Fe(VI)/CaO_2双氧化体系降解水环境中的DMP
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摘要
研究了高铁酸盐(Fe(VI))/过氧化钙(CaO2)联合处理对邻苯二甲酸二甲酯(DMP)的降解性能及机理,分析了共存离子的影响.基于响应面方法中的Box-Behnken实验设计进行了多因素实验,采用二次多项式和逐步回归法拟合了DMP去除率与Fe(VI)投加量、CaO2投加量和反应时间之间的关系,对实验条件进行了优化分析.结果表明,在初始p H值为中性条件下,Fe(VI)/CaO2可以有效去除DMP,降解过程符合准一级动力学模型.当Fe(VI)/CaO2/DMP物质的量比为1.1/4.4/1时,模型预测DMP最大降解率为95.57%,和验证实验得出的降解率90.14%相近,表明该响应面模型具有较好的模拟和预测能力.HCO3-和Mg2+对DMP的降解有一定抑制作用.自由基清除实验结果显示,羟基自由基(HO·)和超氧自由基(O2-·)对DMP的降解具有重要贡献,表明Fe(VI)和CaO2可形成类芬顿试剂协同降解污染物.DMP的主要降解途径包括酯基水解、侧链氧化和苯环的羟基化;主要降解产物为邻苯二甲酸单甲酯,2,5-二羟基苯甲酸,间苯二甲酸,草酸等.
The degradation efficiency and mechanism of ferrite(Fe(VI))/calcium oxide(Ca O2) combined treatment on dimethyl phthalate(DMP) were studied. Multi-factor experiments were carried out based on the Box-Behnken experimental design in Response Surface Method. Relationships between the removal rate of DMP and Fe(VI)dosage, CaO2 dosage and reaction time were fitted by quadratic polynomial and stepwise regression method, and the experimental conditions were optimized. DMP could be effectively removed by Fe(VI)/CaO2 under neutral pH conditions, and the degradation process conformed to the pseudo-second-order kinetic model. The maximum degradation rate of DMP predicted by the model reached 95.57% when the molar ratio of Fe(VI)/Ca O2/DMP was 1.1/4.4/1, which was close to 90.14% obtained by verification experiments, indicating that the model possessed a good simulation and predictive performance. HCO3-and Mg(Ⅱ) inhibited the degradation of DMP to a certain extent. The results of free radical scavenging experiments revealed that hydroxyl radical(HO·) and superoxide radical(O2-·) made significant contributions to the degradation of DMP, demonstrating that Fe(VI)and CaO2 could form Fenton-like reagents to synergistically degrade pollutants. The main degradation pathways of DMP included hydrolysis of ester group, oxidation of side chain and hydroxylation of benzene rings. The main degradation products were monomethyl phthalate, 2,5-dihydroxybenzoic acid, isophthalic acid, oxalic acid, etc.
The degradation efficiency and mechanism of ferrite(Fe(VI))/calcium oxide(Ca O2) combined treatment on dimethyl phthalate(DMP) were studied. Multi-factor experiments were carried out based on the Box-Behnken experimental design in Response Surface Method. Relationships between the removal rate of DMP and Fe(VI)dosage, CaO2 dosage and reaction time were fitted by quadratic polynomial and stepwise regression method, and the experimental conditions were optimized. DMP could be effectively removed by Fe(VI)/CaO2 under neutral pH conditions, and the degradation process conformed to the pseudo-second-order kinetic model. The maximum degradation rate of DMP predicted by the model reached 95.57% when the molar ratio of Fe(VI)/Ca O2/DMP was 1.1/4.4/1, which was close to 90.14% obtained by verification experiments, indicating that the model possessed a good simulation and predictive performance. HCO3-and Mg(Ⅱ) inhibited the degradation of DMP to a certain extent. The results of free radical scavenging experiments revealed that hydroxyl radical(HO·) and superoxide radical(O2-·) made significant contributions to the degradation of DMP, demonstrating that Fe(VI)and CaO2 could form Fenton-like reagents to synergistically degrade pollutants. The main degradation pathways of DMP included hydrolysis of ester group, oxidation of side chain and hydroxylation of benzene rings. The main degradation products were monomethyl phthalate, 2,5-dihydroxybenzoic acid, isophthalic acid, oxalic acid, etc.
引文
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[26]Teel A L,Warberg C R,Atkinson D A,et al.Comparison of mineral and soluble iron Fenton's catalysts for the treatment of trichloroethylene[J].Water Research,2001,35(4):977-984.
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[31]Chen J,Xu X,Zeng X,et al.Ferrate(VI)oxidation of polychlorinated diphenyl sulfides:Kinetics,degradation,and oxidized products[J].Water Research,2018,143:1-9.
[32]Jiang W,Joens J A,Dionysiou D D,et al.Optimization of photocatalytic performance of TiO2 coated glass microspheres using response surface methodology and the application for degradation of dimethyl phthalate[J].Journal of Photochemistry and Photobiology A:Chemistry,2013,262:7-13.
[33]Du E,Feng X X,Guo Y Q,et al.Dimethyl phthalate degradation by UV/H2O2:combination of experimental methods and quantum chemical calculation[Z].2014.
[34]殷雪妍,张艾,刘亚男.过氧化钙去除水中糖皮质激素的响应面分析[J].中国环境科学,2018,38(2):608-615.Yin X Y,Zhang A,Liu Y N,et al.Response surface analysis of glucocorticoid removal by calcium peroxide[J].China Environmental Science,2018,38(2):608-615.
[35]贺强礼,刘文斌,杨海君,等.1株对叔丁基邻苯二酚降解菌的筛选鉴定及响应面法优化其降解[J].环境科学,2015,36(7):2695-2706.He Q L,Liu W B,Yang H J,et al.Isolation,identification of a p-tert-butylcatechol-degradaing strains and optimization for its degradation by response surface methodology[J].Environmental Science,2015,36(7):2695-2706.
[36]Tang P,Jiang W,Lyu S,et al.Ethanol enhanced carbon tetrachloride degradation in Fe(II)activated calcium peroxide system[J].Separation and Purification Technology,2018,205:105-112.
[37]Wang H,Zhao Y,Su Y,et al.Fenton-like degradation of 2,4-dichlorophenol using calcium peroxide particles:performance and mechanisms[J].RSC Advances,2017,7(8):4563-4571.
[38]Zhang X,Gu X,Lu S,et al.Application of ascorbic acid to enhance trichloroethene degradation by Fe(III)-activated calcium peroxide[J].Chemical Engineering Journal,2017,325:188-198.
[39]Liao C H,Kang S F,Wu F A.Hydroxyl radical scavenging role of chloride and bicarbonate ions in the H2O2/UV process[J].Chemosphere,2001,44(5):1193-1200.
[40]Verma S,Nakamura S,Sillanp??M.Application of UV-C LEDactivated PMS for the degradation of anatoxin-a[J].Chemical Engineering Journal,2016,284:122-129.
[41]Sharma V K.Potassium ferrate(VI):an environmentally friendly oxidant[J].Advances in Environmental Research,2002,6(2):143-156.
[2]Chao W L,Lin C M,Shiung I I,et al.Degradation of di-butylphthalate by soil bacteria[J].Chemosphere,2006,63(8):1377-1383.
[3]贺涛,白小舰,陈隽,等.饮用水源地塑化剂类污染物环境健康风险评估[J].中国环境科学,2013,33(S1):26-31.He T,Bai X J,Chen J,et al.Environmental health risk assessment of plasticizer contaminants in drinking water source[J].China Environmental Science,2013,33(S1):26-31.
[4]Benjamin S,Masai E,Kamimura N,et al.Phthalates impact human health:Epidemiological evidences and plausible mechanism of action[J].Journal of Hazardous Materials,2017,340:360-383.
[5]王夫美,陈丽,焦姣,等.住宅室内降尘中邻苯二甲酸酯污染特征及暴露评价[J].中国环境科学,2012,32(5):780-786.Wang F M,Chen L J J,et al.Pollution characteristics of phthalate esters derived from household dust and exposure assessment[J].China Environmental Science,2012,32(5):780-786.
[6]Huygh J,Clotman K,Malarvannan G,et al.Considerable exposure to the endocrine disrupting chemicals phthalates and bisphenol-A in intensive care unit(ICU)patients[J].Environment International,2015,81:64-72.
[7]杜娴,罗固源,许晓毅.长江重庆段两江水相、间隙水和沉积物中邻苯二甲酸酯的分布与分配[J].环境科学学报,2013,33(2):557-562.Du X,Luo G Y,Xu X X,et al.Distribution and partition of phthalate esters in water phase,ore water andsediments from Chongqing section of the Yangtze River[J].Acta Scientiae Circumstantiae.
[8]Zhang T,Huang Z,Chen X,et al.Degradation behavior of dimethyl phthalate in an anaerobic/anoxic/oxic system[J].Journal of Environmental Management,2016,184:281-288.
[9]Shi J,Li F,Yin D,et al.Sorption and degradation of phthalate esters by a novel functional hyper-cross-linked polymer[J].Chemosphere,2017,171:149-157.
[10]Zhang J,Zhang C,Zhu Y,et al.Biodegradation of seven phthalate esters by Bacillus mojavensis B1811[J].International Biodeterioration&Biodegradation,2018,132:200-207.
[11]Usman M,Hanna K,Faure P.Remediation of oil-contaminated harbor sediments by chemical oxidation[J].Science of The Total Environment,2018,634:1100-1107.
[12]Watts R J,Ahmad M,Hohner A K,et al.Persulfate activation by glucose for in situ chemical oxidation[J].Water Research,2018,133:247-254.
[13]Vorontsov A V.Advancing Fenton and photo-Fenton water treatment through the catalyst design[J].Journal of Hazardous Materials,2018.
[14]Liu X,Zhou Y,Zhang J,et al.Insight into electro-Fenton and photoFenton for the degradation of antibiotics:Mechanism study and research gaps[J].Chemical Engineering Journal,2018,347:379-397.
[15]Quadrado R F N,Fajardo A R.Fast decolorization of azo methyl orange via heterogeneous Fenton and Fenton-like reactions using alginate-Fe2+/Fe3+films as catalysts[J].Carbohydrate Polymers,2017,177:443-450.
[16]Xue Y,Rajic L,Chen L,et al.Electrolytic control of hydrogen peroxide release from calcium peroxide in aqueous solution[J].Electrochemistry Communications,2018,93:81-85.
[17]Qian Y,Zhou X,Zhang Y,et al.Performance and properties of nanoscale calcium peroxide for toluene removal[J].Chemosphere,2013,91(5):717-723.
[18]Qian Y,Zhang J,Zhang Y,et al.Degradation of 2,4-dichlorophenol by nanoscale calcium peroxide:Implication for groundwater remediation[J].Separation and Purification Technology,2016,166:222-229.
[19]Arienzo M.Degradation of 2,4,6-trinitrotoluene in water and soil slurry utilizing a calcium peroxide compound[J].Chemosphere,2000,40(4):331-337.
[20]Lewis S,Lynch A,Bachas L,et al.Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems[J].Environmental engineering science,2009,26(4):849-859.
[21]Zhu Z,Chen Y,Gu Y,et al.Catalytic degradation of recalcitrant pollutants by Fenton-like process using polyacrylonitrile-supported iron(II)phthalocyanine nanofibers:Intermediates and pathway[J].Water Research,2016,93:296-305.
[22]Jho E H,Singhal N,Turner S.Fenton degradation of tetrachloroethene and hexachloroethane in Fe(II)catalyzed systems[J].Journal of Hazardous Materials,2010,184(1):234-240.
[23]Zhang X,Gu X,Lu S,et al.Application of calcium peroxide activated with Fe(II)-EDDS complex in trichloroethylene degradation[J].Chemosphere,2016,160:1-6.
[24]Xue Y,Gu X,Lu S,et al.The destruction of benzene by calcium peroxide activated with Fe(II)in water[J].Chemical Engineering Journal,2016,302:187-193.
[25]Yehia F Z,Kandile N G,Badawi A M,et al.Glutamic Acid Modified Fenton System for Degradation of BTEX Contamination[J].CleanSoil,Air,Water,2012,40(7):692-697.
[26]Teel A L,Warberg C R,Atkinson D A,et al.Comparison of mineral and soluble iron Fenton's catalysts for the treatment of trichloroethylene[J].Water Research,2001,35(4):977-984.
[27]Fu X,Gu X,Lu S,et al.Enhanced degradation of benzene in aqueous solution by sodium percarbonate activated with chelated-Fe(II)[J].Chemical Engineering Journal,2016,285:180-188.
[28]Zhou Y,Fang X,Wang T,et al.Chelating agents enhanced CaO2oxidation of bisphenol A catalyzed by Fe3+and reuse of ferric sludge as a source of catalyst[J].Chemical Engineering Journal,2017,313:638-645.
[29]Anquandah GaK,Sharma V K,Knight D A,et al.Oxidation of trimethoprim by ferrate(VI):kinetics,products,and antibacterial activity[J].Environmental science&technology,2011,45(24):10575-10581.
[30]Yang B,Ying G G.Oxidation of benzophenone-3during water treatment with ferrate(VI)[J].Water Research,2013,47(7):2458-2466.
[31]Chen J,Xu X,Zeng X,et al.Ferrate(VI)oxidation of polychlorinated diphenyl sulfides:Kinetics,degradation,and oxidized products[J].Water Research,2018,143:1-9.
[32]Jiang W,Joens J A,Dionysiou D D,et al.Optimization of photocatalytic performance of TiO2 coated glass microspheres using response surface methodology and the application for degradation of dimethyl phthalate[J].Journal of Photochemistry and Photobiology A:Chemistry,2013,262:7-13.
[33]Du E,Feng X X,Guo Y Q,et al.Dimethyl phthalate degradation by UV/H2O2:combination of experimental methods and quantum chemical calculation[Z].2014.
[34]殷雪妍,张艾,刘亚男.过氧化钙去除水中糖皮质激素的响应面分析[J].中国环境科学,2018,38(2):608-615.Yin X Y,Zhang A,Liu Y N,et al.Response surface analysis of glucocorticoid removal by calcium peroxide[J].China Environmental Science,2018,38(2):608-615.
[35]贺强礼,刘文斌,杨海君,等.1株对叔丁基邻苯二酚降解菌的筛选鉴定及响应面法优化其降解[J].环境科学,2015,36(7):2695-2706.He Q L,Liu W B,Yang H J,et al.Isolation,identification of a p-tert-butylcatechol-degradaing strains and optimization for its degradation by response surface methodology[J].Environmental Science,2015,36(7):2695-2706.
[36]Tang P,Jiang W,Lyu S,et al.Ethanol enhanced carbon tetrachloride degradation in Fe(II)activated calcium peroxide system[J].Separation and Purification Technology,2018,205:105-112.
[37]Wang H,Zhao Y,Su Y,et al.Fenton-like degradation of 2,4-dichlorophenol using calcium peroxide particles:performance and mechanisms[J].RSC Advances,2017,7(8):4563-4571.
[38]Zhang X,Gu X,Lu S,et al.Application of ascorbic acid to enhance trichloroethene degradation by Fe(III)-activated calcium peroxide[J].Chemical Engineering Journal,2017,325:188-198.
[39]Liao C H,Kang S F,Wu F A.Hydroxyl radical scavenging role of chloride and bicarbonate ions in the H2O2/UV process[J].Chemosphere,2001,44(5):1193-1200.
[40]Verma S,Nakamura S,Sillanp??M.Application of UV-C LEDactivated PMS for the degradation of anatoxin-a[J].Chemical Engineering Journal,2016,284:122-129.
[41]Sharma V K.Potassium ferrate(VI):an environmentally friendly oxidant[J].Advances in Environmental Research,2002,6(2):143-156.