超声-浸渍法制备污泥负载型高效非均相Fenton催化剂及其催化性能
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摘要
基于简易的超声-浸渍法将铁元素成功掺杂于污泥载体上,得到了一种高效稳定的非均相Fenton催化剂,并运用X射线衍射(XRD)、扫描电子显微镜(SEM)、电感耦合等离子体发射光谱(ICP)和傅立叶变化红外光谱(FT-IR)等对合成催化剂的结构和性能等进行表征,探究了所制备催化剂对亚甲基蓝(MB)模拟废水的降解行为。结果表明,以脱水污泥为载体,可快速有效将铁元素掺杂于污泥中,并主要以Fe_2O_3的形式存在,且负载铁元素和载体形成了Fe—O、Fe—O—H和Si—O—Fe等化学键,保证催化剂的稳定性。对50mg/L MB的降解实验表明,在初始pH为4、催化剂用量为0.6g/L、H_2O_2投加量为5mL/L的最优实验条件下,反应120min后对MB的降解率可达99.8%,并且循环实验5次仍能保持较好的催化性能。同时阐明了非均相Fenton催化体系对MB可能的降解机理。
Heterogeneous Fenton catalyst with high stability and catalytic ability was prepared by ultrasound-enhanced impregnation method and fully characterized by means of X-ray diffraction(XRD),scanning electron microscope(SEM),inductively coupled plasma(ICP)and Fourier transform infrared spectrometer(FT-IR).The catalytic performance of the catalyst was analyzed by degradation of methylene blue.The results indicated that iron element was present in the catalyst in the form of Fe_2O_3,and new chemical bonds Fe—O,Fe—O—H and Si—O—Fe were formed between iron element and dewatered sludge.In the degradation experiment of 50 mg/L simulated methylene blue wastewater(MB),under the optimal experimental conditions of initial pH=4,amount of the catalyst of 0.6 g/L and the H_2O_2 concentration of 5 mL/L,the degradation rate of the catalyst for MB was found to be 99.8% after reaction of 120 min.Moreover,there were no distinct changes in the degradation capacity during the 5 cycles under the optimum conditions,which suggested that the catalytic material had excellent stability of catalytic activity.Meanwhile,the possible degradation mechanism was analyzed for the heterogeneous Fenton system in the degradation of MB.
Heterogeneous Fenton catalyst with high stability and catalytic ability was prepared by ultrasound-enhanced impregnation method and fully characterized by means of X-ray diffraction(XRD),scanning electron microscope(SEM),inductively coupled plasma(ICP)and Fourier transform infrared spectrometer(FT-IR).The catalytic performance of the catalyst was analyzed by degradation of methylene blue.The results indicated that iron element was present in the catalyst in the form of Fe_2O_3,and new chemical bonds Fe—O,Fe—O—H and Si—O—Fe were formed between iron element and dewatered sludge.In the degradation experiment of 50 mg/L simulated methylene blue wastewater(MB),under the optimal experimental conditions of initial pH=4,amount of the catalyst of 0.6 g/L and the H_2O_2 concentration of 5 mL/L,the degradation rate of the catalyst for MB was found to be 99.8% after reaction of 120 min.Moreover,there were no distinct changes in the degradation capacity during the 5 cycles under the optimum conditions,which suggested that the catalytic material had excellent stability of catalytic activity.Meanwhile,the possible degradation mechanism was analyzed for the heterogeneous Fenton system in the degradation of MB.
引文
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[2] GUPTA V K,JAIN R,MITTAL A,et al.Photo-catalytic degradation of toxic dye amaranth on TiO2/UV in aqueous suspensions[J].Materials Science&Engineering C:Materials for Biological Applications,2012,32(1):12-17.
[3] FARZANA M H,MEENAKSHI S.Synergistic effect of chitosan and titanium dioxide on the removal of toxic dyes by the photodegradation technique[J].Industrial&Engineering Chemistry Research,2014,53(1):55-63.
[4] TUNC S,DUMAN O,GURKAN T.Monitoring the decolorization of acid orange 8and acid red 44from aqueous solution using Fenton’s reagents by online spectrophotometric method:effect of operation parameters and kinetic study[J].Industrial&Engineering Chemistry Research,2013,52(4):1414-1425.
[5] IDELAOUAD R,VALIENTE M,YAACOUBI A,et al.Rapid decolourization and mineralization of the azo dye C.I.acid red14by heterogeneous Fenton reaction[J].Journal of Hazardous Materials,2011,186(1):745-750.
[6] SOON A N,HAMEED B H.Heterogeneous catalytic treatment of synthetic dyes in aqueous media using Fenton and photo-assisted Fenton process[J].Desalination,2011,269(1/2/3):1-16.
[7] MKHALID I A,ABDULSALAM A A.Photocatalytic reduction of Hg using core-shell Fe/CeO2hollow sphere nanocomposites[J].Ceramics International,2015,41(4):5614-5620.
[8] DUKKANCI M,GUNDUZ G,YILMAZ S,et al.Heterogeneous Fenton-like degradation of rhodamine 6G in water using CuFeZSM-5zeolite catalyst prepared by hydrothermal synthesis[J].Journal of Hazardous Materials,2010,181(1/2/3):343-350.
[9] WANG Z Z,XIN Y,ZHANG Z L,et al.Synthesis of Fe-doped CeO2nanorods by a widely applicable coprecipitation route[J].Chemical Engineering Journal,2011,178(24):436-442.
[10] WANG L,YAO Y Y,ZHANG Z H,et al.Activated carbon fibers as an excellent partner of Fenton catalyst for dyes decolorization by combination of adsorption and oxidation[J].Chemical Engineering Journal,2014,251(4):348-354.
[11] BEHZADNIA A,MONTAZER M,RAD M M.In-situ sonosynthesis of nano N-doped ZnO on wool producing fabric with photo and bio activities,cell viability and enhanced mechanical properties[J].Journal of Photochemistry and Photobiology BBiology,2015,149:103-115.
[12] PANAHI P N,NIAEI A,SALARI D,et al.Ultrasound-assistant preparation of Cu-SAPO-34 nanocatalyst for selective catalytic reduction of NO by NH3[J].Journal of Environmental Sciences,2015,35(9):135-143.
[13] DUARTE F,MORAIS V,MALDONADO HDAR F J,et al.Treatment of textile effluents by the heterogeneous Fenton process in a continuous packed-bed reactor using Fe/activated carbon as catalyst[J].Chemical Engineering Journal,2013,232:34-41.
[14] KIWI J,DENISOV N,GAK Y,et al.Catalytic Fe3+clusters and complexes in nafion active in photo-Fenton processes.High-resolution electron microscopy and femtosecond studies[J].Langmuir,2002,18(23):9054-9066.
[15] LIU W,QIAN J,WANG K,et al.Magnetically separable Fe3O4nanoparticles-decorated reduced graphene oxide nanocomposite for catalytic wet hydrogen peroxide oxidation[J].Journal of Inorganic and Organometallic Polymers and Materials,2013,23(4):907-916.
[16]MUNOZ M,DE PEDRO Z M,CASAS J A.Preparation of magnetite-based catalysts and their application in heterogeneous Fenton oxidation-a review[J].Applied Catalysis B:Environmental,2015,176/177:249-265.
[17] YANG G,ZHANG G M,WANG H C.Current state of sludge production,management,treatment and disposal in China[J].Water Research,2015,78:60-73.
[18]王建俊,王格格,李刚,等.污泥资源化利用[J].当代化工,2015,44(1):98-100.
[19]杨雷,罗树琼,张印民.利用城市污泥烧制页岩陶粒[J].环境工程学报,2010,4(5):1177-1180.
[20] BJRKLUND K,LI L Y.Adsorption of organic stormwater pollutants onto activated carbon from sewage sludge[J].Journal of Environmental Management,2017,197:490-497.
[21] KONG L J,ZHU Y T,LIU M X,et al.Conversion of Fe-rich waste sludge into nano-flake Fe-SC hybrid Fenton-like catalyst for degradation of AOⅡ[J].Environmental Pollution,2016,216:568-574.
[22] ZHANG H,XUE G,CHEN H,et al.Magnetic biochar catalyst derived from biological sludge and ferric sludge using hydrothermal carbonization:preparation,characterization and its circulation in Fenton process for dyeing wastewater treatment[J].Chemosphere,2018,191:64-71.
[23] DOELSCH E,MASION A,ROSE J,et al.Chemistry and structure of colloids obtained by hydrolysis of Fe(Ⅲ)in the presence of SiO4ligands[J].Colloids and Surfaces A-Physicochemical and Engineering Aspects,2003,217(1/2/3):121-128.
[24] FANG X B,FANG Z Q,TSANG P,et al.Selective adsorption of Cr(Ⅵ)from aqueous solution by EDA-Fe3O4nanoparticles prepared from steel pickling waste liquor[J].Applied Surface Science,2014,314(10):655-662.
[25] ARNOLD S M,HICKEY W J,HARRIS R F.Degradation of atrazine by Fentons reagent-condition optimization and product quantification[J].Environmental Science&Technology,1995,29(8):2083-2089.
[26] YANG S J,HE H P,WU D Q,et al.Degradation of methylene blue by heterogeneous fenton reaction using titanomagnetite at neutral pH values:process and affecting factors[J].Industrial&Engineering Chemistry Research,2009,48(22):9915-9921.
[27] HERNEY RAMIREZ J,VICENTE M A,MADEIRA L M.Heterogeneous photo-Fenton oxidation with pillared claybased catalysts for wastewater treatment:a review[J].Applied Catalysis B:Environmental,2010,98(1/2):10-26.
[28] LIANG C J,SU H W.Identification of sulfate and hydroxyl radicals in thermally activated persulfate[J].Industrial&Engineering Chemistry Research,2009,48(11):5558-5562.
[29] KWAN W P,VOELKER B M.Decomposition of hydrogen peroxide and organic compounds in the presence of dissolved iron and ferrihydrite[J].Environmental Science&Technology,2002,36(7):1467-1476.
[30] GUO S,ZHANG G K,WANG J Q.Photo-Fenton degradation of rhodamine B using Fe2O3-Kaolin as heterogeneous catalyst:characterization,process optimization and mechanism[J].Journal of Colloid and Interface Science,2014,433:1-8.