铁碳微电解技术在难治理废水中的研究进展

doi:10.16085/j.issn.1000-6613.2017-2272

摘要/Abstract

摘要： 铁碳微电解技术具有处理效率高、操作方便、占地面积小、原材料廉价和适用范围广等优点。但在机理研究以及具体的实际应用过程中，仍存在一些问题有待解决。因此，本文综合分析了铁碳微电解技术去除难治理废水中污染物的过程和机理，指出微电解作用机理的定量化及耦合关系是一个重要研究方向。在应用研究方面，目前主要存在两个问题：①微电解材料的板结和钝化问题；②如何提高微电解工艺适用的pH范围。本文从材料合成和反应器的改进方面进行分析，针对前者问题，提出可采用纳米技术以及高温烧结技术合成新型微电解材料，以及采用流化床和内循环微电解反应器也可解决该问题；针对后者问题，提出可改性微电解材料，以及在微电解反应器上外加电场和采用臭氧曝气微电解。最后，系统总结了该技术在印染废水、垃圾渗沥液、制药废水和重金属废水的应用概况。

关键词: 铁碳, 电解, 材料, 反应器, 废水, 环境

Abstract: The iron-carbon micro-electrolysis technology has obvious advantages, such as high efficiency, ease of operation, less area requirement and cheap raw materials, and has a broad application prospect as well. But there are still some problems remaining to be solved for the mechanism research and practical application. Therefore, the removal mechanism of contaminant from refractory wastewater was comprehensively analyzed. The quantification and coupling relationship of the micro-electrolysis functional mechanism is an important research direction. There are still two major problems in the applied research. The first is agglomeration and passivation of the material. The second is how to improve the applicable pH range of micro-electrolysis. Synthesis of materials and improvement of the reactor were systematically analyzed in this paper. For the former problem, the nanotechnology and high-temperature sintering process could be applied to synthesize new material, and the employment of fluidized bed and internal circulation micro-electrolysis reactor were the solution to the problem. For the latter, modification of the micro-electrolysis material, and employment of electric assist and ozone aeration were the solution. Finally, research and application of the technology were also systematically summarized in dye wastewater, landfill leachate, pharmaceutical wastewater and heavy metal wastewater.

Key words: iron-carbon, electrolysis, material, reactor, wastewater, environment

中图分类号:

X703

王毅博, 冯民权, 刘永红, 李耀中. 铁碳微电解技术在难治理废水中的研究进展[J]. 化工进展, 2018, 37(08): 3188-3196.

WANG Yibo, FENG Minquan, LIU Yonghong, LI Yaozhong. Recent advances on iron-carbon micro-electrolysis technology for refractory wastewater[J]. Chemical Industry and Engineering Progress, 2018, 37(08): 3188-3196.

参考文献

[1] SEGURA Y, MARTINEZ F, MELERO J A. Effective pharmaceutical wastewater degradation by Fenton oxidation with zero-valent iron[J]. Applied Catalysis B:Environmental, 2013, 136:64-69.
[2] 刘晓冉, 李金花, 周保学, 等. 铁碳微电解处理中活性炭吸附作用及其影响[J]. 环境科学与技术, 2011, 34(1):128-131. LIU X R, LI J H, ZHOU B X, et al. Role of activated carbon adsorption in iron-carbon micro-electrolysis process for wastewater treatment[J]. Environmental Science and Technology, 2011, 34(1):128-131.
[3] ZHOU H M, LV P, SHEN Y Y, et al. Identification of degradation products of ionic liquids in an ultrasound assisted zero-valent iron activated carbon micro-electrolysis system and their degradation mechanism[J]. Water Research, 2013, 47(10):3514-3522.
[4] DOU X, LI R, ZHAO B, et al. Arsenate removal from water by zero-valent iron/activated carbon galvanic couples[J]. Journal of Hazardous Materials, 2010, 182(1):108-114.
[5] GHAUCH A. Rapid removal of flutriafol in water by zero-valent iron powder[J]. Chemosphere, 2008, 71(5):816-826.
[6] NING X A, WEN W, ZHANG Y P, et al. Enhanced dewaterability of textile dyeing sludge using micro-electrolysis pretreatment[J]. Journal of Environmental Management, 2015, 161:181-187.
[7] LAI B, ZHOU Y, QIN H, et al. Pretreatment of wastewater from acrylonitrile-butadiene-styrene (ABS) resin manufacturing by micro-electrolysis[J]. Chemical Engineering Journal, 2012, 179:1-7.
[8] BRILLAS E, SIRES I, OTURAN M A. Electro-Fenton process and related electrochemical technologies based on Fenton's reaction chemistry[J]. Chemical Reviews, 2009, 109(12):6570.
[9] SUN Y, PIGNATELLO J J. Photochemical reactions involved in the total mineralization of 2,4-D by iron(3+)/hydrogen peroxide/UV[J]. Environmental Science and Technology, 1993, 27(2):304-310.
[10] NAMKUNG K C, BURGESS A E, BREMNER D H. A Fenton-like oxidation process using corrosion of iron metal sheet surfaces in the presence of hydrogen peroxide:a batch process study using model pollutants[J]. Environmental Technology, 2005, 26(3):341.
[11] YING D, PENG J, XU X, et al. Treatment of mature landfill leachate by internal micro-electrolysis integrated with coagulation:a comparative study on a novel sequencing batch reactor based on zero valent iron[J]. Journal of Hazardous Materials, 2012, 229(5):426-433.
[12] JU F, HU Y Y. Removal of EDTA-chelated copper from aqueous solution by interior microelectrolysis[J]. Separation and Purification Technology, 2011, 78(1):33-41.
[13] YANG D, ENGLEHARDT J D. Hydrogen peroxide-enhanced iron-mediated aeration for the treatment of mature landfill leachate[J]. Journal of Hazardous Materials, 2008, 153(1/2):293-299.
[14] FATEMINIA F S, FALAMAKI C. Zero valent nano-sized iron/clinoptilolite modified with zero valent copper for reductive nitrate removal[J]. Process Safety and Environmental Protection, 2013, 91(4):304-310.
[15] HUANG Y H, ZHANG T C. Effects of low pH on nitrate reduction by iron powder[J]. Water Research, 2004, 38(11):2631-2642.
[16] LUO J H, SONG G Y, LIU J Y, et al. Mechanism of enhanced nitrate reduction via micro-electrolysis at the powdered zero-valent iron/activated carbon interface[J]. Journal of Colloid and Interface Science, 2014, 435:21-25.
[17] WANG X Q, GONG X K, ZHANG Q X, et al. Degradation mechanism of direct pink 12B treated by iron-carbon micro-electrolysis and Fenton reaction[J]. Journal of Environmental Sciences, 2013, 25:S63-S68.
[18] LAI B, ZHOU Y X, YANG P, et al. Degradation of 3,3'-iminobis-propanenitrile in aqueous solution by Fe^0/GAC micro-electrolysis system[J]. Chemosphere, 2013, 90(4):1470-1477.
[19] WANG L Q, YANG Q, WANG D B, et al. Advanced landfill leachate treatment using iron-carbon microelectrolysis-Fenton process:Process optimization and column experiments[J]. Journal of Hazardous Materials, 2016, 318:460-467.
[20] YING D W, XU X Y, LI K, et al. Design of a novel sequencing batch internal micro-electrolysis reactor for treating mature landfill leachate[J]. Chemical Engineering Research and Design, 2012, 90(12):2278-2286.
[21] 李胜海, 程谣, 许晓毅, 等. 铁碳微电解预处理含吡啶的有机废水[J]. 水处理技术, 2017, 43(2):98-101, 106. LI S H, CHENG Y, XU X Y, et al. Pretreatment of organic wastewater containing pyridines by iron-carbon micro-electrolysis[J]. Technology of Water Treatment, 2017, 43(2):98-101, 106.
[22] QIN Z, LIU S, LIANG S X, et al. Advanced treatment of pharmaceutical wastewater with combined micro-electrolysis, Fenton oxidation, and coagulation sedimentation method[J]. Desalination and Water Treatment, 2016, 57(53):1-10.
[23] 涂传青.金属铁与电解法还原难降解有机物反应机理和影响因素的研究[D]. 上海:同济大学, 2006. TU C Q. Study on mechanism and influencing factors of the degradation of recalcitrant organic compounds by metallic iron and electrolytic reduction[D]. Shanghai:Tongji University, 2006.
[24] ZONGO I, LECLERC J P, MAIGA H A, et al. Removal of hexavalent chromium from industrial wastewater by electrocoagulation:a comprehensive comparison of aluminium and iron electrodes[J]. Separation and Purification Technology, 2009, 66(1):159-166.
[25] SUN L, WANG C, JI M, et al. Treatment of mixed chemical wastewater and the agglomeration mechanism via an internal electrolysis filter[J]. Chemical Engineering Journal, 2013, 215:50-56.
[26] 周伟, 庄晓伟, 陈顺伟, 等. 铁碳微电解预处理工业废水研究进展[J]. 工业水处理, 2017, 37(7):5-9. ZHOU W, ZHUANG X W, CHEN S W, et al. Research progress in the pretreatment of industrial wastewater by iron-carbon micro-electrolysis process[J]. Industrial Water Treatment, 2017, 37(7):5-9.
[27] LAI B, ZHOU Y X, WANG J L, et al. Passivation process and the mechanism of packing particles in the Fe⁰/GAC system during the treatment of ABS resin wastewater[J]. Environmental Technology, 2014, 35(8):973-983.
[28] ZHANG D, WEI S Y, KAILA C, et al. Carbon stabilized iron nanoparticles for environmental remediation[J]. Nanoscale, 2010, 2(6):917-919.
[29] HUANG D Y, YUE Q Y, FU K F, et al. Application for acrylonitrile wastewater treatment by new micro-electrolysis ceramic fillers[J]. Desalination and Water Treatment, 2016, 57(10):4420-4428.
[30] 刘啸乾, 李剑超, 刘琰, 等. 新型铁碳复合材料合成及其对染料废水脱色性能的试验研究[J]. 水处理技术, 2012, 38(8):43-46, 50. LIU X Q, LI J C, LIU Y, et al. Experiment on preparation and performance of iron-carbon composite material for treating dye wastewater[J]. Technology of Water Treatment, 2012, 38(8):43-46, 50.
[31] WANG Y B, FENG M Q, LIU Y H. Treatment of dye wastewater by continuous iron-carbon micro-electrolysis[J]. Environmental Engineering Science, 2016, 33(5):333-340.
[32] WANG Y B, LIU Y H, FU W, et al. Treatment of actual dyeing wastewater by continuous iron-carbon micro-electrolysis process[J]. Advanced Materials Research, 2014, 838:2395-2399.
[33] 刘磊, 刘永红, 王利娜, 等. 微电解材料的制备及其废水连续化处理工艺研究[J]. 工业水处理, 2015, 35(2):60-63. LIU L, LIU Y H, WANG L N, et al. Preparation of iron carbon micro-electrolysis materials and research on its continuous treatment process of actual wastewater[J]. Industrial Water Treatment, 2015, 35(2):60-63.
[34] ZHANG C, ZHOU M H, YU X M, et al. Modified iron-carbon as heterogeneous electro-Fenton catalyst for organic pollutant degradation in near neutral pH condition:Characterization, degradation activity and stability[J]. Electrochimica Acta, 2015, 160:254-262.
[35] ZHOU H M, SHEN Y Y, LV P, et al. Degradation of 1-butyl-3-methylimidazolium chloride ionic liquid by ultrasound and zero-valent iron/activated carbon[J]. Separation and Purification Technology, 2013, 104:208-213.
[36] WANG K, LIU S, ZHANG Q, et al. Pharmaceutical wastewater treatment by internal micro-electrolysis-coagulation, biological treatment and activated carbon adsorption[J]. Environmental Technology, 2009, 30(13):1469-1474.
[37] 傅强根, 胡勇有. 铝炭微电解处理刚果红废水的效果及脱色机理研究[J]. 环境科学学报, 2013, 33(6):1527-1534. FU Q G, HU Y Y. Treatment effect and decolorization mechanism of Congo Red wastewater by aluminum-carbon microelectrolysis[J]. Acta Scientiae Circumstantiae, 2013, 33(6):1527-1534.
[38] XIE R, WU M, QU G, et al. Treatment of coking wastewater by a novel electric assisted micro-electrolysis filter[J]. Journal of Environmental Sciences, 2017. DOI:10.1016/j.jes.2017.05.034.
[39] ZHANG X, DONG W, SUN F, et al. Degradation efficiency and mechanism of azo dye RR2 by a novel ozone aerated internal micro-electrolysis filter[J]. Journal of Hazardous Materials, 2014, 276(9):77.
[40] HAN Y, LI H, LIU M, et al. Purification treatment of dyes wastewater with a novel micro-electrolysis reactor[J]. Separation and Purification Technology, 2016, 170:241-247.
[41] 李洵, 张万友, 苗宇, 等. 炭循环微电解反应器处理腈纶废水的Design-Expert设计优化[J]. 工业水处理, 2011, 31(10):75-78. LI X, ZAHNG W Y, MIAO Y, et al. Design-Expert software design and optimization of the treatment of acrylic fiber wastewater with the charcoal cycle micro-electrolysis reactor[J]. Industrial Water Treatment, 2011, 31(10):75-78.
[42] YING D, XU X, LI K, et al. Design of a novel sequencing batch internal micro-electrolysis reactor for treating mature landfill leachate[J]. Chemical Engineering Research and Design, 2012, 90(12):2278-2286.
[43] FU J, XU Z, LI Q, et al. Treatment of simulated wastewater containing reactive red 195 by zero-valent iron/activated carbon combined with microwave discharge electrodeless lamp/sodium hypochlorite[J]. Journal of Environmental Sciences, 2010, 22(4):512-518.
[44] 马丹丹, 文晨, 季民. 微电解-铁碳内电解耦合预处理高浓度染料废水[J]. 化工进展, 2013, 32(1):205-208. MA D D, WEN C, JI M. Study on treatment of high concentration of dye-wastewater with coupling technique of electrochemical oxidation and internal-electrolysis[J]. Chemical Industry and Engineering Progress, 2013, 32(1):205-208.
[45] YANG S Y, LIANG Z W, YU H D, et al. Chemical oxygen demand removal efficiency and limited factors study of aminosilicone polymers in a water emulsion by iron-carbon micro-electrolysis[J]. Water Environment Research, 2014, 86(2):156-162.
[46] RUAN X C, LIU M Y, ZENG Q F, et al. Degradation and decolorization of reactive red X-3B aqueous solution by ozone integrated with internal micro-electrolysis[J]. Separation and Purification Technology, 2010, 74(2):195-201.
[47] HUANG J G, CHEN J J, XIE Z M, et al. Treatment of nanofiltration concentrates of mature landfill leachate by a coupled process of coagulation and internal micro-electrolysis adding hydrogen peroxide[J]. Environmental Technology, 2015, 36(8):1001-1007.
[48] WANG L Q, YANG Q, WANG D B, et al. Advanced landfill leachate treatment using iron-carbon microelectrolysis-Fenton process:Process optimization and column experiments[J]. Journal of Hazardous Materials, 2016, 318:460-467.
[49] 于昕, 林庚. 微电解-UASB组合工艺处理城市垃圾渗滤液[J]. 工业水处理, 2011, 31(3):30-32. YU X, LIN G. Urban landfill leachate treatment by microelectrolysis-UASB[J]. Industrial Water Treatment, 2011, 31(3):30-32.
[50] ZHOU J, DUAN S H, CHEN Y, et al. Nitrogen removal efficiency of iron-carbon micro-electrolysis system treating high nitrate nitrogen organic pharmaceutical wastewater[J]. J. Cent. S. Univ., Tech, 2009, 16(1):368-373.
[51] WU S Q, QI Y F, FAN C Z, et al. Improvement of anaerobic biological treatment effect by catalytic micro-electrolysis for monensin production wastewater[J]. Chemical Engineering Journal, 2016, 296:260-267.
[52] QI Y F, HE S B, WU S Q, et al. Utilization of micro-electrolysis, up-flow anaerobic sludge bed, anoxic/oxic-activated sludge process, and biological aerated filter in penicillin G wastewater treatment[J]. Desalination and Water Treatment, 2015, 55(6):1480-1487.
[53] 张帆, 李菁, 谭建华, 等. 吸附法处理重金属废水的研究进展[J]. 化工进展, 2013, 32(11):2749-2756. ZAHNG F, LI J, DAN J H, et al. Advance of the treatment of heavy metal wastewater by adsorption[J]. Chemical Industry and Engineering Progress, 2013, 32(11):2749-2756.
[54] WU L M, LIAO L B, LV G C, et al. Micro-electrolysis of Cr(Ⅵ) in the nanoscale zero-valent iron loaded activated carbon[J]. Journal of Hazardous Materials, 2013, 254:277-283.
[55] JU F, HU Y Y, CHENG J H. Removal of chelated Cu(Ⅱ) from aqueous solution by adsorption-coprecipitation with iron hydroxides prepared from micro-electrolysis process[J]. Desalination, 2011, 274:130-135.
[56] LI T C, JIANG B, FENG X, et al. Purification of organic wastewater containing Cu²⁺ and Cr³⁺ by a combined process of micro electrolysis and biofilm[J].Chinese Journal of Chemical Engineering, 2003, 11(6):146-150.
[57] 陈晓鸿, 李天国, 徐晓军, 等. 曝气微电解-曝气絮凝法处理高铅锌含量冶炼废水[J]. 水处理技术, 2013, 39(6):99-104. CHEN X H, LI T G, XU X J, et al. Treatment of high concentrations of lead and zinc smelting wastewater by micro-electrolysis and aerated flocculation[J]. Technology of Water Treatment, 2013, 39(6):99-104.