Mn-Al_2O_3/O_3催化氧化深度处理制药废水
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摘要
以活性氧化铝球为载体,采用静置、搅拌、超声3种方法制备了Mn-Al_2O_3催化剂,通过XRD、SEM等手段比较了不同方法制备的催化剂的性能。并采用以搅拌法制备的Mn-Al_2O_3催化剂与臭氧联用来处理制药废水,分析了臭氧投加量、Mn-Al_2O_3催化剂投加量、pH值和反应时间对处理效果的影响,同时对反应过程进行了动力学分析。试验结果表明,当制药废水体积为1 L、臭氧投加量为4. 8 g/h、Mn-Al_2O_3催化剂投加量为300 g、pH值为7、反应时间为30 min时,对COD的去除率高达55. 6%,且Mn-Al_2O_3/O_3催化氧化过程符合拟一级动力学方程,对COD的降解速率常数为0. 026 41 min~(-1)。
Mn-Al_2O_3 catalysts were prepared by standing,stirring and sonication methods by using activated aluminum oxide balls as the carrier,and properties of the catalyst prepared by different methods were compared by means of X-ray diffraction( XRD) and scanning electron microscopy( SEM).Pharmaceutical wastewater was treated by the Mn-Al_2O_3 catalysts prepared by stirring method combined with ozone. Meanwhile,the effect of ozone dosage,catalyst dosage,p H value and reaction time on treatment efficiency was explored,and kinetics of the reaction process was analyzed. The results showed that the removal rate of COD was up to 55. 6% when volume of the pharmaceutical wastewater was 1 L,the dosage of ozone was 4. 8 g/h,the dosage of the catalyst was 300 g,pH value was 7 and reaction time was 30 min. Moreover,the Mn-Al_2O_3/O_3 catalytic oxidation process conformed to pseudo-first-order kinetic equation,and the degradation rate constant of COD was 0. 026 41 min~(-1).
Mn-Al_2O_3 catalysts were prepared by standing,stirring and sonication methods by using activated aluminum oxide balls as the carrier,and properties of the catalyst prepared by different methods were compared by means of X-ray diffraction( XRD) and scanning electron microscopy( SEM).Pharmaceutical wastewater was treated by the Mn-Al_2O_3 catalysts prepared by stirring method combined with ozone. Meanwhile,the effect of ozone dosage,catalyst dosage,p H value and reaction time on treatment efficiency was explored,and kinetics of the reaction process was analyzed. The results showed that the removal rate of COD was up to 55. 6% when volume of the pharmaceutical wastewater was 1 L,the dosage of ozone was 4. 8 g/h,the dosage of the catalyst was 300 g,pH value was 7 and reaction time was 30 min. Moreover,the Mn-Al_2O_3/O_3 catalytic oxidation process conformed to pseudo-first-order kinetic equation,and the degradation rate constant of COD was 0. 026 41 min~(-1).
引文
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[2]李亚峰,高颖.制药废水处理技术研究进展[J].水处理技术,2014,40(5):1-4.Li Yafeng,Gao Ying.Research progress in the treatment technologies of pharmaceutical wastewater[J].Technology of Water Treatment,2014,40(5):1-4(in Chinese).
[3]宋鑫,任立人,吴丹,等.制药废水深度处理技术的研究现状及进展[J].广州化工,2012,40(12):29-31.Song Xin,Ren Liren,Wu Dan,et al.The present situation and research progress in the advanced treatment of pharmaceutical wastewater[J].Guangzhou Chemical Industry,2012,40(12):29-31(in Chinese).
[4]程晓东,禚青倩,余正齐,等.非均相催化臭氧化污水处理技术研究进展[J].工业用水与废水,2017,48(1):6-9.Cheng Xiaodong,Zhuo Qingqian,Yu Zhengqi,et al.Research progress of sewage treatment by heterogeneous catalytic ozonation[J].Industrial Water&Wastewater,2017,48(1):6-9(in Chinese).
[5]Zhao L,Ma J,Sun Z Z,et al.Catalytic ozonation for the degradation of nitrobenzene in aqueous solution by ceramic honeycomb-supported manganese[J].Applied Catalysis B:Environmental,2008,83(3):256-264.
[6]Xing S T,Hu C,Qu J H,et al.Characterization and reactivity of MnOxsupported on mesoporous zirconia for herbicide 2,4-D mineralization with ozone[J].Environ Sci Technol,2008,42(9):3363-3368.
[7]Alsheyab M A,Mun~oz A H.Comparative study of ozone and MnO2/O3effects on the elimination of TOC and COD of raw water at the Valmayor station[J].Desalination,2007,207(1/3):179-183.
[8]王烨,杨文忠.γ-Al2O3负载氧化锰催化臭氧化苯酚的研究[J].工业用水与废水,2017,48(2):32-37.Wang Ye,Yang Wenzhong.Catalytic ozonation of phenol in water byγ-Al2O3supported manganese oxide[J].Industrial Water&Wastewater,2017,48(2):32-37(in Chinese).
[9]刘越男,吕效平,韩萍芳.超声浸渍法制备Fe3O4/γ-Al2O3催化剂及其表征、活化研究[J].化工学报,2007,58(11):2805-2809.Liu Yuenan,LüXiaoping,Han Pingfang.Preparation of Fe3O4/γ-Al2O3catalyst by ultrasonic impregnation and its characterization and catalytic activity[J].CIESCJournal,2007,58(11):2805-2809(in Chinese).
[10]尚会建,蒋梁鹤,允川,等.活性炭催化臭氧化处理含氰废水的试验研究[J].黄金,2011,32(3):56-59.Shang Huijian,Jiang Lianghe,Yun Chuan,et al.Catalytic ozonation with activated carbon for treating cyanide wastewater[J].Gold,2011,32(3):56-59(in Chinese).
[11]Shukla P R,Wang S B,Sun H Q,et al.Activated carbon supported cobalt catalysts for advanced oxidation of organic contaminants in aqueous solution[J].Applied Catalysis B:Environmental,2010,100(3/4):529-534.
[12]王春雨,侯永江,刘璇,等.不同晶型二氧化锰催化臭氧化降解亚甲基蓝废水[J].环境工程学报,2017,11(2):908-914.Wang Chunyu,Hou Yongjiang,Liu Xuan,et al.Degradation of methylene blue by catalytic ozonation with different crystalline MnO2[J].Chinese Journal of Environmental Engineering,2017,11(2):908-914(in Chinese).
[13]王宏伟,王天来,齐岩,等.臭氧催化氧化工艺中p H值对催化剂活性的影响研究[J].化工科技,2017,25(5):53-56.Wang Hongwei,Wang Tianlai,Qi Yan,et al.Effect of p H value on catalytic activity in catalytic ozonation process[J].Science&Technology in Chemical Industry,2017,25(5):53-56(in Chinese).