臭氧催化氧化降解2,2′-亚甲基-双(4-甲基-6-叔丁基苯酚)效能及机制研究  

Study on degradation efficiency and mechanism of 2,2′-methylenebis(4-methyl-6-tertbutylphenol)by catalytic ozonation

作　　者：马翠 刘亚琦 何争光[2] MA Cui;LIU Ya-qi;HE Zheng-guang(School of Environmental and Municipal Engineering,North China University of Water Resources and Electric Power,Zhengzhou 450046,China;School of Ecological and Environmental Science,Zhengzhou University,Zhengzhou 450000,China)

机构地区：[1]华北水利水电大学环境与市政工程学院,郑州450046 [2]郑州大学生态与环境学院,郑州450000

出　　处：《安全与环境学报》2022年第2期1045-1051,共7页Journal of Safety and Environment

摘　　要：采用牛粪灰(CDA)负载纳米Fe_(3)O_(4)催化臭氧降解2,2′-亚甲基-双(4-甲基-6-叔丁基苯酚)(AO2246)。Fe_(3)O_(4)@CDA催化剂通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能量色散谱仪(EDS)和高分辨透射电子显微镜(HR-TEM)进行表征。负载在牛粪灰表面的纳米Fe_(3)O_(4)颗粒分布更分散,团聚程度较小。Fe_(3)O_(4)@CDA的HR-TEM检测表明在纳米Fe_(3)O_(4)颗粒周围呈现CDA的无序晶格结构,根据晶格边缘的d间距反射(约0.287 nm)推断出立方磁铁矿Fe_(3)O_(4)的220晶格平面。在初始pH值为7.0、反应温度为25℃、AO2246质量浓度为10 mg/L、催化剂质量浓度为0.20 g/L,臭氧质量浓度为10 mg/L的条件下,AO2246的去除率可达47.6%。采用电子顺磁共振(EPR)、气相色谱-质谱联用仪(GC-MS)对AO2246臭氧催化降解过程进行分析。由GC-MS试验结果可知:目标污染物苯环中间的碳碳键最先受到羟基自由基(·OH)的攻击,碳碳键发生断裂;在·OH继续攻击下,不断发生加成、取代反应,AO2246苯环打开,最终形成一系列简单的有机物,检测出(3,5-双(1,1-二甲基乙基)-苯酚)、4-(1,1-二甲基乙基)-苯甲酸(3,5-双(1,1-二甲基乙基)-苯酚)、4-(1,1-二甲基乙基)-苯甲酸、(E)-4-(2,6,6-三甲基-1-环己烯-1-基)-3-丁烯-2-酮、1-(1,4-二甲基-3-环己烯-1-基)-乙酮、2-叔丁基环己酮、2-乙酰基环己酮、5-叔丁基-六-3,5-二烯-2-酮、2-羟基己酸丙戊酸乙烯基酯、异戊酸甲酯、丙酸等10余种中间产物,·OH在催化臭氧降解AO2246的过程中起主要作用,提出了AO2246的降解途径及机理。研究结果表明CDA负载纳米Fe_(3)O_(4)催化臭氧氧化更有利于羟基自由基的产生,对合成酚类抗氧化剂的降解具有一定的指导意义。Composite magnetic oxide at cow dung ash,nano-Fe_(3)O_(4)@cow dung ash(nano-Fe_(3)O_(4)@CDA),was used as the catalytic material for the degradation of 2,2′-methylenebis(4-methyl-6-tert-butylphenol)(AO 2246).The Fe_(3)O_(4)@CDA catalyst was characterized by XRD,SEM,EDS and HR-TEM.The nano-Fe_(3)O_(4)particles binding on the cow dung ash surface were seen to be more dispersed and less agglomerated.The HR-TEM of the Fe_(3)O_(4)@CDA was investigated and showed that the disordered lattice structure of CDA was presented around the Fe_(3)O_(4)NPs and the(220)lattice plane of cubic magnetite Fe_(3)O_(4)was reflected according to the d-spacing of the lattice fringes(about 0.287 nm).The Fe_(3)O_(4)@CDA composite exhibited catalytic ozonation activity and allowed material separation and magnetic recovery.The effects of several operating parameters including O;concentration,catalyst dosage,temperature,and scavengers were evaluated in parallel.Under the conditions of initial pH of 7.0,the temperature of 25℃,AO2246 concentration of 10 mg/L,catalyst dosage of 0.20 g/L,ozone concentration of 10 mg/L,the AO2246 removal reached 47.6%.The EPR and GC-MS experiments expatiated the mechanism of this degradation process.It was confirmed that the AO 2246 was degraded efficiently in this catalytic micro-ozonation process.Additionally,GC-MS analysis state clearly that the addition and substitution reactions occurred continuously under the attack of·OH.A series of simple organic matter was finally formed after the benzene ring of AO2246 was open.Additionally,GC-MS analysis state clearly that the 3,5-bis(1,1-dimethylethyl)phenol,4-(1,5-dihydroxy-2,6,6-trimethylcyclohex-2-enyl)but-3-en-2-one,ethanone,1-(1,4-dimethyl-3-cyclohexen-1-yl)-,5-tert-butyl-6-3,5-diene-2-one,2-hydroxyhexanoic acid,2-propenoic acid 1,1-dimethylethyl ester,butanoic acid,2-methyl-,methyl ester and propanoic acid,2,2-dimethyl-were the dominant oxidation products(OPs)during the catalytic micro-ozonation degradation of the AO 2246.The possible degradation pathways wer

关 键 词：环境工程学 合成分类抗氧化剂 臭氧催化氧化 纳米四氧化三铁 

分 类 号：X52[环境科学与工程—环境工程]