不同高级氧化工艺处理焦化废水二级生化工艺出水研究
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摘要
针对焦化废水二级生化处理工艺出水化学需氧量(COD)难以达标的问题,采用实际焦化废水,通过开展半连续实验室小试试验,对比研究了单独臭氧氧化、O_3/H_2O_2氧化和UV-Fenton氧化3种工艺深度处理焦化废水的效果,并对不同工艺出水的UV_(254)、BOD_5/COD、发光细菌毒性、三维荧光光谱进行分析,研究不同高级氧化工艺对出水水质的影响规律。结果表明:增加臭氧投加量和添加H_2O_2能显著提高焦化废水二级生化工艺出水中有机物的去除效果。进水COD为(200±10)mg/L、O_3投加量为30 mg/L时,反应120 min后单独臭氧氧化对COD的去除率仅为36%;而对于UV-Fenton氧化,进水COD为(200±10)mg/L、H_2O_2(30%)投加浓度为2 g/L、Fe~(2+)与H_2O_2摩尔比为1∶10时,COD的去除率为50%;单独臭氧氧化和UV-Fenton均不能满足排放标准。进水COD为(200±10)mg/L、O_3投加量为30 mg/L、H_2O_2(30%)投加浓度为2 g/L,反应120 min后COD去除率达到63%,O_3/H_2O_2氧化工艺出水COD达到74 mg/L,满足GB 16171—2012《炼焦化学工业污染物排放标准》的要求。3种工艺中,O_3/H_2O_2氧化的COD去除效果最好,这主要归因于O_3和H_2O_2协同产生强氧化性自由基,但当H_2O_2浓度过高时,体系中产生的·OH反而与H_2O_2反应,从而导致O_3/H_2O_2体系的氧化能力下降。3种工艺都能有效降低出水毒性,出水发光细菌急性毒性试验显示,单独O_3氧化、O_3/H_2O_2氧化处理15 min后,相对发光度分别上升到90%和87%,UV-Fenton氧化处理30 min后,出水的相对发光度上升到71.57%。与单独臭氧氧化和O_3/H_2O_2氧化工艺相比,UV-Fenton工艺处理出水急性毒性相对较高,可能与臭氧的消毒作用有关。3种工艺对废水可生化性的提高程度不明显,BOD_5/COD从0.02最大提升到0.1左右。UV_(254)和三维荧光光谱的对比分析表明,3种工艺对出水中芳香族化合物和荧光物质具有明显的分解作用。单独O_3氧化可优先降解废水中腐植酸类物质中的共轭双键结构,而O_3/H_2O_2氧化工艺对环状共轭污染物的氧化效果更显著。随着UV-Fenton氧化处理,焦化废水中大分子的类腐植酸以及紫外区类富里酸优先被氧化降解,最终转化为可见区类富里酸和类蛋白质,而类蛋白质和可见区类富里酸物质在出水中仍存在较高浓度,UV-Fenton氧化工艺对荧光物质去除能力最差。
The COD of the effluent from the secondary biological treatment process of coking wastewater couldn't meet the standard.In order to resolve the problem,the effects of advanced treatment of coking wastewater by single ozonation,O_3/H_2O_2oxidation and UV-Fenton processes respectively,were investigated through laboratory test,which were carried out in semi-continuous mode.The quality of effluent from the different processes were analyzed,where UV_(254),BOD_5/COD,the luminescent bacteria toxicity,three-dimensional fluorescence spectrum were evaluated.The influence of different advanced oxidation processes on effluent quality was explored.The results show that the increase of ozone dosage and addition of H_2O_2can significantly enhance the removal of organic compounds in the secondary biochemical effluent from coking wastewater.When the COD of the influent is(200±10)mg/L,the average COD removal rate for 120 min reaction in single ozonation process is 36%with the ozone dosage of 30 mg/L.When the COD of the influent is(200±10)mg/L,the average COD remov-al rate for 120 min reaction in UV-Fenton process is 50%with the H_2O_2dosage of 2 g/L and the molar ratio of Fe~(2+)and H_2O_2of 1∶10.When the COD of the influent is(200±10)mg/L,the average COD removal rate for 120 min reaction in O_3/H_2O_2oxidation process is63%with the ozone dosage of 30 mg/L and H_2O_2dosage of 2 g/L,which meets the Emission Standard of Pollutants for Coking Chemical Industry,China(GB 16171—2012).Among the three processes,the O_3/H_2O_2oxidation process is the most effective for organic compounds removal.This is mainly attributed to the synergistic production of strong oxidizing radicals by O_3and H_2O_2.However,when the concentration of H_2O_2is too high,·OH produced in the system reacts with H_2O_2instead,resulting in the decline of oxidation capacity of O_3/H_2O_2system.All the three processes can reduce its toxicity.The results of acute toxicity test of with luminescent bacteria shows that the relative luminosity of effluent after single ozonation and O_3/H_2O_2oxidation for 15 min increaseto 90%and 87%,respectively.After UV-Fenton oxidation for 30 min,the relative luminescence of effluent increases to 71.57%.Compared with single ozonation and O_3/H_2O_2oxidation process,the effluent of UV-Fenton treatment has relatively higher acute toxicity,which may be related to the disinfection effect of ozone.The three processes can hardly improve its biodegradability,while BOD_5/COD only increases from 0.02 to about 0.1.The comparative analysis of UV_(254)and EEM(Excitation-emission Matrix)show that the three processes have obvious decomposition effect on aromatic compounds and fluorescent substances in the secondary biochemical effluent.The conjugated double-bond substances of humic acid-like substances in wastewater can be preferentially degraded in single ozonation process,while O_3/H_2O_2oxidation process has more significant oxidation effect on cyclic conjugated pollutants.In the UV-Fenton process,humic acid-like substances and UV-fulvic acid-like in coking wastewater are oxidized preferentially,and eventually converted into visible fulvic acid-like and protein-like,which still have relatively high concentration in the effluent.Among the three oxidation processes,the removal of fluorescent substances by UV-Fenton oxidation process is the worst.
The COD of the effluent from the secondary biological treatment process of coking wastewater couldn't meet the standard.In order to resolve the problem,the effects of advanced treatment of coking wastewater by single ozonation,O_3/H_2O_2oxidation and UV-Fenton processes respectively,were investigated through laboratory test,which were carried out in semi-continuous mode.The quality of effluent from the different processes were analyzed,where UV_(254),BOD_5/COD,the luminescent bacteria toxicity,three-dimensional fluorescence spectrum were evaluated.The influence of different advanced oxidation processes on effluent quality was explored.The results show that the increase of ozone dosage and addition of H_2O_2can significantly enhance the removal of organic compounds in the secondary biochemical effluent from coking wastewater.When the COD of the influent is(200±10)mg/L,the average COD removal rate for 120 min reaction in single ozonation process is 36%with the ozone dosage of 30 mg/L.When the COD of the influent is(200±10)mg/L,the average COD remov-al rate for 120 min reaction in UV-Fenton process is 50%with the H_2O_2dosage of 2 g/L and the molar ratio of Fe~(2+)and H_2O_2of 1∶10.When the COD of the influent is(200±10)mg/L,the average COD removal rate for 120 min reaction in O_3/H_2O_2oxidation process is63%with the ozone dosage of 30 mg/L and H_2O_2dosage of 2 g/L,which meets the Emission Standard of Pollutants for Coking Chemical Industry,China(GB 16171—2012).Among the three processes,the O_3/H_2O_2oxidation process is the most effective for organic compounds removal.This is mainly attributed to the synergistic production of strong oxidizing radicals by O_3and H_2O_2.However,when the concentration of H_2O_2is too high,·OH produced in the system reacts with H_2O_2instead,resulting in the decline of oxidation capacity of O_3/H_2O_2system.All the three processes can reduce its toxicity.The results of acute toxicity test of with luminescent bacteria shows that the relative luminosity of effluent after single ozonation and O_3/H_2O_2oxidation for 15 min increaseto 90%and 87%,respectively.After UV-Fenton oxidation for 30 min,the relative luminescence of effluent increases to 71.57%.Compared with single ozonation and O_3/H_2O_2oxidation process,the effluent of UV-Fenton treatment has relatively higher acute toxicity,which may be related to the disinfection effect of ozone.The three processes can hardly improve its biodegradability,while BOD_5/COD only increases from 0.02 to about 0.1.The comparative analysis of UV_(254)and EEM(Excitation-emission Matrix)show that the three processes have obvious decomposition effect on aromatic compounds and fluorescent substances in the secondary biochemical effluent.The conjugated double-bond substances of humic acid-like substances in wastewater can be preferentially degraded in single ozonation process,while O_3/H_2O_2oxidation process has more significant oxidation effect on cyclic conjugated pollutants.In the UV-Fenton process,humic acid-like substances and UV-fulvic acid-like in coking wastewater are oxidized preferentially,and eventually converted into visible fulvic acid-like and protein-like,which still have relatively high concentration in the effluent.Among the three oxidation processes,the removal of fluorescent substances by UV-Fenton oxidation process is the worst.
引文
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[13]彭思伟,戴子瑜,何绪文.煤制油废水中溶解性有机物(DOM)在生物处理过程中的变化特性[J].矿业科学学报,2018,3(6):77-85.PENG Siwei,DAI Ziyu,HE Xuwen. Variation characteristics of dissolved organic matter(DOM)in coal-to-liquids wastewater during biological treatment process[J].Journal of Mining Science and Technology,2018,3(6):77-85.
[14] YANG Zili,YANG Chaoxia,CHANG Jiewei. New flotation flowsheet for recovering combustible matter from fine waste coking coal[J]. Journal of Cleaner Production,2019,225:209-219.
[15]桂玉明.用臭氧法处理焦化废水的研究[D].鞍山:辽宁科技大学,2008.
[16]刘金泉,李天增,王发珍,等.O3、H2O2/O3及UV/O3在焦化废水深度处理中的应用[J].环境工程学报,2009,3(3):501-505.LIU Jinquan,LI Tianzeng,WANG Fazhan,et al. Application of O3,H2O2/O3and UV/O3in advanced treatment of coking wastewater[J]. Chinese Journal of Environmental Engineering,2009,3(3):501-505.
[17]李东伟,高先萍,蓝天.UV-Fenton试剂处理焦化废水的研究[J].水处理技术,2008,34(10):42-45.LI Dongwei,GAO Xianping,LAN Tian. Study on coking wastewater treatment by UV-Fenton system[J]. Technology of Water Treatment,2008,34(10):42-45.
[18]国家环境保护总局.水和废水监测分析方法[M].北京:中国环境出版社,2002.
[19] ANDREOZZI R,CAPRIO V,MAROTTA R.Iron hydroxidemediated photooxidation of aminophenol in aqueous solution a kinetic study[J].Water Research,2003,37(15):3682-3688.
[20] COBLE P G. Characterization of marine and terrestrial DOM in seawater using excitation emission matrix spectroscopy[J]. Marine Chemistry,1995,51(4):325-346.
[21] BAKER A,INVERARITY R,CHARLTON M,et al.Detecting river pollution using fluorescence spectrophotometry:Case studies from the Ouseburn,NE England[J]. Environmental Pollution,2003,124(1):57-70.
[22] MOUNIER S,PATEL N,QUILICI L,et al.Three-dimensional fluorescence of the dissolved organ carbon in the Amazon River[J].Water Research,1999,33(6):1523-1533.
[23] YANG W,LI X,PAN B,et al.Effective removal of effluent organic matter(EfOM)from bio-treated coking wastewater by a recyclable aminated hyper-cross-linked polymer[J]. Water Research,2013,47(13):4730-4738.
[2] NA C,ZHANG Y,QUAN X,et al.Evaluation of the detoxification efficiencies of coking wastewater treated by combined anaerobicanoxic-oxic(A2O)and advanced oxidation process[J].Journal of Hazardous Materials,2017,338:186-193.
[3] SHI L,WANG D,CAO D,et al.Is A/A/O process effective in toxicity removal? Case study with coking wastewater[J].Ecotoxicology and Environmental Safety,2018,142:363-368.
[4]单明军,吕艳丽,丛蕾.焦化废水处理技术[M].北京:化学工业出版社,2007.
[5] MARTINS R C,QUINTA-FERREIRA R M. Comparison of advanced oxidation processes(AOPs)based on O3and H2O2for the remediation of real wastewaters[J].Journal of Advanced Oxidation Technologies,2011,14(2):282-291.
[6] HWANG T M,OH B S,YOON Y,et al.Continuous determination of hydrogen peroxide formed in advanced oxidation and electrochemical processes[J]. Desalination and Water Treatment,2012,43(13):267-273.
[7] BEDUK F,AYDIN M E,OZCAN S.Degradation of malathion and parathion by ozonation,photolytic ozonation and heterogeneous catalytic ozonation processes[J]. Clean-Soil Air Water,2012,40(2):179-187.
[8] MA Dehua,CHEN Lujun,LIU Cong,et al.Biological removal of antiandrogenic activity in gray wastewater and coking wastewater by membrane reactor process[J]. Journal of Environmental Sciences,2015,33(7):195-202.
[9] XIE R,WU M,QU G,et al.Treatment of coking wastewater by a novel electric assisted micro-electrolysis filter[J].Journal of Environmental Sciences,2018,66:165-172.
[10] WEI Z,LIANG F,LIU Y,et al.Photoelectrocatalytic degradation of phenol-containing wastewater by Ti O2/g-C3N4hybrid heterostructure thin film[J].Applied Catalysis B:Environmental,2017,201:600-606.
[11]何灿,刘鲤粽,何文丽.臭氧催化氧化深度处理焦化废水的试验研究[J].洁净煤技术,2016,22(5):53-58.HE Can,LIU Lizong,HE Wenli. Advanced treatment of coking waste water by ozone catalytic oxidation technology[J]. Clean Coal Technology,2016,22(5):53-58.
[12]章丽萍,项俊,严振宇,等.O3降解水杨羟肟酸选矿废水机理研究[J].矿业科学学报2019,4(1):79-85.ZHANG Liping,XIANG Jun,YAN Zhenyu,et al.Mechanism study on ozonization degradation of salicylhydroxamic acid in flotation wastewater[J].Journal of Mining Science and Technology,2019,4(1):79-85.
[13]彭思伟,戴子瑜,何绪文.煤制油废水中溶解性有机物(DOM)在生物处理过程中的变化特性[J].矿业科学学报,2018,3(6):77-85.PENG Siwei,DAI Ziyu,HE Xuwen. Variation characteristics of dissolved organic matter(DOM)in coal-to-liquids wastewater during biological treatment process[J].Journal of Mining Science and Technology,2018,3(6):77-85.
[14] YANG Zili,YANG Chaoxia,CHANG Jiewei. New flotation flowsheet for recovering combustible matter from fine waste coking coal[J]. Journal of Cleaner Production,2019,225:209-219.
[15]桂玉明.用臭氧法处理焦化废水的研究[D].鞍山:辽宁科技大学,2008.
[16]刘金泉,李天增,王发珍,等.O3、H2O2/O3及UV/O3在焦化废水深度处理中的应用[J].环境工程学报,2009,3(3):501-505.LIU Jinquan,LI Tianzeng,WANG Fazhan,et al. Application of O3,H2O2/O3and UV/O3in advanced treatment of coking wastewater[J]. Chinese Journal of Environmental Engineering,2009,3(3):501-505.
[17]李东伟,高先萍,蓝天.UV-Fenton试剂处理焦化废水的研究[J].水处理技术,2008,34(10):42-45.LI Dongwei,GAO Xianping,LAN Tian. Study on coking wastewater treatment by UV-Fenton system[J]. Technology of Water Treatment,2008,34(10):42-45.
[18]国家环境保护总局.水和废水监测分析方法[M].北京:中国环境出版社,2002.
[19] ANDREOZZI R,CAPRIO V,MAROTTA R.Iron hydroxidemediated photooxidation of aminophenol in aqueous solution a kinetic study[J].Water Research,2003,37(15):3682-3688.
[20] COBLE P G. Characterization of marine and terrestrial DOM in seawater using excitation emission matrix spectroscopy[J]. Marine Chemistry,1995,51(4):325-346.
[21] BAKER A,INVERARITY R,CHARLTON M,et al.Detecting river pollution using fluorescence spectrophotometry:Case studies from the Ouseburn,NE England[J]. Environmental Pollution,2003,124(1):57-70.
[22] MOUNIER S,PATEL N,QUILICI L,et al.Three-dimensional fluorescence of the dissolved organ carbon in the Amazon River[J].Water Research,1999,33(6):1523-1533.
[23] YANG W,LI X,PAN B,et al.Effective removal of effluent organic matter(EfOM)from bio-treated coking wastewater by a recyclable aminated hyper-cross-linked polymer[J]. Water Research,2013,47(13):4730-4738.