Mn-Ce/γ-Al_(2) O_(3)催化臭氧氧化深度处理石化废水中试研究  

Pilot Study of Advanced Treatment of Petrochemical Wastewater by Mn-Ce/γ-Al_(2)O_(3) Catalytic Ozonation

作　　者：李敏[1,2] 付丽亚[1,2] 谭煜 赵檬 周岳溪 吴昌永[1,2] LI Min;FU Liya;TAN Yu;ZHAO Meng;ZHOU Yuexi;WU Changyong(Research Center of Water Pollution Control Technology,Chinese Research Academy of Environmental Sciences,Beijing 100012,China;State Key Laboratory of Environmental Criteria and Risk Assessment,Chinese Research Academy of Environmental Sciences,Beijing 100012,China)

机构地区：[1]中国环境科学研究院环境污染控制工程技术研究中心,北京100012 [2]中国环境科学研究院,环境标准与风险评估国家重点实验室,北京100012

出　　处：《环境科学研究》2021年第10期2380-2388,共9页Research of Environmental Sciences

基　　金：国家水体污染控制与治理科技重大专项(No.2017ZX07402002)。

摘　　要：针对臭氧催化氧化深度处理石化废水时催化剂适配性不高和臭氧利用率低下的问题,以我国北方某典型石化废水为中试平台,采用课题组自主研发的催化臭氧催化剂Mn-Ce/γ-Al_(2)O_(3),研究以臭氧催化氧化为核心的7种工艺深度处理石化废水的效果.结果表明:①单独臭氧氧化工艺对石化二级废水COD、TOC和UV_(254)(254 nm处的UV吸光度)的去除率分别为15.45%、9.04%和30.72%.与单独臭氧氧化工艺相比,Mn-Ce/γ-Al_(2)O_(3)催化臭氧氧化工艺下,COD、TOC和UV 254的去除率分别提高了26.18%、18.25%和5.81%,同时三维荧光光谱(3D-EEM)结合区域积分法(FRI)分析结果显示,对荧光类有机物中溶解性微生物代谢产物和类腐殖酸的去除率分别提高了21.13%和29.47%.②单独臭氧氧化工艺中,序批式和连续流出水处理效果影响不大.Mn-Ce/γ-Al_(2)O_(3)催化臭氧氧化工艺下,序批式优于连续流,但序批式需增加人力和运营成本,在实际应用中受限.③微絮凝+臭氧催化氧化+回流联合工艺中,COD、TOC和UV_(254)的去除率分别可达53.20%、37.56%和50.90%,去除效果显著高于仅臭氧催化氧化工艺(COD、TOC和UV_(254)的去除率分别为41.63%、27.29%和36.53%)时;同时,类富里酸、类溶解性微生物代谢产物和类腐殖酸的去除率分别达到79.49%、50.70%和75.12%;Mn-Ce/γ-Al_(2)O_(3)催化剂运用72 d后,COD去除率基本稳定在30%左右.研究显示,臭氧催化氧化工艺深度处理石化废水中,Mn-Ceγ-Al_(2)O_(3)是一种高效稳定型催化剂,絮凝预处理、回流均可增强有机物的去除率,可为石化废水处理工程实现减排降耗提供技术支撑.Taking the typical petrochemical wastewater in northern China as a pilot test platform,the ozone catalyst Mn-Ce/γ-Al_(2)O_(3) independently developed by the research group was used to study the effects of seven processes of catalytic ozonation in advanced treatment of petrochemical wastewater.The results showed that:(1)The removal rates of COD,TOC,and UV_( 254)(UV absorbance at 254 nm)in secondary petrochemical wastewater by ozonation process were 15.45%,9.04%and 30.72%,respectively.Compared with ozonation process,in the Mn-Ce/γ-Al_(2)O_(3) catalytic ozonation process,the removal rates of COD,TOC,and UV 254 increased by 26.18%,18.25%and 5.81%,respectively.Three-dimensional fluorescence spectroscopy(3D-EEM)combined with fluorescence regional integration(FRI)analysis results showed that the removal of soluble microbial metabolites and humic acids in fluorescent organic compounds increased by 21.13%and 29.47%,respectively.(2)In the ozonation process,sequential batch and continuous flow had little effect on effluent treatment.In the Mn-Ce/γ-Al_(2)O_(3) catalytic ozonation process,the sequential batch was better than the continuous flow,but the sequential batch required additional labor and operating costs,which makes limited its practical application.(3)In the combined process of micro flocculation+catalytic ozonation+reflux,the removal rates of COD,TOC,and UV _(254) reached 53.20%,37.56%and 50.90%,respectively,and the removal efficiency was significantly higher than that of catalytic ozonation process only(the removal rates of COD,TOC,and UV 254 were 41.63%,27.29%and 36.53%,respectively).The removal rates of fulvic acids,soluble microbial metabolites,and humic acids reached 79.49%,50.70%and 75.12%,respectively.After using the catalyst for 72 days,the COD removal stabilized at about 30%.The research indicates that Mn-Ce/γ-Al_(2)O_(3) is an efficient and stable catalyst for the advanced treatment of petrochemical wastewater by catalytic ozonation process.Both micro flocculation pretreatment and reflux can increase

关 键 词：臭氧氧化 催化剂 石化废水 深度处理 微絮凝 回流 

分 类 号：X703.1[环境科学与工程—环境工程]