氯苯类污染物超临界水氧化反应动力学研究
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摘要
利用石英微反应器,以H_2O_2为氧化剂,研究了氯苯类有机污染物(邻二氯苯和间氯甲苯)去除和CO_2生成反应的动力学.结果表明:超临界水氧化法可有效地去除废水中的含氯有机物,邻二氯苯和间氯甲苯的去除反应和CO_2生成反应均遵循一级反应动力学.在360~440℃范围内邻二氯苯去除反应和CO_2生成反应的活化能分别为96.3,172.4kJ/mol;在260~340℃范围内间氯甲苯去除反应的活化能为128.8kJ/mol,在360~460℃范围内CO_2生成的活化能为76.3kJ/mol.
The kinetics of the chlorobenzene compounds(o-dichlorobenzene and 3-chlorotoluene)removal and the CO_2formation were studied at quartz microreactor by using H_2O_2as oxidant.The results showed that the supercritical water oxidation could effectively remove the chlorinecontaining organic compounds from the wastewater.The removal of o-dichlorobenzene or 3-chlorotoluene and CO_2generation followed the first-order reaction kinetics.In the range of 360-440℃,the activation energy of o-dichlorobenzene removal reaction and CO_2formation reaction were 96.3 and 172.4 kJ/mol,respectively.The activation energy for the removal of 3-chlorotoluene is 128.8kJ/mol in the range of 260℃to 340℃,and the activation energy for the formation of CO_2is 76.3kJ/mol in the range of 360℃to 460℃.
The kinetics of the chlorobenzene compounds(o-dichlorobenzene and 3-chlorotoluene)removal and the CO_2formation were studied at quartz microreactor by using H_2O_2as oxidant.The results showed that the supercritical water oxidation could effectively remove the chlorinecontaining organic compounds from the wastewater.The removal of o-dichlorobenzene or 3-chlorotoluene and CO_2generation followed the first-order reaction kinetics.In the range of 360-440℃,the activation energy of o-dichlorobenzene removal reaction and CO_2formation reaction were 96.3 and 172.4 kJ/mol,respectively.The activation energy for the removal of 3-chlorotoluene is 128.8kJ/mol in the range of 260℃to 340℃,and the activation energy for the formation of CO_2is 76.3kJ/mol in the range of 360℃to 460℃.
引文
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[3]胡欢杰,胡斯翰,林春绵.超临界水氧化法测定TOC的氧化剂选择研究[J].浙江工业大学学报,2015,43(5):543-546,551.
[4]杨馗,徐明仙,林春绵.超临界水的物理化学性质[J].浙江工业大学学报,2001,29(4):386-390.
[5]张鹤楠,韩萍芳,徐宁.超临界水氧化技术研究进展[J].环境工程,2014,32:9-11.
[6]WANG Qi,LV Yongkang,ZHANG Rong,et al.Supercritical water oxidation kinetics of textiles dyeing wastewater[J].Advanced materials research,2013,634-638(1):302-306.
[7]林春绵,陶雪文,郑启富,等.催化超临界水氧化降解1,5-萘二磺酸的动力学研究[J].工业用水与废水,2007,38(5):35-37,41.
[8]VADILLO V,SANCHEZ-ONETO J,PORTELA J R,et al.Problems in supercritical water oxidation process and proposed solutions[J].Industrial&engineering chemistry research,2013,52(23):7617-7629.
[9]LI R,THORNTON T D,SAVAGE P E.Kinetics of carbon dioxide formation from the oxidation of phenols in supercritical water[J].Environmental science&technology,1992,26(12):2388-2395.
[10]LIU Huicheng,PAN Zhiyan.Visual observations and Raman spectroscopic studies of supercritical water oxidation of chlorobenzene in an anticorrosive fused-silica capillary reactor[J].Environmental science&technology,2012,46(6):3384-3389.
[11]YAO Xingjun,ZHANG Yan,DU Lingyun,et al.Review of the applications of microreactors[J].Renewable&sustainable energy reviews,2015,47:519-539.
[12]BEI Ke,ZHANG Chuanyong,WANG Junliang,et al.Solubility and dissolution mechanism of 4-chlorotoluene in subcritical water investigated in a fused silica capillary reactor by in situ Raman spectroscopy[J].Fluid phase equilibria,2016,425:93-97.
[13]董重,潘志彦.石英毛细管法测定乙醇在超临界二氧化碳中的溶解度[J].浙江工业大学学报,2012,40(4):418-421.
[14]WANG J L,ZHOU S Y,BEI K,et al.Using fused silica capillary cell and in situ Raman spectroscopy to develop a setup for measurement the volume expansion of carbon dioxide+N-hexane[J].Energy&fuels,2017,31(6):6314-6319.
[15]欧阳创,申哲民,张亚南,等.六种有机物在亚/超临界水中氧化的反应动力学研究[J].安全与环境工程,2013,20(4):67-70,75.
[16]潘志彦,林春绵,周红艺,等.乙酸在超临界水中氧化分解的动力学研究[J].高校化学工程学报,2003,17(1):101-105.