Cu-Mn/Fe_3O_4@SiO_2@KCC纳米催化剂制备及其催化臭氧化降解对苯二甲酸性能
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摘要
采用微乳法及浸渍法合成负载型铜锰单分散核壳磁性纤维状纳米催化剂(Cu-Mn/Fe_3O_4@SiO_2@KCC),利用XRD、TEM、BET、VSM等手段对其表征;并通过构建类均相催化臭氧化降解对苯二甲酸(100 mg·L~(-1))的研究,考察其催化性能。结果表明:臭氧通入量13.92 mg·min~(-1)、催化剂投加量40 mg·L~(-1)和pH=9时,对苯二甲酸去除率高达90.97%,TOC去除率可达30%。五次循环试验后对苯二甲酸降解率仍稳定在88.23%。
Through a surfactant-templated microemulsion formation process and impregnation method,supported copper and manganese fibrous monodisperse core-shell structured Cu-Mn/Fe_3O_4@SiO_2@ KCC nanocatalyst were synthesised,and characterized by XRD,TEM,BET and VSM. In order to investigate the catalytic properties,homogeneous-like phase catalytic ozonation system has been established and further treatment of terephthalic acid simulated wastewater( 100 mg·L~(-1)). The results showed that the terephthalic acid removal rate can up to 90. 97% and TOC removal rate can up to 30% under optimum conditions( ozone dosage is 13. 92 mg·min~(-1); catalyst dosage is40 mg·L~(-1),pH = 9). It was also verified that the activity of the catalyst remained stable about 88. 23% after 5 times of recycle.
Through a surfactant-templated microemulsion formation process and impregnation method,supported copper and manganese fibrous monodisperse core-shell structured Cu-Mn/Fe_3O_4@SiO_2@ KCC nanocatalyst were synthesised,and characterized by XRD,TEM,BET and VSM. In order to investigate the catalytic properties,homogeneous-like phase catalytic ozonation system has been established and further treatment of terephthalic acid simulated wastewater( 100 mg·L~(-1)). The results showed that the terephthalic acid removal rate can up to 90. 97% and TOC removal rate can up to 30% under optimum conditions( ozone dosage is 13. 92 mg·min~(-1); catalyst dosage is40 mg·L~(-1),pH = 9). It was also verified that the activity of the catalyst remained stable about 88. 23% after 5 times of recycle.
引文
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22 Chen C,Wei L,Guo X,et al.Investigation of heavy oil refinery wastewater treatment by integrated ozone and activated carbon-supported manganese oxides.Fuel Processing Technology,2014;124(4):165—173
2 官宝红,徐根良,赵德明,等.对苯二甲酸废水的处理技术.水处理技术,2002;28(3):129—133Guan Baohong,Xu Genliang,Zhao Deming,et al.Treatment technology of wastewater containing terphthalic acid.Technology of Water Treatment,2002;28(3):129—133
3 张家发,白玲,范浩军,等.超细纤维合成革碱减量废水中对苯二甲酸的分离提纯.中国皮革,2016;45(9):29—34Zhang Jiafa,Bai Ling,Fan Haojun,et al.Separation and purification of terephthalic acid from alkali weight-reduction wastewater of microfine fiber synthetic leather.China Leather,2016;45(9):29—34
4 王海玲,徐炎华,吕力行,等.树脂吸附-Fenton氧化法处理精对苯二甲酸废水.化工环保,2006;26(6):498—501Wang Hailing,Xu Yanhua,Lülixing,et al.Treatment of PTA wastewater by resin adsorption-Fenton reagent oxidation process.Environmental Protection of Chemical Industry,2006;26(6):498 —501
5 严文瑶,陈银合,汤庆华,等.非均相催化氧化处理对苯二甲酸工业废水.工业水处理,2007;27(12):22—24Yan Wenyao,Chen Yinhe,Tang Qinghua,et al.The treatment of terephthalic acid industrial wastewater by heterogeneous catalytic oxidation.Industrial Water Treatment,2007;27(12):22—24
6 王冠华,韩艳萍.预处理-两级好氧生化工艺处理PTA污水.炼油技术与工程,2003;33(12):35—38Wang Guanhua,Han Yanping.Treating PTA unit waste water with pre-treatment-two stage aerobic biochemical process.Petroleum Refinery Engineering,2003;33(12):35—38
7 杨忠林,钟中,韩萍芳,等.厌氧折流板反应器处理PTA废水及其相分离特性.生物加工过程,2012;10(6):60—64Yang Zhonglin,Zhong Zhong,Han Pingfang,et al.Terephthalic acid(PTA)wastewater treated by anaerobic baffled reactor and its phase separation characteristics.Chinese Journal of Bioprocess Engineering,2012;10(6):60—64
8 管国强,徐晓晨,柳丽芬,等.A/O-MBR处理PTA综合废水中试研究.工业水处理,2011;31(10):64—67Guan Guoqiang,Xu Xiaochen,Liu Lifen,et al.A/O-MBR for treating PTA comprehensive wastewater.Industrial Water Treatment,2011;31(10):64—67
9 Zhao H,Dong Y,Jiang P,et al.An insight into the kinetics and interface sensitivity for catalytic ozonation:the case of nano-sized Ni Fe2O4.Catalysis Science and Technology,2014;4(2):494—501
10 Yu K,Zhang X,Tong H,et al.Synthesis of fibrous monodispersecore-shel Fe3O4/Si O2/KCC-1.Materials Letters,2013;106(9):151 —154
11 LüA,Hu C,Nie Y,et al.Catalytic ozonation of toxic pollutants over magnetic cobalt-doped Fe3O4suspensions.Applied Catalysis B Environmental,2012;117—118:246—252
12 Liu J,Qiao S Z,Hu Q H,et al.Magnetic nanocomposites with mesoporous structures:synthesis and applications.Small,2015;7(4):418—418
13 Lopes R J G,Perdigoto M L N,Quinta-Ferreira R M.Tailored investigation and characterization of heterogeneous{Mn,Cu}/Ti O2catalysts embedded within a ceria-based framework for the wet peroxide oxidation of hazardous pollutants.Applied Catalysis B Environmental,2012;117—118:292—301
14 Polshettiwar V,Cha D,Zhang X,et al.High-surface-area silica nanospheres(KCC-1)with a fibrous morphology.Angewandte Chemie,2010;49(50):9652—9656
15 Fihri A,Bouhrara M,Patil U,et al.Fibrous nano-silica supported ruthenium(KCC-1/Ru):a sustainable catalyst for the hydrogenolysis of alkanes with good catalytic activity and lifetime.ACS Catalysis,2012;2(7):1425—1431
16 Dong Z,Le X,Li X,et al.Silver nanoparticles immobilized on fibrous nano-silica as highly efficient and recyclable heterogeneous catalyst for reduction of 4-nitrophenol and 2-nitroaniline.Applied Catalysis Benvironmental,2014;158—159:129—135
17 Chen J,Wen W,Kong L,et al.Magnetically separable and durable Mn Fe2O4for efficient catalytic ozonation of organic pollutants.Industrial and Engineering Chemistry Research,2014;53(15):6297—6306
18 Zhao L,Sun Z,Ma J.Novel relationship between hydroxyl radical initiation and surface group of ceramic honeycomb supported metals for the catalytic ozonation of nitrobenzene in aqueous solution.Environmental Science and Technology,2009;43(11):4157—4163
19 Pera-Titus M,GarcíA-Molina V,Ba1os M A,et al.Degradation of chlorophenols by means of advanced oxidation processes:a general review.Applied Catalysis B Environmental,2004;47(4):219 —256
20 Graham N,Jiang C C,Li X Z,et al.The influence of p H on the degradation of phenol and chlorophenols by potassium ferrate.Chemosphere,2004;56(10):949—956
21 Bing J,Hu C,Zhang L.Enhanced mineralization of pharmaceuticals by surface oxidation over mesoporousγ-Ti-Al2O3suspension with ozone.Applied Catalysis B Environmental,2017;202:118—126
22 Chen C,Wei L,Guo X,et al.Investigation of heavy oil refinery wastewater treatment by integrated ozone and activated carbon-supported manganese oxides.Fuel Processing Technology,2014;124(4):165—173