超临界水氧化降解有机物的定量构效关系研究
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摘要
研究了邻苯二甲酸氢钾、辛基酚、硝基苯等20种有机物在超临界水氧化中的降解效果,探究了温度(325~525℃)和停留时间(30~360s)对超临界水氧化降解有机物的影响,并分析了20种有机物降解速率常数与量子化学参数之间的关系.结果表明,超临界水氧化法能够有效降解有机物,TOC去除率最高可达99%以上.随着反应温度的升高、停留时间的延长,TOC的去除率也随之提高,并且降解规律符合一级动力学.采用密度泛函理论,通过计算得到目标物的量子化学参数,再结合有机物降解的动力学常数进行相关性分析,结果发现,q(H+)、f(-)_(min)和f(0)_(min)与目标物降解率显著相关.
To study the degradation rules of organic compounds by supercritical water oxidation,20 kinds of organics were selected,such as potassium acid phthalate,4-tert-octylphenol and nitrobenzene etc. The degradation effect of temperature( 325 ~ 525 ℃) and retention time( 30 ~ 360 s) of organic compounds by supercritical water oxidation( SCWO) were studied. Additionally,the correlation between quantum chemical descriptors and TOC removal rates were analyzed. The results showed that organic compounds can be decomposed effectively by SCWO. The maximum of TOC removal rate reached was over 99%. TOC removal rate increased with the increase of temperature and retention time,and the degradation law in line with the first order kinetics.The quantitative parameters of each compound were obtained by density functional calculation. The correlation between the quantitative parameters and reaction kinetics constant,were analyzed. The results showed that q( H+) 、f(-)_(min)and f( 0)_(min)had higher correlations with the color removal rates than others.
To study the degradation rules of organic compounds by supercritical water oxidation,20 kinds of organics were selected,such as potassium acid phthalate,4-tert-octylphenol and nitrobenzene etc. The degradation effect of temperature( 325 ~ 525 ℃) and retention time( 30 ~ 360 s) of organic compounds by supercritical water oxidation( SCWO) were studied. Additionally,the correlation between quantum chemical descriptors and TOC removal rates were analyzed. The results showed that organic compounds can be decomposed effectively by SCWO. The maximum of TOC removal rate reached was over 99%. TOC removal rate increased with the increase of temperature and retention time,and the degradation law in line with the first order kinetics.The quantitative parameters of each compound were obtained by density functional calculation. The correlation between the quantitative parameters and reaction kinetics constant,were analyzed. The results showed that q( H+) 、f(-)_(min)and f( 0)_(min)had higher correlations with the color removal rates than others.
引文
程诚,王黎.2016.焦化脱硫废液中POPs的SCWO实验及动力学研究[J].应用化工,45(11):2047-2051
段明峰,赵纪豪,李穗.2004.超临界水氧化动力学研究进展[J].石油化工腐蚀与防护,21(6):1-4
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Heilingt R K,Tester J W.1988.Oxidation of simple compounds and mixtures in supercritical water,carbon monoxide,ammonia and ethanol[J].Environ Sci Technol,22(11):1319-1324
Lee H C,In J H,Kim J H,et al.2005.Kinetic analysis for decomposition of 2,4-dichlorophenol by supercritical water oxidation[J].Korean JChem Eng,22(6):882-888
Lachance R,Paschkewitz J,Di Naro J,et al.1999.Thiodiglycol hydrolysis and oxidation in sub-and supercritical water[J].Journal o Supercritical Fluids,16:133-147
Leea S H,Park K C,Mahikoa T,et al.2006.Supercritical water oxidation of polychlorinated biphenyls based on the redox reactions promoted by nitrate and nitrite salts[J].J of Supercritical Fluids,39:54-62
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王涛,刘崇义,沈忠耀,等.1997.超临界水氧化法去除废水COD的动力学研究[J].环境科学研究,10(4):32-35
Xiao R,Zammit I,Wei Z S,et al.2015.Kinetics and mechanism of the oxidation of cyclic methylsiloxanes by hydroxyl radical in the gas phase:An experimental and theoretical study[J].Environ Sci Technol,49(22):13322-30
向波涛,王涛,沈忠耀等.2003.含乙醇废水的超临界水氧化反应动力学及反应机理[J].化工学报,54(1):80-85
谢成,晏波,韦朝海等.2007.焦化废水Fenton氧化预处理过程中主要有机污染物的去除[J].环境科学学报,27(7):1101-1106
袁亚茹.2017.臭氧氧化难降解有机物的定量构效关系研究[D].上海:上海交通大学
Zhang F M,Xu C Y,Zhang Y,et al.2014.Experimental study on the operating characteristics of an inner preheating transpiring wall reactor for supercritical water oxidation:Temperature profiles and product properties[J].Energy,66:577-587
Zhu H C,Guo W M,Shen Z M,et al.2015.QSAR models for degradation of organic pollutants in ozonation process under acidic condition[J].Chemosphere,119:65-71
张世国,杨频.2004.用量子化学密度泛函理论研究环状含氮化合物分子结构与缓蚀性能的关系[J].中国腐蚀与防护学报,24(4):240-244
段明峰,赵纪豪,李穗.2004.超临界水氧化动力学研究进展[J].石油化工腐蚀与防护,21(6):1-4
Gong Y M,Guo Y,Wang S Z,et al.2016.Supercritical water oxidation o quinazoline:Effects of conversion parameters and reaction mechanism[J].Water Res,100:116-125
Heilingt R K,Tester J W.1988.Oxidation of simple compounds and mixtures in supercritical water,carbon monoxide,ammonia and ethanol[J].Environ Sci Technol,22(11):1319-1324
Lee H C,In J H,Kim J H,et al.2005.Kinetic analysis for decomposition of 2,4-dichlorophenol by supercritical water oxidation[J].Korean JChem Eng,22(6):882-888
Lachance R,Paschkewitz J,Di Naro J,et al.1999.Thiodiglycol hydrolysis and oxidation in sub-and supercritical water[J].Journal o Supercritical Fluids,16:133-147
Leea S H,Park K C,Mahikoa T,et al.2006.Supercritical water oxidation of polychlorinated biphenyls based on the redox reactions promoted by nitrate and nitrite salts[J].J of Supercritical Fluids,39:54-62
Li L X,Chen P S,Gloyna E F.1991.Generalized kinetic model for we oxidation of organic compounds[J].AICh E Journal,37(11):1687-1697
林春绵,袁细宁,沈雁,等.2000.ε-酸在超临界水中的氧化降解[J].高校化学工程学报,14(5):480-483
林春绵,袁细宁,杨馗,等.2000.超临界水氧化法降解甲胺磷的研究[J].环境科学学报,20(6):714-718
林少琴,陈玉峰,郑曦,等.2005.电催化氧化降解酚类废水的研究[J].福建师范大学学报,21(3):22-26
刘春明,董秀芹,张敏华.2012.响应面法优化超临界水氧化降解喹啉废[J].环境工程学报,6(10):3568-3572
欧阳创.2013.超临界水氧化法处理有机污染物研究[D].上海:上海交通大学
欧阳创,申哲民,张亚南,等.2013.六种有机物在亚/超临界水中氧化的反应动力学研究[J].安全与环境工程,20(4):67-70
Qu R J,Liu H X,Zhang Q,et al.2012.The effect of hydroxyl groups on the stability and thermodynamic properties of polyhydroxylated xanthones as calculated by density functional theory[J].Thermochimica Acta,527:99-111
Rice S F,Steeper R R.1997.Oxidation rates of common organic compounds in supercritical water[J].Journal of Hazardous Materials,59:261-278
Svishchev I M,Plugatyr A.2006.Supercritical water oxidation of odichlorobenzene:degradation studies and simulation insights[J].The Journal of Supercritical Fluids,37(1):94-101
Vogel F,Blanchard D N,Marrone P A,et al.2005.Critical review of kinetic data for the oxidation of methanol in supercritical water[J].The Journal of Supercritical Fluids,34(3):249-286
Wang Z Y,Zhai Z C,Wang L S,et al.2004.Prediction of gas phase thermodynamic function of polychlorinated dibenzo-p-dioxins using DFT[J].Journal of Molecular Structure Theochem,672(1):97-104
Wiktor Beker,Anna Stachowicz-Kus'nierz,Jarosaw Zaklika,et al.2015.Atomic polarization justified Fukui indices and the affinity indicators in aromatic heterocycles and nucleobases[J].Computational and Theoretical Chemistry,1065:42-49
王齐,吕永康,张荣,等.2012.超临界水氧化处理棉纺织品印染废水[J].环境工程学报,6(11):3959-3906
王涛,刘崇义,沈忠耀,等.1997.超临界水氧化法去除废水COD的动力学研究[J].环境科学研究,10(4):32-35
Xiao R,Zammit I,Wei Z S,et al.2015.Kinetics and mechanism of the oxidation of cyclic methylsiloxanes by hydroxyl radical in the gas phase:An experimental and theoretical study[J].Environ Sci Technol,49(22):13322-30
向波涛,王涛,沈忠耀等.2003.含乙醇废水的超临界水氧化反应动力学及反应机理[J].化工学报,54(1):80-85
谢成,晏波,韦朝海等.2007.焦化废水Fenton氧化预处理过程中主要有机污染物的去除[J].环境科学学报,27(7):1101-1106
袁亚茹.2017.臭氧氧化难降解有机物的定量构效关系研究[D].上海:上海交通大学
Zhang F M,Xu C Y,Zhang Y,et al.2014.Experimental study on the operating characteristics of an inner preheating transpiring wall reactor for supercritical water oxidation:Temperature profiles and product properties[J].Energy,66:577-587
Zhu H C,Guo W M,Shen Z M,et al.2015.QSAR models for degradation of organic pollutants in ozonation process under acidic condition[J].Chemosphere,119:65-71
张世国,杨频.2004.用量子化学密度泛函理论研究环状含氮化合物分子结构与缓蚀性能的关系[J].中国腐蚀与防护学报,24(4):240-244