臭氧氧化降解水中青霉素G特性和动力学特征
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摘要
为考察水中PCN(青霉素G)在臭氧氧化过程中的降解规律与特征,采用臭氧直接氧化法处理模拟废水中的PCN,研究了初始pH、ρ(臭氧)、初始ρ(PCN)、自由基抑制剂TBA(叔丁醇)、反应温度等对水中PCN去除效果的影响,并分析了PCN在臭氧氧化降解过程中的降解特性和动力学特征.结果表明:①在溶液体积为1 L、初始ρ(PCN)为50 mg/L、初始pH为11、ρ(臭氧)为15 mg/L、反应温度为20℃时,反应5 min时PCN去除率为100%,反应2 h时TOC去除率为28. 98%.②PCN的降解速率和TOC去除效果随pH的增大而升高,碱性环境有利于PCN的矿化.③臭氧氧化过程中,PCN的降解以臭氧直接氧化为主,其降解中间产物的矿化主要以臭氧间接氧化为主,TBA可抑制强氧化性羟基自由基的产生效率,因而对TOC的矿化有明显的抑制作用.④对PCN的降解过程进行一级、伪一级和二级动力学方程拟合,结果表明,伪一级动力学方程拟合相关性(R~2=0. 999 7)最高,k(反应速率常数)最大值为0. 825 5 min~(-1).研究显示,臭氧直接氧化可有效降解水中PCN,但对中间产物的矿化去除效果较为有限,臭氧氧化降解PCN的过程遵循伪一级反应动力学方程.
In order to investigate the degradation characteristics of PCN (Penicillin G) by ozone oxidation,the PCN in simulated wastewater was treated by direct ozone oxidation. The effects of initial pH,ρ (ozone),ρ (PCN),radical scavenger TBA (t-butanol) and temperature etc. on the removal of PCN in water were investigated,and the degradation characteristics and kinetics of PCN were analyzed.The results showed that: (1) When the solution volume was 1 L,the initial ρ (PCN) was 50 mg/L,the initial pH was 11,the ρ (ozone)was 15 mg/L,and the reaction temperature was 20 ℃,the PCN removal could reach 100% after 5 min of reaction,and the TOC removal was 28. 89% at 2 h. (2) The degradation of PCN and TOC removal efficiency increased with the increase of initial pH,and the alkaline environment was beneficial to the mineralization of PCN. (3) During the process of ozone oxidation,the degradation of PCN was mainly caused by direct ozone oxidation,while the mineralization of PCN and its degradation intermediates was mainly dominated by indirect oxidation of free radicals; TBA could inhibit the production efficiency of strong oxidative hydroxyl radicals, thus inhibiting the mineralization of TOC obviously. (4) The first-order,pseudo-first-order and second-order kinetic equations fitted the degradation process of PCN,and it showed that the pseudo-first-order kinetic equation had the highest correlation,R~2= 0. 9997,and the maximum value of k was 0. 8255 min~(-1). It showed that direct ozone oxidation could effectively degrade PCN in water,but the mineralization removal of the intermediate products was limited. The ozone oxidative degradation process of PCN followed the pseudo first-order reaction kinetics.
In order to investigate the degradation characteristics of PCN (Penicillin G) by ozone oxidation,the PCN in simulated wastewater was treated by direct ozone oxidation. The effects of initial pH,ρ (ozone),ρ (PCN),radical scavenger TBA (t-butanol) and temperature etc. on the removal of PCN in water were investigated,and the degradation characteristics and kinetics of PCN were analyzed.The results showed that: (1) When the solution volume was 1 L,the initial ρ (PCN) was 50 mg/L,the initial pH was 11,the ρ (ozone)was 15 mg/L,and the reaction temperature was 20 ℃,the PCN removal could reach 100% after 5 min of reaction,and the TOC removal was 28. 89% at 2 h. (2) The degradation of PCN and TOC removal efficiency increased with the increase of initial pH,and the alkaline environment was beneficial to the mineralization of PCN. (3) During the process of ozone oxidation,the degradation of PCN was mainly caused by direct ozone oxidation,while the mineralization of PCN and its degradation intermediates was mainly dominated by indirect oxidation of free radicals; TBA could inhibit the production efficiency of strong oxidative hydroxyl radicals, thus inhibiting the mineralization of TOC obviously. (4) The first-order,pseudo-first-order and second-order kinetic equations fitted the degradation process of PCN,and it showed that the pseudo-first-order kinetic equation had the highest correlation,R~2= 0. 9997,and the maximum value of k was 0. 8255 min~(-1). It showed that direct ozone oxidation could effectively degrade PCN in water,but the mineralization removal of the intermediate products was limited. The ozone oxidative degradation process of PCN followed the pseudo first-order reaction kinetics.
引文
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[28]RAHMANI A R,NEMATOLLAHI D,SAMARGHANDI M R,et al.A combined advanced oxidation process:electrooxidation-ozonation for antibiotic ciprofloxacin removal from aqueous solution[J].Journal of Electroanalytical Chemistry,2018,808:82-89.
[29]GOMES J,COSTA R,QUINTA-FERREIRA R M,et al.Application of ozonation for pharmaceuticals and personal care products removal from water[J].Science of the Total Environment,2017,586:265-283.
[30]PHATTARANAWIK J,LEIKNES T,PRONK W.Mass transfer studies in flat-sheet membrane contactor with ozonation[J].Journal of Membrane Science,2005,247(12):153-167.
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[32]DE-WITTE B,DEWULF J,DEMEESTERE K,et al.Ozonation and advanced oxidation by the peroxone process of ciprofloxacin in water[J].Journal of Hazardous Materials,2009,161(23):701-708.
[33]URBANO V R,MANIERO M G,PEREZ-MOYA M,et al.Influence of pH and ozone dose on sulfaquinoxaline ozonation[J].Journal of Environmental Management,2017,195:224-231.
[2]ZHAO L,JI Y,YAO J Y,et al.Quantifying the fate and risk assessment of different antibiotics during wastewater treatment using a Monte Carlo simulation[J].Journal of Cleaner Production,2017,168:626-631.
[3]MOURA D,BARCELOS V,SAMANAMUD G R L,et al.Normal boundary intersection applied as multivariate and multiobjective optimization in the treatment of amoxicillin synthetic solution[J].Environmental Monitoring and Assessment,2018,190(3):140-152.
[4]朱琳,张远,渠晓东,等.北京清河水体及水生生物体内抗生素污染特征[J].环境科学研究,2014,27(2):139-146.ZHU Lin,ZHANG Yuan,QU Xiaodong,et al.Occurrence of antibiotics in aquatic plants and organisms from Qing River,Beijing[J].Research of Environmental Sciences,2014,27(2):139-146.
[5]秦延文,张雷,时瑶,等.大辽河表层水体典型抗生素污染特征与生态风险评价[J].环境科学研究,2015,28(3):361-368.QIN Yanwen,ZHANG Lei,SHI Yao,et al.Contamination characteristics and ecological risk assessment of typical antibiotics in surface water of the Daliao River,China[J].Research of Environmental Sciences,2015,28(3):361-368.
[6]BRUCKNER I,KIRCHNER K,MULLER Y,et al.Status quo report on wastewater treatment plant,receiving water's biococenosis and quality as basis for evaluation of large-scale ozonation process[J].Water Science and Technology,2018,77(2):337-345.
[7]YONAR T,KURT A.Treatability studies of hospital wastewaters with AOPs by Taguchi's experimental design[J].Global Nest Journal,2017,19(3):505-510.
[8]ALHARBI S K,PRICE W E.Degradation and fate of pharmaceutically active contaminants by advanced oxidation processes[J].Current Pollution Reports,2017,3(4):268-280.
[9]YU H,GE P,CHEN J W,et al.The degradation mechanism of sulfamethoxazole under ozonation:a DFT study[J].Environmental Science-Processes and Impacts,2017,19(3):379-387.
[10]JOSS A,ZABCZYNSKI S,GOBEL A,et al.Biological degradation of pharmaceuticals in municipal wastewater treatment:proposing a classification scheme[J].Water Research,2006,40(8):1686-1696.
[11]ARSLAN-ALATON I,CAGLAYAN A E.Ozonation of procaine penicillin G formulation effluent.part I:process optimization and kinetics[J].Chemosphere,2005,59(1):31-39.
[12]ROBERTO A,VINCENZO C,CLAUDIA C,et al.Antibiotics in the environment:occurrence in Italian STPs,fate,and preliminary assessment on algal toxicity of amoxicillin[J].Environmental Science&Technology,2004,38(24):6832-6838.
[13]DANTAS R F,CONTRERAS S,SANS C,et al.Sulfamethoxazole abatement by means of ozonation[J].Journal of Hazardous Materials,2008,150:790-794.
[14]LI G,BEN W W,YE H,et al.Performance of ozonation and biological activated carbon in eliminating sulfonamides and sulfonamide-resistant bacteria:a pilot-scale study[J].Chemical Engineering Journal,2018,341:327-334.
[15]WANG C K,HUANG B M.Degradation of tetracycline by advanced oxidation processes:sono-Fenton and ozonation processes[J].Desalination and Water Treatment,2017,96:161-168.
[16]吕元元,任钟旗,张卫东,等.高效液相色谱法测定青霉素G的方法改进[J].中国药业,2008,17(13):18-19.LV Yuanyuan,REN Zhongqi,ZHANG Weidong,et al.Improvement of HPLC method for determinant of penicillin G[J].China Pharmaceuticals,2008,17(13):18-19.
[17]BADER H,HOIGNJ.Determination of ozone in water by the indigo method[J].Water Research,1981,15(4):449-456.
[18]LI K X,YEDILER A,YANG M,et al.Ozonation of oxytetracycline and toxicological assessment of its oxidation by-products[J].Chemosphere,2008,72(3):473-478.
[19]LING W C,BEN W W,XU K,et al.Ozonation of norfloxacin and levofloxacin in water:specific reaction rate constants and defluorination reaction[J].Chemosphere,2018,195:252-259.
[20]KIDAK R,DOGAN S.Medium-high frequency ultrasound and ozone based advanced oxidation for amoxicillin removal in water[J].Ultrasonics Sonochemistry,2018,40:131-139.
[21]MICHAEL-KORDATOU I,ANDREOU R,IACOVOU M,et al.On the capacity of ozonation to remove antimicrobial compounds,resistant bacteria and toxicity from urban wastewater effluents[J].Journal of Hazardous Materials,2017,323:414-425.
[22]DE OLIVEIRA A M D,MANIERO M G,RODRIGUES-SILVA C,et al.Antimicrobial activity and acute toxicity of ozonated lomefloxacin solution[J].Environmental Science and Pollution Research,2017,24(7):6252-6260.
[23]HONRMANDRAD Z,ASADIPOUR A,MALAKOOTIAN M.Investigating the use of ozonation process with calcium peroxide for the removal of metronidazole antibiotic from aqueous solutions[J].Desalination and Water Treatment,2017,77:315-320.
[24]WU C Y,ZHOU Y X,SUN X M,et al.The recent development of advanced wastewater treatment by ozone and biological aerated filter[J].Environmental Science and Pollution Research,2018,25(9):8315-8329.
[25]BAI Z Y,WANG J L,YANG Q.Iron doped fibrous-structured silica nanospheres as efficient catalyst for catalytic ozonation of sulfamethazine[J].Environmental Science and Pollution Research,2018,25(10):10090-10101.
[26]GOI A,VERESSININA Y,TRAPIDO M.Combination of ozonation and the Fenton processes for landfill leachate treatment:evaluation of treatment efficiency[J].Ozone:Science and Engineering,2009,31(1):28-36.
[27]KERDNAWEE K,KUPTAJIT P,SANO N,et al.Catalytic ozonation of oxy-tetracycline using magnetic carbon nanoparticles[J].Journal of the Japan Institute of Energy,2017,96(9):362-366.
[28]RAHMANI A R,NEMATOLLAHI D,SAMARGHANDI M R,et al.A combined advanced oxidation process:electrooxidation-ozonation for antibiotic ciprofloxacin removal from aqueous solution[J].Journal of Electroanalytical Chemistry,2018,808:82-89.
[29]GOMES J,COSTA R,QUINTA-FERREIRA R M,et al.Application of ozonation for pharmaceuticals and personal care products removal from water[J].Science of the Total Environment,2017,586:265-283.
[30]PHATTARANAWIK J,LEIKNES T,PRONK W.Mass transfer studies in flat-sheet membrane contactor with ozonation[J].Journal of Membrane Science,2005,247(12):153-167.
[31]许恒韬.臭氧氧化法深度处理硝基氯苯类化工废水研究[D].杭州:浙江大学,2006.
[32]DE-WITTE B,DEWULF J,DEMEESTERE K,et al.Ozonation and advanced oxidation by the peroxone process of ciprofloxacin in water[J].Journal of Hazardous Materials,2009,161(23):701-708.
[33]URBANO V R,MANIERO M G,PEREZ-MOYA M,et al.Influence of pH and ozone dose on sulfaquinoxaline ozonation[J].Journal of Environmental Management,2017,195:224-231.