2.湖南农业大学资源环境学院,长沙 410128
1.Hunan Engineering & Technology Research Center for Irrigation Water Purification, Changsha 410128, China
2.College of Resources and Environment, Hunan Agricultural University, Changsha 410128, China
为了高效地去除酸性矿山废水中的Sb(Ⅲ),采用一种基于电芬顿反应的新型反应器进行处理。探讨了新型反应器各项性能(去除率、能耗、·OH产量)的优势;分别考察了电流强度、pH、板间距、曝气速率、电解质浓度对Sb(Ⅲ)去除效果的影响;使用水杨酸和苯醌对电芬顿体系中Sb(Ⅲ)的去除机理进行了分析;并探究新型电芬顿反应器对实际废水中的Sb(Ⅲ)处理效果。结果表明:与吸附、电氧化、传统电芬顿法相比,新型反应器在Sb(Ⅲ)的处理中更加高效,并且能耗更低,通过阴极旋转能够提高·OH的产量,增强电芬顿反应氧化能力;在电流强度为120 mA,pH为3,板间距为2 cm,曝气速率为90 mL·min
·能够共同促进Sb(Ⅲ)的去除;通过该反应器处理实际废水,Sb(Ⅲ)去除率能够达到89%。以上结果可为新型电芬顿反应器高效处理含Sb(Ⅲ)的酸性矿山废水提供参考。
In order to remove Sb(Ⅲ) from acid mine wastewater efficiently, a novel reactor based on electro-Fenton reaction was used to treat acid mine wastewater. The advantages of various performances (removal rate, energy consumption, and ·OH output) of the new reactor were discussed. The effects of current intensity, pH, plate spacing, aeration rate, and electrolyte concentration on the removal rate of Sb(Ⅲ) were investigated. The removal mechanism of Sb(Ⅲ) in the electro-Fenton system was analyzed by using salicylic acid and benzoquinone. The Sb(Ⅲ) treatment in actual wastewater by the novel electro-Fenton reactor was also explored. The results showed that compared with absorption, electro-oxidation, and traditional electro-Fenton method, the novel reactor presented higher efficiency and lower cost in Sb(Ⅲ) treatment. The cathode rotation could increase the output of ·OH and enhance the oxidation capacity of the electro-Fenton system. Under the optimal conditions as follows: current intensity of 120 mA, pH 3, plate spacing of 2 cm, aeration rate of 90 mL·min
, the Sb(Ⅲ) removal efficiency from wastewater could approach 100%. ·OH and HO
· could promote Sb(Ⅲ) removal together in the electro-Fenton system. The Sb(Ⅲ) removal efficiency in actual wastewater could reach 89% by the novel reactor. The above results can provide references for the efficient treatment of Sb(Ⅲ)-containing acid mine wastewater by the novel electro-Fenton reactor.
.
Device of electro-Fenton reaction
Comparison of performance for the novel reactor under different conditions
Effect of pH on the removal efficiency
Effect of current intensity on the removal efficiency
Effect of plate spacing on the removal efficiency
Effect of aeration rate on the removal efficiency
Effect of electrolyte concentration on the removal efficiency
Effect of initial treatment concentration on the removal efficiency
Removal mechanism of Sb(Ⅲ) in electro-Fenton reaction
Comparison of the removal effects between simulated wastewater and actual wastewater
[1] | ZHANG G, OUYANG X, LI H, et al. Bioremoval of antimony from contaminated waters by a mixed batch culture of sulfate-reducing bacteria[J]. International Biodeterioration & Biodegradation, 2016, 115: 148-155. |
[2] | HARGREAVES A J, VALE P, WHELAN J, et al. Mercury and antimony in wastewater: Fate and treatment[J]. Water, Air & Soil Pollution, 2016, 227: 89. |
[3] | MUBARAK H, CHAI L Y, MIRZA N, et al. Antimony (Sb) pollution and removal techniques: Critical assessment of technologies[J]. Toxicological & Environmental Chemistry, 2015, 97(10): 1296-1318. |
[4] | VERBINNEN B, BLOCK C, LIEVENS P, et al. Simultaneous removal of molybdenum, antimony and selenium oxyanions from wastewater by adsorption on supported magnetite[J]. Waste and Biomass Valorization, 2013, 4(3): 635-645. doi: 10.1007/s12649-013-9200-8 |
[5] | ASHLEY P M, CRAW D, GRAHAM B P, et al. Environmental mobility of antimony around mesothermal stibnite deposits, New South Wales, Australia and southern New Zealand[J]. Journal of Geochemical Exploration, 2003, 77(1): 1-14. doi: 10.1016/S0375-6742(02)00251-0 |
[6] | GUO W, FU Z, WANG H, et al. Removal of antimonate (Sb(V)) and antimonite (Sb(III)) from aqueous solutions by coagulation-flocculation-sedimentation (CFS): Dependence on influencing factors and insights into removal mechanisms[J]. Science of the Total Environment, 2018, 644: 1277-1285. doi: 10.1016/j.scitotenv.2018.07.034 |
[7] | DU X, QU F, LIANG H, et al. Removal of antimony (III) from polluted surface water using a hybrid coagulation-flocculation-ultrafiltration (CF-UF) process[J]. Chemical Engineering Journal, 2014, 254: 293-301. doi: 10.1016/j.cej.2014.05.126 |
[8] | SAITO T, TSUNEDA S, HIRATA A, et al. Removal of antimony (III) using polyol-ligand-containing porous hollow-fiber membranes[J]. Separation Science and Technology, 2004, 39(13): 3011-3022. doi: 10.1081/SS-200033727 |
[9] | TERRY L R, KULP T R, WIATROWSKI H, et al. Microbiological oxidation of antimony (Ⅲ) with oxygen or nitrate by bacteria isolated from contaminated mine sediments[J]. Applied and Environment Microbiology, 2015, 81(24): 8478-8488. doi: 10.1128/AEM.01970-15 |
[10] | ZHU J, WU F, PAN X, et al. Removal of antimony from antimony mine flotation wastewater by electrocoagulation with aluminum electrodes[J]. Journal of Environmental Sciences, 2011, 23(7): 1066-1071. doi: 10.1016/S1001-0742(10)60550-5 |
[11] | LIU Y, ZHANG J, LIU F, et al. Ultra-rapid detoxification of Sb(Ⅲ) using a flow-through electro-Fenton system[J]. Chemosphere, 2019, 245: 125604. |
[12] | MIAO Y, HAN F, PAN B, et al. Antimony(V) removal from water by hydrated ferric oxides supported by calcite sand and polymeric anion exchanger[J]. Journal of Environmental Sciences, 2014, 26(2): 307-314. doi: 10.1016/S1001-0742(13)60418-0 |
[13] | ZHAO X, DOU X, MOHAN D, et al. Antimonate and antimonite adsorption by a polyvinyl alcohol-stabilized granular adsorbent containing nanoscale zero-valent iron[J]. Chemical Engineering Journal, 2014, 247: 250-257. doi: 10.1016/j.cej.2014.02.096 |
[14] | SHAN C, MA Z, TONG M. Efficient removal of trace antimony(III) through adsorption by hematite modified magnetic nanoparticles[J]. Journal of Hazardous Materials, 2014, 268: 229-236. doi: 10.1016/j.jhazmat.2014.01.020 |
[15] | 曹岛, 肖发新, 毛建伟. 铜电解液中锑氧化还原规律及其价态转化途径[J]. 铜业工程, 2013, 121(3): 11-16. doi: 10.3969/j.issn.1009-3842.2013.03.004 |
[16] | KONG L, HU X, HE M. Mechanisms of Sb(III) oxidation by pyrite-induced hydroxyl radicals and hydrogen peroxide[J]. Environmental Science & Technology, 2015, 49(6): 3499-3505. |
[17] | KONG L, HE M. Mechanisms of Sb(III) photooxidation by the excitation of organic Fe(III) complexes[J]. Environmental Science & Technology, 2016, 50(13): 6974-6982. |
[18] | 颜军, 苟小军, 邹全付, 等. 分光光度法测定Fenton反应产生的羟基自由基[J]. 成都大学学报(自然科学版), 2009, 28(2): 91-93. |
[19] | ZHU R, YANG C, ZHOU M, et al. Industrial park wastewater deeply treated and reused by a novel electrochemical oxidation reactor[J]. Chemical Engineering Journal, 2015, 260: 427-433. doi: 10.1016/j.cej.2014.09.029 |
[20] | WEN S, NIU Z, ZHANG Z, et al. In-situ synthesis of 3D-GA on titanium wire as a binder-free electrode for electro-Fenton removing of EDTA-Ni[J]. Journal of Hazardous Materials, 2018, 341: 128-137. doi: 10.1016/j.jhazmat.2017.07.014 |
[21] | BRILLAS E, SIRES I, OTURAN M. Electro-Fenton process and related electrochemical technologies based on Fenton’s reaction chemistry[J]. Chemical Reviews, 2009, 109: 6570-6631. doi: 10.1021/cr900136g |
[22] | PANIZZA M, CERISOLA G. Electro-Fenton degradation of synthetic dyes[J]. Water Research, 2009, 43(2): 339-44. doi: 10.1016/j.watres.2008.10.028 |
[23] | HE H, ZHOU Z. Electro-Fenton process for water and wastewater treatment[J]. Critical Reviews in Environmental Science and Technology, 2017, 47(21): 2100-2131. doi: 10.1080/10643389.2017.1405673 |
[24] | WANG C T, CHOU W L, CHUNG M H, et al. COD removal from real dyeing wastewater by electro-Fenton technology using an activated carbon fiber cathode[J]. Desalination, 2010, 253(1/2/3): 129-134. |
[25] | ZHOU W, RAJIC L, CHEN L, et al. Activated carbon as effective cathode material in iron-free electro-Fenton process: Integrated H2O2 electrogeneration, activation, and pollutants adsorption[J]. Electrochimica Acta, 2019, 296: 317-326. doi: 10.1016/j.electacta.2018.11.052 |
[26] | ?ZCAN A, ATILIR ?ZCAN A, DEMIRCI Y. Evaluation of mineralization kinetics and pathway of norfloxacin removal from water by electro-Fenton treatment[J]. Chemical Engineering Journal, 2016, 304: 518-526. doi: 10.1016/j.cej.2016.06.105 |
[27] | AHMADZADEH S, DOLATABADI M. Removal of acetaminophen from hospital wastewater using electro-Fenton process[J]. Environmental Earth Sciences, 2018, 77(2): 1-11. |
[28] | DIEZ A M, IGLESIAS O, ROSALES E, et al. Optimization of two-chamber photo electro Fenton reactor for the treatment of winery wastewater[J]. Process Safety and Environmental Protection, 2016, 101: 72-79. doi: 10.1016/j.psep.2015.09.010 |
[29] | XIA G, LU Y, XU H. Electrogeneration of hydrogen peroxide for electro-Fenton via oxygen reduction using polyacrylonitrile-based carbon fiber brush cathode[J]. Electrochimica Acta, 2015, 158: 390-396. doi: 10.1016/j.electacta.2015.01.102 |
[30] | REN G, ZHOU M, LIU M, et al. A novel vertical-flow electro-Fenton reactor for organic wastewater treatment[J]. Chemical Engineering Journal, 2016, 298: 55-67. doi: 10.1016/j.cej.2016.04.011 |
[31] | LING T, HUANG B, ZHAO M, et al. Repeated oxidative degradation of methyl orange through bio-electro-Fenton in bioelectrochemical system (BES)[J]. Bioresource Technology, 2016, 203: 89-95. doi: 10.1016/j.biortech.2015.12.031 |
[32] | SANTANA-MARTINEZ G, ROA-MORALES G, MARTIN DEL CAMPO E, et al. Electro-Fenton and electro-Fenton-like with in situ electrogeneration of H2O2 and catalyst applied to 4-chlorophenol mineralization[J]. Electrochimica Acta, 2016, 195: 246-256. doi: 10.1016/j.electacta.2016.02.093 |
[33] | ZHANG H, WAN X, LI G, et al. A three-electrode electro-Fenton system supplied by self-generated oxygen with automatic pH-regulation for groundwater remediation[J]. Electrochimica Acta, 2017, 250: 42-48. doi: 10.1016/j.electacta.2017.08.040 |
[34] | ZHAO J, ZHU C, LU J, et al. Electro-catalytic degradation of bisphenol A with modified Co3O4/β-PbO2/Ti electrode[J]. Electrochimica Acta, 2014, 118: 169-175. doi: 10.1016/j.electacta.2013.12.005 |
[35] | YU X, ZHOU M, REN G, et al. A novel dual gas diffusion electrodes system for efficient hydrogen peroxide generation used in electro-Fenton[J]. Chemical Engineering Journal, 2015, 263: 92-100. doi: 10.1016/j.cej.2014.11.053 |