套电吸附装置，用于海水淡化，为军方所用[58]。2003年，Enpar公司(加拿大)研制出新型电吸附装置，可选择性去除水中的铵根离子和硝酸根离子[59]。

21世纪初，我国开始进行电吸附技术的产业化研究，孙晓慰组建的爱思特净化设备有限公司于2001年研制出一套电吸附除盐装置，这是我国的第1套电吸附实用装置，在此基础上，开发了一系列的电吸附除盐装置，对于饮用水的进一步净化和工业废水处理起到了积极作用[60]。目前，国外的电吸附技术应用规模较小，电吸附装置流量仅为几十L/h。2006年12月，我国研发了大型电吸附装置，这是首套用于污水处理装置，已在齐鲁石化投产，处理流量为100 t/h[61]。2007年7月，国内首套万吨级大型污水处理电吸附装置在太原化学工业集团有限公司建成，出水作为工艺用水、锅炉补充水等。

基于电吸附技术环境友好的特点，可进一步与绿色能源相结合(如光伏发电等)；其能耗低，具有向小型化便携式发展的趋势。未来电吸附技术将向工艺优化、高比表面积、高比电容、低成本和易制造的电极材料等方向发展。

电吸附处理技术仍存在诸多缺陷(使用周期短、稳定性差、电极电阻较大、电流效率低、电极材料成本较高以及电催化活性等)，制约了其大规模应用。今后应从以下3个方面改进：

1)作为电吸附系统中最重要的组成部分，吸附材料的吸附容量是研究重点。提高吸附容量将大幅提高系统的除污能力，减少再生频次。此外，吸附材料的再生效果即材料的稳定性也会影响系统使用寿命。

2)结构特殊的电吸附系统可通过增大反应器比电极面积、强化传质，提高反应器的时空产率，完成系统优化。

3)电吸附水处理技术无法对某些污染物进行同时净化，因此可将其与其他水处理技术集成或采用催化电极材料。与国外技术发展相比，国内电化学水处理技术的研究尚缺乏系统性，在反应器优化设计与功能耦合方面尚有较大差距。

5 结 语

以电吸附为核心的一体化多功能耦合系统，兼顾除盐、防垢等功能，可用高效、低能耗去除废水中污染物，在电力行业具有广阔的应用前景。由于目前电吸附技术在电力行业中处于初步探索阶段，电吸附机理、预测模型、吸附材料等方面尚需进一步研究。尤其是在处理脱硫废水方面，由于脱硫废水水质复杂，盐浓度相对较高，仅依靠吸附材料很难有效净化，因此还需耦合其他技术。

参考文献（References）:

[1] 刘铖.基于专利分析的我国海水淡化技术及产业发展建议[D].天津：天津大学,2016.

LIU Cheng. Suggestion for technology and industrial development of desalination based on the results of the patent analysis [D]. Tianjin:Tianjin University,2016.

[2] 国务院.水污染防治行动计划[EB/OL].(2015-04-02)[2020.5.8]. /zhengce/content/2015-04/16/content_9613.htm?gs_ws=tsina_635647798845158909.

State Council. Action Plan for Water Pollution Control [EB/OL].(2015-04-02) [2020-05-08]./zhengce/content/2015-04/16/content_9613.htm?gs_ws=tsina_635647798845158909.

[3] 刘海洋,江澄宇,谷小兵,等.燃煤电厂湿法脱硫废水零排放处理技术进展[J]. 环境工程,2016,34(4):33-36.

LIU Haiyang,JIANG Chengyu,GU Xiaobing,et al. Development of zero liquid disge technologies for desulfurization wastewater from coal-fired power plant[J]. Environmental Engineering,2016,34(4):33-36.

[4] ANDERSON M A,CUDERO A L,PALMA J. Capacitive deionization as an electrochemical means of saving energy and delivering clean water. Comparison to present desalination practices:Will it compete? [J]. Electrochimica Acta,2010,55(12):3845-3856.

[5] SUSS M E,PORADA S,SUN X,et al. Water desalination via capacitive deionization[J]. Energy Environ. Sci.,2015,8(8):2296-2319.

[6] 蒋涛,王付超,李欲如,等.废水处理中的电吸附技术及应用[J].水能经济,2015(3):76-78.

JIANG Tao,WANG Fuchao,LI Xiru,et al. Application of electrosorption technology in advanced treatment of papermaking wastewater[J]. Water Research,2015(3):76-78.

[7] AGARTAN L,AKUZUM B,MATHIS T,et al. Influence of thermal treatment conditions on capacitive deionization performance and ge efficiency of carbon electrodes[J]. Separation and Purification Technology,2018,202:67-75.

[8] 胡承志,刘会娟,曲久辉.电化学水处理技术研究进展[J].环境工程学报,2018,12(3):677-696．

HU Chengzhi,LIU Huijuan,QU Jiuhui. Research progress of electrochemical technologies of water treatment[J]. Chinese Journal of Environmental Engineering,2018,12(3):677-696.

[9] 张瑞,赵霞,李庆维,等. 电化学水处理技术的研究及应用进展[J]. 水处理技术,2019,45(4):11-16.

ZHANG rui,ZHAO xia,LI qingwei,et al.Research and application progress of electrochemical technology in wastewater treatment [J]. Technology of Water Treatment,2019,45(4):11-16.

[10] 张思韬,韩严和,张晓飞,等.用于处理工业废水的电极材料研究进展[J].工业水处理,2019,39(11):1-6.

ZHANG Sitao,HAN Yanhe,ZHANG Xiaofei,et al. Advances in research on electrode materials for industrial wastewater treatment[J]. Industrial Water Treatment,2019,39(11):1-6.

[11] NIGHTINGALE E R J. Phenomenological theory of ion solvation effective radii of hydrated ions[J]. The Journal of Physical Chemistry,1958,63(9):566-567.

[12] 吴旭冉,贾志军,马洪运，等.电化学基础(Ⅲ)—双电层模型及其发展[J].储能科学与技术,2013,2(2):152-156.

WU Xuran,JIA Zhijun,MA Hongyun,et al. Fundamentals of electrochemistry(Ⅲ)：Electrical double layer model and its development [J]. Energy Storage Science and Technology,2013,2(2):152-156.

[13] WANG G,DONG Q,LING Z,et al. Hierarchical activated carbon nanofiber webs with tuned structure fabricated by electrospinning for capacitive deionization[J]. Journal of Materials Chemistry,2012,22(41):21819-21823.

[14] WANG G,QIAN B,DONG Q,et al. Highly mesoporous activated carbon electrode for capacitive deionization[J]. Separation & Purification Technology,2013,103:216-221.

[15] ZHAI Y,DOU Y,ZHAO D,et al. Carbon materials for chemical capacitive energy storage[J]. Advanced Materials,2011,23(42):4828-4850.

[16] OSCHATZ M,LEE J T,KIM H,et al. Micro- and mesoporous carbide-derived carbon prepared by a sacrificial template method in high performance lithium sulfur battery cathodes[J]. Journal of Materials Chemistry A,2014,41:17649-17654.

[17] YANG C M,CHOI W H,NA B K,et al. Capacitive deionization of NaCl solution with carbon aerogel-silicagel composite electrodes[J]. Desalination,2005,174(2):125-133.

[18] OREN Y. Capacitive deionization(CDI) for desalination and water treatment：Past,present and future(a review)[J].Desalination,2008,228(1/3):10-29.

[19] MORENO-CASTILLA C,MALDONADO-HDAR F J. Carbon aerogels for catalysis applications:An overview[J].Carbon,2005,43(3):455-465.

[20] YOSHIZAWA N,HATORI H,SONEDA Y,et al. Structure and electrochemical properties of carbon aerogels polymerized in the presence of Cu2[J]. Journal of Non Crystalline Solids,2003,330(1/3):100-105.

[21] LANDON J,GAO X,KULENGOWSKI B,et al. Impact of pore size acteristics on the electrosorption capacity of carbon xerogel electrodes for capacitive deionization[J]. Journal of the Electrochemical Society,2012,159(11):1861-1866.

[22] CHRISTOPHER J Gabelich,PEI Xu,YORAM Cohen. Chapter 10 concentrate treatment for inland desalting[J]. Sustainability Science & Engineering,2010,2(9):295-326.

[23] PRESSER V,HEON M,GOGOTSI Y. Carbide-derived carbons-from porous networks to nanotubes and graphene[J]. Advanced Functional Materials,2011,21(5):800-833.

[24] PORADA S,SCHIPPER F,ASLAN M,et al. Capacitive deionization using biomass-based microporous salt-templated heteroatom-doped carbons[J]. Chemsuschem,2015,8(11):1867-1874.

[25] STOECKLI F,GUILLOT A,SLASLI A M,et al. Microporosity in carbon blacks[J]. Carbon,2002,40(2):211-215.

[26] 许春玲,张小勇.电容吸附法脱盐技术研究进展[J].广州化工,2011,39(12):17-19.

XU Chunling,ZHANG Xiaoyong. Research progress of capacitance adsorption desalination technology [J]. Guangzhou Chemical Industry,2011,39(12):17-19.

[27] 贾景超,杨庆.Gouy-Chapman双电层模型在蒙脱石长程膨胀中应用[J].大连理工大学学报,2010,50(2):239-244.

JIA Jingchao,YANG Qing. Application of gouy-chapman double layer model to long-range swelling of montmorillonite [J]. Journal of Dalian University of Technology,2010,50(2):239-244.

[28] 徐文东,陈进富,李术元. 高表面活性炭电极的制备及其在双电层电容器中的应用[J]. 现代化工,2004(24):55-58.

XU Wendong,CHEN Jinfu,LI Shuyuan. Preparation of high surface area active carbon electrode and its application in electric double layer capacitor [J]. Modern Chemical Industry,2004(24):55-58.

[29] 徐艳辉,耿海龙.电极过程动力学:基础、技术与应用[M].北京：化学工业出版社,2015.

XU Yanhui,GENG Hailong. Electrode process dynamics:Fundamentals,technology and applications [M]. Beijing:Chemical Industry Press,2015.

[30] OLDHAM K B. A Gouy-chapman-stern model of the double layer at a(metal)/(ionic liquid) interface[J]. Journal of Electroanalytical Chemistry,2008,613(2):131-138.

[31] 丁宁,王晓琳.膜动电现象的研究进展[C]//第一届全国化学工程与生物化工年会.南京：南京工业大学，2004.

DING Ning,WANG Xiaolin.Research progress of membrane electrokinetic phenomena[C]//1stChinese National Chemical and Biochemical Engineering Annual Meeting.Nangjing:Nanjing Tech. University,2004.

[32] 王建,营爱玲.表界面现象及双电层模型[J].连云港化工高等专科学校学报,2000(1):13-15.

WANG Jian,YING Ailing. Surface interface phenomenon and double electric layer model [J]. Journal of Lianyungang Chemical College,2000(1):13-15.

[33] YING T Y,YANG K L,YIACOUMI S,et al. Electrosorption of ions from aqueous solutions by nanostructured carbon aerogel[J]. J. Colloid Interface Sci.,2002,250(1):18-27.

[34] HOU C H,LIANG C,YIACOUMI S,Et Al. Electrosorption capacitance of nanostructured carbon-based materials[J]. Journal of Colloid & Interface Science,2006,302(1):54-61.

[35] AVRAHAM E,NOKED M,SOFFER A,et al. The feasibility of boron removal from water by capacitive deionization[J].Electrochimica Acta,2011,56(18):6312-6317.

[36] JEON S I,PARK H R,YEO J G,et al. Desalination via a new membrane capacitive deionization process utilizing flow-electrodes[J]. Energy & Environmental Science,2013,6(5):1471-1475.

[37] 邓述波,余刚.环境吸附材料及应用原理[M]．北京:科学出版社，2012:1-4.

DENG Shubo,YU Gang. Environmental adsorbent and its application principle [M]. Beijing:Science Press,2012:1-4.

[38] 沈叔云,冯向东,施国忠. 电吸附技术在火电厂循环冷却排污水处理中的应用可行性研究[J].浙江电力,2015,34(11):89-99.

SHEN Shuyun,FENG Xiangdong,SHI Guozhong. Feasibility study on application of electroadsorption technique in circulating cooling water treatment in thermal power plant [J]. Zhejiang Electric Power,2015,34(11):89-99.

[39] 关民普,刘盟. 电除尘器的除尘原理、过程及优缺点[J]. 科技信息,2011(25):99-101.

GUAN Minpu,LIU Meng. Dust removal principle,process and advantages and disadvantages of electrostatic precipitator [J]. Science and Technology Information,2011(25):99-101.

[40] SUSS M E,BIESHEUVEL P M,BAUMANN T F,et al. In situ spatially and temporally resolved measurements of salt concentration between ging porous electrodes for desalination by capacitive deionization[J]. EnvironmentalEnce & Technology,2014,48(3):2008-2015.

[41] JIA B,ZHANG W. Preparation and application of electrodes in capacitive deionization(CDI):A state-of-art review[J]. Nanoscale Research Letters,2016,11(1):64-89.

[42] 尹广军,陈福明.电容去离子研究进展[J].水处理技术,2003,29(2):63-66．

YIN Guangjun,CHEN Fuming. Progress in capacitive deionization[J]. Technology of Water Treatment,2003,29(2):63-66.

[43] 唐朝春,许荣明.电吸附水处理技术研究进展[J].现代化工,2019,39(10):15-23.

TANG Chaochun,XU Rongming. Research progress in electro-adsorption water treatment technology [J]. Modern Chemical Industry,2019,39(10):15-23.

[44] NIGHTINGALE E R J. Phenomenological theory of ion solvation. effective radii of hydrated ions[J]. The Journal of Physical Chemistry,1958,63(9):566-567.

[45] MA S,MA L,CHEN G,et al. Experimental study on desalination using electro-sorption technology with plate-type activated carbon fiber electrode[J]. Desalination and Water Treatment,2018,126:116-126.

[46] 李永辉.电吸附技术在循环冷却排污水系统排污水处理中的应用[J].工业用水与废水,2012,43(5):71-73.

LI Yonghui. Application of electrosorb technology in treatment of sewage disged from circulating cooling water system [J]. Industrial Water and Wastewater,2012,43(5):71-73.

[47] 中华人民共和国生态环境部.关于发布《火电厂污染防治技术政策》的公告[EB/OL].(2017-01-11). .cn/gkml/hbb/bgg/201701/t20170117_394809.htm.

Ministry of Ecology and Environment,PRC. Announement on the release of "pollution control technology policy of thermal power plant" [EB/OL].(2017-01-11)..cn/gkml/hbb/bgg/201701/t20170117_394809.htm.

[48] 叶春松,罗珊,张弦,等. 燃煤电厂脱硫废水零排放处理工艺[J]. 热力发电,2016,45(9):105-108,139.

YE Chunsong,LUO Shan,ZHANG Xian,et al. Key problems and developing trend of zero disge technology of desulfurization waste water [J]. Thermal Power Generation,2016,45(9):105-108,139.

[49] 叶春松,黄建伟,刘通,等. 燃煤电厂烟气脱硫废水处理方法与技术进展[J]. 环境工程,2017(11):15-18.

YE Chunsong,HUANG Jianwei,LIU Tong,et al. Technology progresses and treatment methods of flue gas desulfurization wastewater in coal-fired plants [J]. Environmental Engineering,2017(11):15-18.

[50] 施云芬,王旭晖.湿法烟气脱硫废水处理研究进展[J].工业水处理,2015,35(12):14-17,43.

SHI Yunfen,WANG Xuhui. Research progress in the wastewater treatment of wet fIue gas desuIfurization [J]. Industrial Water Treatment,2015,35(12):14-17,43.

[51] 孙振宇,沈明忠.燃煤电厂脱硫废水零排放工程案例研究[J].工业水处理,2018,38(10):102-105.

SUN Zhenyu,SHEN Mingzhong. Case study on zero disge engineering of desulphurization wastewater in coal-fired power plants [J]. Industrial Water Treatment,2018,38(10):102-105.

[52] 杜梦,邵楠,姜益善.燃煤电厂水处理及脱硫废水零排放技术分析[J].山西建筑,2019,45(4):189-190.

DU Meng,SHAO Nan,JIANG Yishan. Analysis on feasible technology about wastewater treatment and desulfurization wastewater zero disge in thermal power plant [J]. Shanxi Building,2019,45(4):189-190.

[53] 崔丽.火力发电厂脱硫废水深度处理工艺的应用[J]. 吉林电力,2018,46(5):145-146.

CUI Li. Application of advanced desulfurization wastewater treatment technology in thermal power Plants[J]. Jilin Electric Power,2018,46(5):145-146.

[54] 潘利祥,孙国刚.气液撞击流烟气脱硫零排放一体化技术[C]//中国环境科学学会2006年学术年会优秀论文集(下卷).北京：中国环境科学出版社，2006.

PAN Lixiang,SUN Guogang. Integration of zero-emission technology for flue gas desulfurization with gas-liquid impingement flow [C]//Chinese Society for Environmental Science 2006 Annual Conference,Volume II.Beijing:China Environmental Science Press，2006.

[55] FARMER J C,FIX D V,MACK G V,et al．Capacitive deionization of NaCl and NaNO3solution with carbon aerogel electrode[J]. Journal of Electrochemical Society,1996,143(1):159-169.

[56] REN Q D,WANG G,WU T T,et al. Calcined MgAl-layered double hydroxide/graphene hybrids for capacitive deionization[J]. Industrial & Engineering Chemistry Research,2018,57(18):6417-6425.

[57] MA X J,LI M,LIU X,et al. A graphene oxide nanosheet-modified Ti nanocomposite electrode with enhanced electrochemical property and stability for nitrate reduction[J]. Chemical Engineering Journal,2018,348:171-179.

[58] OREN Y. Capacitive deionization(CDI) for desalination and water treatment:past,present and future(a review) [J]. Desalination,2008,228:10-29.

[59] CHRISTEN K. Desalination technology could clean up wastewater from coal-bed methane production[J]. Environmental Science & Technology,2006,40(3):639-647.

[60] 陈兆林,宋存义,孙晓慰,等.电吸附除盐技术的研究及应用进展[J].工业水处理. 2011,31(4):11-14.

CHEN Zhaolin,SSONG Cunyi,SUN Xiaowei,et al. Progress in the research on the electrosorption desalination technology and its application[J]. Industrial Water Treatment,2011,31(4):11-14.

[61] 陈静,李玉道,李小平.曝气生物过滤—多介质过滤—电吸附工艺处理炼油污水[J]. 石化技术与应用,2008,26(2):184-188.

CHEN Jing,LI Yudao,LI Xiaoping. Treatment of refinery wastewater by aerated biofiltration with multi-medium filtration and electric adsorption process [J]. Petrochemical Technology and Application,2008,26(2):184-188.