表面活性剂和螯合剂强化Na_2S_2O_8/Fe~(2+)修复石油污染土壤
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摘要
采用Na_2S_2O_8/Fe~(2+)氧化降解污染土壤中的石油烃(TPH),考察了不同初始pH下Na_2S_2O_8与Fe~(2+)摩尔比对TPH降解的影响,研究了表面活性剂Triton X-100和3种螯合剂(柠檬酸、草酸和β-环糊精)对TPH降解的强化作用.研究结果表明:当pH=7,Na_2S_2O_8与Fe~(2+)摩尔比为2∶1时,TPH降解率最高,为39.8%;当Triton X-100质量浓度为1 250 mg/L时,其增溶作用远大于竞争消耗SO_4~-·的作用,TPH降解率可达最大值48.3%.此条件下进行螯合剂添加实验,结果表明:柠檬酸因竞争消耗SO_4~-·而抑制TPH降解,草酸因螯合Fe~(2+)作用较弱,对TPH降解基本不起促进作用;而β-环糊精因形成一种TPH/β-环糊精/Fe~(2+)三元包合物,使TPH降解率提高至55.6%.Triton X-100和β-环糊精联用能有效促进TPH降解,可能是由于Triton X-100的胶束增溶作用和β-环糊精的包合增溶、螯合Fe~(2+)作用产生的协同效应.
Na_2S_2O_8/Fe~(2+) was adopted to degrade petroleum hydrocarbon(TPH) in contaminated soil. The effect of molar ratio of Na_2S_2O_8 to Fe~(2+) on TPH degradation under different initial pH values was investigated. The enhancement effect of the surfactant Triton X-100 and three kinds of chelating agents(citric acid, oxalic acid and β-cyclodextrin) on TPH degradation was also revealed. The results show that when pH value is 7 and the molar ratio of Na_2S_2O_8 to Fe~(2+) is 2∶1, the TPH degradation efficiency reaches the highest, which is 39.8%. When Triton X-100 concentration is 1 250 mg/L, the TPH degradation efficiency is the maximum and reaches 48.3%, which is resulted from the effect of significant solubilization exceeding that of competition for SO_4~-·. The experiment of chelating agent addition indicates that citric acid can inhibit the TPH degradation due to its competition for SO_4~-·. Oxalic acid hardly promotes the TPH degradation because of the weaker chelation of Fe~(2+). Whereas, β-cyclodextrin enhances the TPH degradation by the formation of a TPH/β-cyclodextrin/Fe~(2+) ternary complex, which increases the TPH degradation efficiency to 55.6%. The combination of Triton X-100 and β-cyclodextrin could effectively promote the TPH degradation, which is possible due to the synergistic effect of the micellar solubilization of Triton X-100 and the inclusion solubilization and the Fe~(2+) chelation of β-cyclodextrin.
Na_2S_2O_8/Fe~(2+) was adopted to degrade petroleum hydrocarbon(TPH) in contaminated soil. The effect of molar ratio of Na_2S_2O_8 to Fe~(2+) on TPH degradation under different initial pH values was investigated. The enhancement effect of the surfactant Triton X-100 and three kinds of chelating agents(citric acid, oxalic acid and β-cyclodextrin) on TPH degradation was also revealed. The results show that when pH value is 7 and the molar ratio of Na_2S_2O_8 to Fe~(2+) is 2∶1, the TPH degradation efficiency reaches the highest, which is 39.8%. When Triton X-100 concentration is 1 250 mg/L, the TPH degradation efficiency is the maximum and reaches 48.3%, which is resulted from the effect of significant solubilization exceeding that of competition for SO_4~-·. The experiment of chelating agent addition indicates that citric acid can inhibit the TPH degradation due to its competition for SO_4~-·. Oxalic acid hardly promotes the TPH degradation because of the weaker chelation of Fe~(2+). Whereas, β-cyclodextrin enhances the TPH degradation by the formation of a TPH/β-cyclodextrin/Fe~(2+) ternary complex, which increases the TPH degradation efficiency to 55.6%. The combination of Triton X-100 and β-cyclodextrin could effectively promote the TPH degradation, which is possible due to the synergistic effect of the micellar solubilization of Triton X-100 and the inclusion solubilization and the Fe~(2+) chelation of β-cyclodextrin.
引文
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[19] HAN D,WAN J,MA Y,et al.New insights into the role of organic chelating agents in Fe(Ⅱ) activated persulfate processes[J].Chemical Engineering Journal,2015,269:425-433.
[20] 王主华,李欣萌,乔显亮,等.环糊精的Fenton氧化特性及产物分析[J].环境化学,2016,35(11):2411-2417.WANG Zhuhua,LI Xinmeng,QIAO Xianliang,et al.Fenton oxidation of cyclodextrin and identification of oxidation products[J].Environmental Chemistry,2016,35(11):2411-2417.
[21] HUANG K C,ZHAO Z,HOAG G E,et al.Degradation of volatile organic compounds with thermally activated persulfate oxidation[J].Chemosphere,2005,61(4):551-560.
[2] 李佳,曹兴涛,隋红,等.石油污染土壤修复技术研究现状与展望[J].石油学报(石油加工),2017,33(5):811-823.LI Jia,CAO Xingtao,SUI Hong,et al.Overview of remediation technologies for petroleum-contaminated soils[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(5):811-823.
[3] MATZEK L W,CARTER K E.Activated persulfate for organic chemical degradation:A review[J].Chemosphere,2016,151:178-188.
[4] LEE Y C,LO S L,CHIUEH P T,et al.Microwave-hydrothermal decomposition of perfluorooctanoic acid in water by iron-activated persulfate oxidation[J].Water Research,2010,44(3):886-892.
[5] LIANG C,GUO Y Y,PAN Y R.A study of the applicability of various activated persulfate processes for the treatment of 2,4-dichlorophenoxyacetic acid[J].International Journal of Environmental Science & Technology,2014,11(2):483-492.
[6] 张成,万金泉,马邕文,等.pH及络合剂对亚铁活化S2O82-氧化去除活性艳蓝的影响研究[J].环境科学,2012,33(3):871-878.ZHANG Cheng,WAN Jinquan,MA Yongwen,et al.Influences of pH and complexing agent on degradation of reactive brilliant blue KN-R by ferrous activated sulfate[J].Environmental Science,2012,33(3):871-878.
[7] 钟燕清,张永清,陈宪方,等.不同螯合剂对零价铁活化过硫酸盐降解对氯苯胺的影响[J].环境化学,2015(4):685-691.ZHONG Yanqing,ZHANG Yongqing,CHEN Xianfang,et al.Effects of different chelating agents on the degradation of p-chloroaniline in Fe0-persulfate system[J].Environmental Chemistry,2015(4):685-691.
[8] LIANG C,BRUELL C J,MARLEY M C,et al.Persulfate oxidation for in situ remediation of TCE.II.Activated by chelated ferrous ion[J].Chemosphere,2004,55(9):1225-1233.
[9] YU X,BAO Z,BARKER J R.Free radical reactions involving Cl-·,Cl-2·,and SO-4· in the 248 nm photolysis of aqueous solutions containing S2O82- and Cl-[J].The Journal of Physical Chemistry A,2004,108(2):295-308.
[10] 骆靖宇,李学艳,李青松,等.紫外活化过硫酸钠去除水体中的三氯卡班[J].中国环境科学,2017,37(9):3324-3331.LUO Jingyu,LI Xueyan,LI Qingsong,et al.Degradation of triclocarban aqueous solution through UV irradiation-activated sodium persulfate process[J].China Environmental Science,2017,37(9):3324-3331.
[11] 曾彪.铁化合物活化过硫酸钠氧化修复多氯联苯污染土壤研究[D].杭州:浙江大学,2014:36-38.ZENG Biao.Remediation of polychorinated biphenyls (PCBs) contaminated soil using sodium persulfate activeted by iron compunds[D].Hangzhou:Zhejiang University,2014:36-38.
[12] LAU T K,CHU W,GRAHAM N J D.The aqueous degradation of butylated hydroxyanisole by UV/S2O82-:Study of reaction mechanisms via dimerization and mineralization[J].Environmental Science & Technology,2007,41(2):613-619.
[13] PERA-TITUS M,GARCíA-MOLINA V,BA?OS M A,et al.Degradation of chlorophenols by means of advanced oxidation processes:A general review[J].Applied Catalysis B:Environmental,2004,47(4):219-256.
[14] ANIPSITAKIS G P,DIONYSIOU DD.Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt[J].Environmental Science & Technology,2003,37(20):4790-4797.
[15] 张金凤,杨曦.柠檬酸-Fe(Ⅱ)/K2S2O8降解泥水体系中敌草隆的研究[J].环境保护科学.2009,35(1):61-63.ZHANG Jinfeng,YANG Xi.Degradation of Diuron by citric acid-Fe(Ⅱ)/K2S2O8 in slurry system[J].Environmental Protection Science,2009,35(1):61-63.
[16] LINDSEY M E,XU G,LU J,et al.Enhanced Fenton degradation of hydrophobic organics by simultaneous iron and pollutant complexation with cyclodextrins[J].Science of the Total Environment,2003,307(1/3):215-229.
[17] LIANG C,HUANG C F,MOHANTY N,et al.Hydroxypropyl-β-cyclodextrin-mediated iron-activated persulfate oxidation of trichloroethylene and tetrachloroethylene[J].Industrial & Engineering Chemistry Research,2007,46(20):6466-6479.
[18] HARA M,TOJO S,MAJIMA T.Inhibition of one-electron oxidation of 1-pyrenesulfonate included in cyclodextrin by sulfate radical anion[J].Chemical Physics Letters,2004,387(4/6):283-286.
[19] HAN D,WAN J,MA Y,et al.New insights into the role of organic chelating agents in Fe(Ⅱ) activated persulfate processes[J].Chemical Engineering Journal,2015,269:425-433.
[20] 王主华,李欣萌,乔显亮,等.环糊精的Fenton氧化特性及产物分析[J].环境化学,2016,35(11):2411-2417.WANG Zhuhua,LI Xinmeng,QIAO Xianliang,et al.Fenton oxidation of cyclodextrin and identification of oxidation products[J].Environmental Chemistry,2016,35(11):2411-2417.
[21] HUANG K C,ZHAO Z,HOAG G E,et al.Degradation of volatile organic compounds with thermally activated persulfate oxidation[J].Chemosphere,2005,61(4):551-560.