纳米锰铈/γ-Al_2O_3复合催化剂的制备及其对抗生素生产废水的催化湿式氧化处理研究
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摘要
制备纳米级锰铈/复合γ-Al_2O_3催化剂,对催化材料的矿物相、微观形貌与成分、官能团组成等分析鉴定,将其应用到不同反应条件下催化湿式氧化处理抗生素废水的研究中,对其动力学过程进行分析。结果表明:Mn和Ce元素被负载在γ-Al_2O_3载体材料上;负载层以纳米级颗粒团聚体组成;该材料具有较强的热稳定性。催化湿式氧化对抗生素废水的去除效果大幅度增加,随着催化剂量的增加、反应温度的提高以及反应时间的延长,催化湿式氧化对抗生素废水的TOC与COD去除率逐渐提高,且催化湿式氧化去除效果均远远高于湿式氧化,190℃反应2 h的TOC与COD去除率均提升了近50%。湿式氧化与催化湿式氧化处理抗生素生产废水的反应过程符合一级动力学方程,催化湿式氧化可大幅度提高反应的速率常数。
A nanometer-scale manganese cerium @ γ-Al_2O_3 catalyst was prepared,and the mineral phase,micro-morphology,composition,and functional group of the catalytic material were analyzed and identified. The catalyst was applied to catalytic wet air oxidation treatment of antibiotic wastewater under different reaction conditions,and the kinetic process was analyzed. The results show that Mn and Ce elements are supported on the γ-Al_2O_3 carrier material,the carrier layer is composed of nanometer particle agglomerates,and the material has a strong thermal stability. In addition,the effect of catalytic wet air oxidation on the removal of antibiotic waste water is greatly increased. With the increasing of the amount of catalyst,reaction temperature and reaction time,the removal rates of TOC and COD of antibiotic wastewaters are gradually improved by catalytic wet air oxidation. Furthermore,the removalefficiency of catalytic wet air oxidation is much higher than that of the wet air oxidation. The TOC and COD removal rates of catalytic wet air oxidation increase nearly 50% at 190 ℃ for 2 h. The reaction process of wet air oxidation and catalytic air wet oxidation treatment of antibiotic production wastewater fitted the first-order kinetic equation,and catalytic wet oxidation improved the reaction rate constant to a large extent.
A nanometer-scale manganese cerium @ γ-Al_2O_3 catalyst was prepared,and the mineral phase,micro-morphology,composition,and functional group of the catalytic material were analyzed and identified. The catalyst was applied to catalytic wet air oxidation treatment of antibiotic wastewater under different reaction conditions,and the kinetic process was analyzed. The results show that Mn and Ce elements are supported on the γ-Al_2O_3 carrier material,the carrier layer is composed of nanometer particle agglomerates,and the material has a strong thermal stability. In addition,the effect of catalytic wet air oxidation on the removal of antibiotic waste water is greatly increased. With the increasing of the amount of catalyst,reaction temperature and reaction time,the removal rates of TOC and COD of antibiotic wastewaters are gradually improved by catalytic wet air oxidation. Furthermore,the removalefficiency of catalytic wet air oxidation is much higher than that of the wet air oxidation. The TOC and COD removal rates of catalytic wet air oxidation increase nearly 50% at 190 ℃ for 2 h. The reaction process of wet air oxidation and catalytic air wet oxidation treatment of antibiotic production wastewater fitted the first-order kinetic equation,and catalytic wet oxidation improved the reaction rate constant to a large extent.
引文
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[2] Deegan A M,Shaik B,Nolan K,et al. Treatment options for waste water effluents from pharmaceutical companies[J]. International Journal of Environmental Science and Technology,2011,8(3):649-666.
[3]姚宏,何永淼,吕开雷,等.高硫酸盐抗生素废水生物处理[J].北京交通大学学报,2012,36(6):97-101.
[4]郭喜丰,肖广全,马丽莉,等.超声波降解四环素类抗生素废水[J].环境工程学报,2014,8(4):1503-1509.
[5]徐武军,张国臣,郑明霞,等.臭氧氧化技术处理含抗生素废水[J].化学进展,2010,22(5):1002-1009.
[6]陈友岚,李炳堂.负载纳米铁活性炭与微波联用处理抗生素废水的研究[J].水处理技术,2013,39(12):91-94.
[7]朱鹏飞,刘梅,张杰,等. Fe-Ni共掺杂Zn O/凹凸棒光催化降解废水中抗生素性能研究[J].安全与环境学报,2015,15(5):230-234.
[8]吴亚帆,孙绍芳,李杰. CoPcS/Bi2WO6复合材料的制备及其光催化性能[J].应用化工,2013,42(7):1230-1233.
[9]黄昱,李小明,杨麒,等.高级氧化技术在抗生素废水处理中的应用[J].工业水处理,2006,26(8):13-17.
[10] Melero J A,Martnez F,Botas J A,et al. Heterogeneous catalytic wet peroxide oxidation systems for the treatment of an industrial pharmaceutical wastewater[J]. Water Research,2009,43:4010-4018.
[11]崔娜,王国文,徐晓晨,等.催化湿式空气氧化处理磷霉素钠、黄连素制药废水试验研究[J],水处理技术,2012,38(2):72-75.
[12] Chen C,Cheng T. Wet air oxidation and catalytic wet air oxidation for refinery spent caustics degradation[J]. J. Chem. Soc. Pak.,2013,35(2):243-249.