臭氧降解水中邻苯二甲酸二甲酯的效能及动力学

doi:10.3969/j.issn.0438-1157.2013.04.039

摘要/Abstract

摘要： 利用臭氧降解含较高浓度邻苯二甲酸二甲酯(DMP)的模拟废水,考察了pH、DMP初始浓度、臭氧投加量和温度对臭氧降解DMP效果的影响,并对臭氧降解DMP的效能及动力学进行了研究。结果表明,pH为5～10时DMP的降解效果较好;DMP初始浓度越大,DMP降解率越小,但DMP降解量增加;臭氧投加量的增加有利于DMP降解,但臭氧利用效率降低;温度低时,升高温度DMP降解率增大,24℃后提高温度对DMP降解率影响不大。在pH为5～10、DMP初始浓度为14～66 mg·L^-1、O₃投加量为14～24 mg·min^-1、20～30℃条件下反应40 min,DMP降解率达85%以上。在实验条件范围内,臭氧降解DMP符合拟一级动力学,建立了幂指数表达的动力学模型。在pH为2～12范围内,因臭氧反应机理不同,表观动力学常数k_obs与pH不呈线性关系,pH为2～5时,k_obs快速增加,pH为5～9时,k_obs缓慢增加,pH大于9时k_obs反而降低,pH为9时k_obs最大,为0.0929 min^-1。

关键词: 邻苯二甲酸二甲酯, 废水, 臭氧氧化, 效能, 动力学

Abstract: Ozone was employed for degradation of dimethyl phthalate (DMP) in a simulated wastewater, and the effects of pH, DMP initial concentration, ozone dosage and reaction temperature on DMP degradation and its kinetics were investigated.The experimental results showed that the degradation efficiency of DMP was better in the range of pH 5—10, decreased with increase of DMP initial concentration although degradation total amount of DMP increased gradually, and increased with increase of ozone dosage but ozone utilization efficiency decreased.The reaction temperature had no remarkable effect on the degradation efficiency over 24℃, although below this temperature it increased with rise of temperature. The degradation efficiency could reach up to 85% at the conditions of pH 5—10, DMP concentration 14—66 mg·L^-1, ozone dosage 14—24 mg·min^-1,temperature 20—30℃ and time 40 min.The degradation of DMP by ozonation followed pseudo-first-order kinetics under the experimental conditions, and its kinetic model was determined.There was no correlation between k_obs and pH in the range of pH 2—12, because of different reaction mechanism of ozonation degradation.The k_obs increased quickly in pH 2—5 and slightly in pH 5—9, but the decrease of k_obs was observed over pH 9, and the biggest k_obs was 0.0929 min^-1.

Key words: dimethyl phthalate, waste water, ozonation, efficiency, kinetics

中图分类号:

X783.2

于丽, 张培龙, 庞立飞, 李越, 侯甲才, 贾寿华. 臭氧降解水中邻苯二甲酸二甲酯的效能及动力学[J]. 化工学报, 2013, 64(4): 1408-1414.

YU Li, ZHANG Peilong, PANG Lifei, LI Yue, HOU Jiacai, JIA Shouhua. Degradation efficiency and kinetics of dimethyl phthalate in aqueous solution by ozonation[J]. CIESC Journal, 2013, 64(4): 1408-1414.

参考文献 25

[1]	Cai Shaoqing(蔡少卿), He Yuefeng(何月峰), Dai Qizhou(戴启洲), Chen Jianmeng(陈建孟).Kinetic model on ozonation of p-toluene sulfonic acid[J].CIESC Journal(化工学报), 2011, 62(5):1414-1420
[2]	Yu Zhongchen(于忠臣), Wang Song(王松), Lü Bingnan(吕炳南), Wang Qiuyan(王秋艳), Wu Zengyan(吴增炎), He Jianping(何建平), Guo Ying(郭英).Study on influence factors of acrylic fiber wastewater degradation by Fe2+/UV catalysis ozonation system[J].Chemical Industry and Engineering Progress(化工进展), 2008, 27(12):1972-1976
[3]	Chen Lan(陈岚), Quan Yuheng(权宇珩).Effect of initial pH value in aqueous solution on direct reaction kinetics of 2,4-D with ozone[J].CIESC Journal(化工学报), 2011, 62(6):1569-1573
[4]	Shen Yuanli(申元丽), Ma Jinfeng(马金锋), Zhao Xu(赵旭), Liu Shuangyue(刘双跃), Lan Huachun(兰华春).Ozonation of herbicide glyphosate[J].Journal of Acta Scientiae Circumstanitiae(环境科学学报), 2011, 31(8):1647-1652
[5]	Leitner N K V, Roshani B.Kinetic of benzotriazole oxidation by ozone and hydroxyl radical[J].Water Research, 2010, 44(6):2058-2066
[6]	Pratarn W, Pornsiri T, Thanit S, Tawatchai C, Wiwut T.Adsorption and ozonation kinetic model for phenolic wastewater treatment[J].Chinese Journal of Chemical Engineering, 2011, 19(1):76-82
[7]	An Jibin(安继斌), Feng Huixia(冯辉霞), Yang Hai(阳海), Gao Yanpeng(高艳蓬), Li Guiying(李桂英), An Taicheng(安太成).The contribution of different reactive species to the kinetics of photocatalytic degradation of dimethyl phthalate in water[J].Journal of Ecology and Environmental Sciences(生态环境学报), 2010, 19(6):1369-1373
[8]	Hu Xiaoyu(胡晓宇), Zhang Kerong(张克荣), Sun Junhong(孙俊红), Wu Desheng(吴德生).Environmental contamination by phthalates in China[J].Chinese Journal of Health Laboratory Technology(中国卫生检验杂志), 2003, 13(1):9-14
[9]	Zhou Wenmin(周文敏), Fu Deqian(傅德黔), Sun Zongguang(孙宗光).Determination of black list of China’s priority pollutants in water[J].Research of Environmental Sciences(环境科学研究), 1991, 4(6):9-12
[10]	Matsumoto M, Koizumi M H, Ema M.Potential adverse effects of phthalic acid esters on human health:a review of recent studies on reproduction[J].Regulatory Toxicology and Pharmacology, 2008, 50(1):37-49
[11]	Rui Min(芮旻), Gao Naiyun(高乃云), Xu Bin(徐斌), Zhao Jianfu(赵建夫), Le Linsheng(乐林生), Wu Jinming(吴今明).Removal effect of dimethyl phthalate in water by UV, H2O2, O3 and combination processes and corresponding mechanism analysis[J].Acta Scientiae Circumstantiae(环境科学学报),2005, 25(11):1457-1463
[12]	Salim C J, Liu H, Kennedy J F.Comparative study of the adsorption on chitosan beads of phthlalate esters and their degradation products[J].Carbohydrate Polymers, 2010, 81(3):640-644
[13]	Kaneco S, Katsumata H, Suzuki T, Kunihiro F, Ohta K.Solar photo-catalytic degradation of endocrine disruptor di-n-butyl phthalate in aqueous solution using zinc oxide[J].Bulletin of the Catalysis Society of India, 2007, 6:22-33
[14]	Roslev P, Vorkamp K, Aarup J, Frederiksen K, Nielsen P H.Degradation of phthalate esters in an activated sludge wastewater treatment plant[J].Water Research, 2007, 41:969-976
[15]	Jurgen B.Mixed results:latest study adds skepticism, hope to ozone debate[J].Textile Rental, 1995,2:78-84
[16]	William H G, Joon W K.Advanced oxidation processes test of a kinetic model for the oxidation of organic compounds with ozone and hydrogen peroxide in a semibatch reactor[J].Ind.Eng.Chem.Res., 1989, 28(11):1580-1587
[17]	Zhong Li(钟理),Hai K C, Edward Z M.Experimental study of liquid phase oxidation of trichloroethylene with ozone[J].Journal of Chemical Industry and Engineering(China)(化工学报), 1998, 49(1):116-120
[18]	Roth J A, Sullivan D E.Solubility of ozone in water[J].Ind.Eng.Chem.Fundamen., 1981, 20(2):137-141
[19]	Sevimli M F, Sarikaya H Z.Ozone treatment of textile effluents and dyes:effect of applied ozone dose, pH and dye concentration[J].J.Chem.Technol.Biotechnol., 2002, 77(7):842-850
[20]	Elovitz M S, Gunten V U, Kaiser H P.Hydroxyl radical/ozone ratios during ozonation processes(Ⅱ):The effect of temperature, pH, alkalinity, and DOM properties[J].Journal of the International Ozone Association, 2000, 22(2):123-150
[21]	Sotelo J L, Beltrán F J, Benitez F J.Henry’s law constant for the ozone-water system[J].Water Research, 1989, 23(10):1239- 1246
[22]	Shi Huixiang(史惠祥), Xu Xianwen(徐献文), Wang Dahui(汪大翚).Influencing factors and mechanism of decomposition of 4-nitrophenol by US/O3[J].Journal of Chemical Industry and Engineering(China)(化工学报), 2006, 57(2):390-396
[23]	Zhang Ling(张凌), Tao Ying(陶莹), Chang Zhixian(常志显), Li Deliang(李德亮).Kinetics of p-toluene sulfonic acid degradation by ozone in aqueous solutions[J].Acta Scientiae Circumstantiae(环境科学学报), 2011, 31(10):2185-2191
[24]	Zhao Deming(赵德明), Zhang Jianting(张建庭), Jin Ningren(金宁人), Xu Xinhua(徐新华).Kinetics of phenol degradation in water using microwave/O3 system[J].Journal of Zhejiang University(浙江大学学报),2011, 45(4):770-774
[25]	He Zhiqiao(何志桥), Song Shuang(宋爽), Zhou Huamin(周华敏), Ying Haiping(应海萍), Chen Jianmeng(陈建孟).Kinetics of degradation of 4-aminophenol in aqueous solution by ozonation combined with sonolysis[J].Journal of Chemical Industry and Engineering(China)(化工学报),2006, 57(12):2964-2968