芬顿氧化水中甲基叔丁基醚影响因素及机理
|
摘要
采用芬顿氧化工艺降解水中污染物甲基叔丁基醚(MTBE),使用Box-Behnken设计方法进行实验设计,基于响应面分析考察了MTBE初始浓度、H_2O_2浓度、Fe~(2+)浓度、反应时间和pH等条件对MTBE降解率的影响,对反应条件进行了优化。结果表明,在MTBE初始浓度1.1 mmol·L~(-1)、H_2O_2浓度18.0 mmol·L~(-1)、Fe~(2+)浓度3.0 mmol·L~(-1)、反应时间20 min、溶液pH=3.0时,MTBE降解率高达99.3%,与模型预测结果较接近,表明模型具有较好的模拟和预测能力。MTBE芬顿氧化过程检出了乙酸甲酯、叔丁醇和丙酮等中间产物,推测其主要降解过程有两种途径:一是在甲氧基上发生反应,生成甲酸叔丁酯、叔丁醇和丙酮;二是在甲基上发生反应,生成乙酸甲酯和丙酮。
Fenton oxidation process is applied for methyl tert-butyl ether(MTBE) degradation. The experimental design is established by Box-Behnken design method(BBD) of response surface methodology(RSM), where influencing factors, namely MTBE initial concentration, H_2O_2 concentration, Fe~(2+) concentration, reaction time and solution pH are fitted. Optimized results show that at initial concentration 1.1 mmol·L~(-1), H_2O_2 concentration 18.0 mmol·L~(-1), Fe~(2+) concentration 3.0 mmol·L~(-1) reaction time 20 min and pH of 3.0, the degradation rate of MTBE reaches 99.3%, which is consistent with prediction, indicating good simulation and a forecasting model. Intermediates, namely methyl acetate, tert-butanol and acetone are detected during degradation. Thus it is speculated that there are two main pathways. One occurs on the methoxy group producing tert-butyl formate, tert-butyl alcohol and acetone; the other is on the methyl group, producing methyl acetate and acetone.
Fenton oxidation process is applied for methyl tert-butyl ether(MTBE) degradation. The experimental design is established by Box-Behnken design method(BBD) of response surface methodology(RSM), where influencing factors, namely MTBE initial concentration, H_2O_2 concentration, Fe~(2+) concentration, reaction time and solution pH are fitted. Optimized results show that at initial concentration 1.1 mmol·L~(-1), H_2O_2 concentration 18.0 mmol·L~(-1), Fe~(2+) concentration 3.0 mmol·L~(-1) reaction time 20 min and pH of 3.0, the degradation rate of MTBE reaches 99.3%, which is consistent with prediction, indicating good simulation and a forecasting model. Intermediates, namely methyl acetate, tert-butanol and acetone are detected during degradation. Thus it is speculated that there are two main pathways. One occurs on the methoxy group producing tert-butyl formate, tert-butyl alcohol and acetone; the other is on the methyl group, producing methyl acetate and acetone.
引文
[1]松文.甲基叔丁基醚生产与发展趋势[J].精细化工原料及中间体,2011,41(2):33-38.
[2]于晓章.汽油添加剂甲基叔丁基醚(MTBE)对环境的危害性[J].生态科学,2003,22(3):257-260.
[3]王鹏,周瑞静,宋炜,等.加油站地下水甲基叔丁基醚(MTBE)的迁移模拟研究[J].城市地质,2016,11(1):10-15.
[4]王禹,薛惠中,高明,等.甲基叔丁基醚致人B淋巴母细胞系DNA损伤和氧化应激损伤的研究[J].环境与职业医学,2016,33(12):1138-1142.
[5]马俊香,陈帆,陈丽,等.甲基叔丁基醚诱导的HT-22细胞氧化应激体外研究[J].山西医科大学学报,2016,47(12):1066-1070.
[6]AXEL K,WILHELM P.Methyl tert-butyl ether (MTBE) in finisheddrinking water in Germany[J].Environmental Pollution,2006,140(3):294-303.
[7]EWA M S,ANNA W,PIOTR S.In?uence of inorganic ions on MTBE degradation by Fenton’s reagent[J].Journal of Hazardous Materials,2007,147(1/2):497-502.
[8]BURBANO A A,DIONYSIOU D D,SUIDAN M T.Effect of oxidant-to-substrate ratios on the degradation of MTBE with Fenton reagent[J].Water Research,2008,42(12):3225-3239.
[9]涂宁宇,刘洋,刘国光.基于均匀设计的响应面优化油页岩吸附铜离子的研究[J].环境工程,2013,31(4):48-52.
[10]张帆,张进明,肖梅,等.响应面法优化催化臭氧氧化处理邻苯二甲酸二甲酯废水的研究[J].环境污染与防治,2017,39(10):1092-1096.
[11]王利平,李祥梅,倪可,等.响应面方法优化硅藻土处理甲萘酚废水[J].环境科学与技术,2014,37(7):103-106.
[12]樊蓉,周鑫,张泽乾,等.响应面法优化电芬顿预处理焦化废水[J].太原理工大学学报,2016,47(6):717-722.
[13]刘学卿,刘武平,王新刚.铁炭微电解预处理增塑剂生产废水的研究[J].江苏科技大学学报(自然科学版),2016,30(1):94-98.
[14]石晓康,王黎.SCWO处理轮胎裂解脱硫废液的响应面法优化[J].工业水处理,2017,37(10):72-77.
[15]杜尔登,张申耀,冯欣欣,等.光催化降解内分泌干扰物双酚A的响应面分析与优化[J].环境工程学报,2014,8(12):5124-5128.
[16]彭明国,李志宏,周浩,等.抗生素类污染物磺胺嘧啶的UV/H2O2降解技术研究[J].常州大学学报(自然科学版),2016,28(6):95-99.
[17]DONG C D,TSAI M L,CHEN C W,et al.Heterogeneous persulfate oxidation of BTEX and MTBE using Fe3O4-CB magnetite composites and the cytotoxicity of degradation products[J].International Biodeterioration & Biodegradation,2017,124:109-118.
[18]姜成春,庞素艳,江进,等.Fe(Ⅲ)催化过氧化氢分解影响因素分析[J].环境科学学报,2007,27(7):1197-1202.
[19]HWANG S,HULING S G,KO S.Fenton-like degradation of MTBE:effects of iron counter anion and radical scavengers[J].Chemosphere,2010,78(5):1-568.
[20]林天来,刘秀峰,黄灿克.光源强度对UV活化过硫酸盐降解甲基叔丁基醚效果的影响研究[J].环境与可持续发展,2017,42(5):103-105.
[21]SOHEILA M.Degradation of methyl t-butyl ether (MTBE) by photochemical process in nanocrystalline TiO2 slurry:Mechanism,by-products and carbonate ion effect[J].Journal of Environmental Chemical Engineering,2013,1(4):1070-1078.
[22]齐健平.高级氧化法降解水中甲基叔丁基醚的研究[D].南京:南京理工大学,2013.
[23]毛柯辉.甲基叔丁基醚(MTBE)的O3和O3/H2O2降解试验[D].杭州:浙江大学,2007.
[2]于晓章.汽油添加剂甲基叔丁基醚(MTBE)对环境的危害性[J].生态科学,2003,22(3):257-260.
[3]王鹏,周瑞静,宋炜,等.加油站地下水甲基叔丁基醚(MTBE)的迁移模拟研究[J].城市地质,2016,11(1):10-15.
[4]王禹,薛惠中,高明,等.甲基叔丁基醚致人B淋巴母细胞系DNA损伤和氧化应激损伤的研究[J].环境与职业医学,2016,33(12):1138-1142.
[5]马俊香,陈帆,陈丽,等.甲基叔丁基醚诱导的HT-22细胞氧化应激体外研究[J].山西医科大学学报,2016,47(12):1066-1070.
[6]AXEL K,WILHELM P.Methyl tert-butyl ether (MTBE) in finisheddrinking water in Germany[J].Environmental Pollution,2006,140(3):294-303.
[7]EWA M S,ANNA W,PIOTR S.In?uence of inorganic ions on MTBE degradation by Fenton’s reagent[J].Journal of Hazardous Materials,2007,147(1/2):497-502.
[8]BURBANO A A,DIONYSIOU D D,SUIDAN M T.Effect of oxidant-to-substrate ratios on the degradation of MTBE with Fenton reagent[J].Water Research,2008,42(12):3225-3239.
[9]涂宁宇,刘洋,刘国光.基于均匀设计的响应面优化油页岩吸附铜离子的研究[J].环境工程,2013,31(4):48-52.
[10]张帆,张进明,肖梅,等.响应面法优化催化臭氧氧化处理邻苯二甲酸二甲酯废水的研究[J].环境污染与防治,2017,39(10):1092-1096.
[11]王利平,李祥梅,倪可,等.响应面方法优化硅藻土处理甲萘酚废水[J].环境科学与技术,2014,37(7):103-106.
[12]樊蓉,周鑫,张泽乾,等.响应面法优化电芬顿预处理焦化废水[J].太原理工大学学报,2016,47(6):717-722.
[13]刘学卿,刘武平,王新刚.铁炭微电解预处理增塑剂生产废水的研究[J].江苏科技大学学报(自然科学版),2016,30(1):94-98.
[14]石晓康,王黎.SCWO处理轮胎裂解脱硫废液的响应面法优化[J].工业水处理,2017,37(10):72-77.
[15]杜尔登,张申耀,冯欣欣,等.光催化降解内分泌干扰物双酚A的响应面分析与优化[J].环境工程学报,2014,8(12):5124-5128.
[16]彭明国,李志宏,周浩,等.抗生素类污染物磺胺嘧啶的UV/H2O2降解技术研究[J].常州大学学报(自然科学版),2016,28(6):95-99.
[17]DONG C D,TSAI M L,CHEN C W,et al.Heterogeneous persulfate oxidation of BTEX and MTBE using Fe3O4-CB magnetite composites and the cytotoxicity of degradation products[J].International Biodeterioration & Biodegradation,2017,124:109-118.
[18]姜成春,庞素艳,江进,等.Fe(Ⅲ)催化过氧化氢分解影响因素分析[J].环境科学学报,2007,27(7):1197-1202.
[19]HWANG S,HULING S G,KO S.Fenton-like degradation of MTBE:effects of iron counter anion and radical scavengers[J].Chemosphere,2010,78(5):1-568.
[20]林天来,刘秀峰,黄灿克.光源强度对UV活化过硫酸盐降解甲基叔丁基醚效果的影响研究[J].环境与可持续发展,2017,42(5):103-105.
[21]SOHEILA M.Degradation of methyl t-butyl ether (MTBE) by photochemical process in nanocrystalline TiO2 slurry:Mechanism,by-products and carbonate ion effect[J].Journal of Environmental Chemical Engineering,2013,1(4):1070-1078.
[22]齐健平.高级氧化法降解水中甲基叔丁基醚的研究[D].南京:南京理工大学,2013.
[23]毛柯辉.甲基叔丁基醚(MTBE)的O3和O3/H2O2降解试验[D].杭州:浙江大学,2007.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |