Cu/Al_2O_3催化剂用于H_2O_2分解生成羟基自由基的效率
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摘要
非均相Fenton催化反应是降解废水中有机污染物的有效方法。提高H_2O_2分解生成羟基自由基(·OH)的利用率是提升废水处理效率、降低成本的关键。使用溶胶-凝胶法制备了Cu/Al_2O_3催化剂,基于·OH的生成效率,通过单因素实验发现反应温度、反应溶液pH及H_2O_2初始浓度是决定H_2O_2利用率的主要因素。通过响应面法进行实验设计,分析响应面方程,考察了H_2O_2初始浓度、溶液pH及反应温度三个因素之间的交互作用及其对反应过程的影响。以H_2O_2利用率的最大化为目标优化反应条件,当H_2O_2初始浓度、溶液pH及反应温度分别为707mg·L~(-1)、5.12及59.4℃时,H_2O_2利用率可高达0.57,与实验结果相对误差仅为3.5%。所得结果对降低废水处理成本、提高降解效率具有重要的指导作用。
Heterogeneous Fenton reaction is an effective method for the degradation of organic pollutants in the waste water.The improvement of H_2O_2 utilization efficiency for hydroxyl(·OH)production is the primary challenge to enhance the efficiency and reduce the cost for waste water degradation.Cu/Al_2O_3 catalysts were prepared through a sol-gel method.Based on the formation efficiency of·OH,the reaction temperature,the pH of the reaction solution and the initial concentration of H_2O_2 were the main factors determining the utilization of H_2O_2 by single factor experiments.Through the design of experiments via response surface methodology and the analysis of the regression equation,the influence of three independent variables,initial H_2O_2 concentration,pH and reaction temperature,and their interactions on H_2O_2 utilization efficiency was evaluated.To achieve the highest H_2O_2 utilization efficiency,the optimum parameters were determined as 707 mg·L~(-1) of H_2O_2 initial concentration,5.12 of pH and 59.4℃of reaction temperature.The corresponding H_2O_2 utilization efficiency is 0.57 and the relative error is only 3.5%compared with experimental value,suggesting that response surface methodology can provide important guidance on reducing cost and improving efficiency for waste water treatment.
Heterogeneous Fenton reaction is an effective method for the degradation of organic pollutants in the waste water.The improvement of H_2O_2 utilization efficiency for hydroxyl(·OH)production is the primary challenge to enhance the efficiency and reduce the cost for waste water degradation.Cu/Al_2O_3 catalysts were prepared through a sol-gel method.Based on the formation efficiency of·OH,the reaction temperature,the pH of the reaction solution and the initial concentration of H_2O_2 were the main factors determining the utilization of H_2O_2 by single factor experiments.Through the design of experiments via response surface methodology and the analysis of the regression equation,the influence of three independent variables,initial H_2O_2 concentration,pH and reaction temperature,and their interactions on H_2O_2 utilization efficiency was evaluated.To achieve the highest H_2O_2 utilization efficiency,the optimum parameters were determined as 707 mg·L~(-1) of H_2O_2 initial concentration,5.12 of pH and 59.4℃of reaction temperature.The corresponding H_2O_2 utilization efficiency is 0.57 and the relative error is only 3.5%compared with experimental value,suggesting that response surface methodology can provide important guidance on reducing cost and improving efficiency for waste water treatment.
引文
[1]HU Y,CHENG H.Water pollution during China’s industrial transition[J].Environmental Development,2013,8:57-73.
[2]HUANG C,DONG C,TANG Z.Advanced chemical oxidation:its present role and potential future in hazardous waste treatment[J].Waste Management,1993,13(5):361-377.
[3]KUZNETSOVA E V,SAVINOV E N,VOSTRIKOVA L A,et al.Heterogeneous catalysis in the Fenton-type system FeZSM-5/H2O2[J].Applied Catalysis B Environmental,2004,51(3):165-170.
[4]HERMANEK M,ZBORIL R,MEDRIK I,et al.Catalytic efficiency of iron(Ⅲ)oxides in decomposition of hydrogen peroxide:?competition between the surface area and crystallinity of nanoparticles[J].Journal of the American Chemical Society,2007,129(35):10929-10936.
[5]POURAN S R,AZIZ A,WAN M,et al.Estimation of the effect of catalyst physical characteristics on Fenton-like oxidation efficiency using adaptive neuro-fuzzy computing technique[J].Measurement,2015,59:314-328.
[6]HE J,MA W,HE J,et al.Photooxidation of azo dye in aqueous dispersions of H2O2/α-FeOOH[J].Applied Catalysis BEnvironmental,2002,39(3):211-220.
[7]ZHONG X,ROYER S,ZHANG H,et al.Mesoporous silica irondoped as stable and efficient heterogeneous catalyst for the degradation of C.I.Acid Orange 7 using sono-photo-Fenton process[J].Separation&Purification Technology,2011,80(1):163-171.
[8]YANG X J,XU X M,XU J,et al.Iron oxychloride(Fe OCl):an efficient Fenton-like catalyst for producing hydroxyl radicals in degradation of organic contaminants[J].Journal of the American Chemical Society,2013,135:16058-16061.
[9]YANG X J,TIAN P F,ZHANG X M,et al.The generation of hydroxyl radicals by hydrogen peroxide decomposition on FeOCl/SBA-15catalysts for phenol degradation[J].AIChE Journal,2015,61:166-176.
[10]BOKARE A D,CHOI W.Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes[J].Journal of Hazardous Materials,2014,275:121-135.
[11]ZHANG L,XU D,HU C,et al.Framework Cu-doped Al PO4 as an effective Fenton-like catalyst for bisphenol A degradation[J].Applied Catalysis B:Environmental,2017,207:9-16.
[12]GRANATO T,KATOVIC A,VALKAJ K M,et al.Cu-silicalite-1catalyst for the wet hydrogen peroxide oxidation of phenol[J].Journal of Porous Materials,2009,16(2):227-232.
[13]GUZMAN-VARGAS A,DE LA ROSA-PINEDA J E,OLIVER-TOLENTINO M A,et al.Stability of Cu species and zeolite structure on ecological heterogeneous Fenton discoloration-degradation of yellow 5 dye:efficiency on reusable Cu-Y catalysts[J].Environmental Progress&Sustainable Energy,2015,34(4):990-998.
[14]PAN W,ZHANG G,ZHENG T,et al.Degradation of p-nitrophenol using CuO/Al2O3 as a Fenton-like catalyst under microwave irradiation[J].RSC Advances,2015,5(34):27043-27051.
[15]SUBBARAMAIAH V,SRIVASTAVA V C,MALL I D.Catalytic activity of Cu/SBA-15 for peroxidation of pyridine bearing wastewater at atmospheric condition[J].AIChE Journal,2013,59(7):2577-2586.
[16]TARAN O P,ZAGORUIKO A N,AYUSHEEV A B,et al.Wet peroxide oxidation of phenol over Cu-ZSM-5 catalyst in a flow reactor.Kinetics and diffusion study[J].Chemical Engineering Journal,2015,282:108-115.
[17]BJ?RKBACKA?,YANG M,GASPARRINI C,et al.Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides[J].Dalton Transactions,2015,44(36):16045-16051.
[18]LYU L,ZHANG L,HU C.Enhanced Fenton-like degradation of pharmaceuticals over framework copper species in copper-doped mesoporous silica microspheres[J].Chemical Engineering Journal,2015,274:298-306.
[19]LYU L,ZHANG L,HU C,et al.Enhanced Fenton-catalytic efficiency by highly accessible active sites on dandelion-like copper-aluminumsilica nanospheres for water purification[J].Journal of Materials Chemistry A,2016,4(22):8610-8619.
[20]LYU L,ZHANG L,WANG Q,et al.Enhanced Fenton catalytic efficiency ofγ-Cu-Al2O3 byσ-Cu2+-ligand complexes from aromatic pollutant degradation[J].Environmental Science&Technology,2015,49(14):8639-8647.
[21]WANG H,ZHANG L,HU C,et al.Enhanced degradation of organic pollutants over Cu-doped La AlO3 perovskite through heterogeneous Fenton-like reactions[J].Chemical Engineering Journal,2018,332:572-581.
[22]ZHANG Y,LIU C,XU B,et al.Degradation of benzotriazole by a novel Fenton-like reaction with mesoporous Cu/MnO2:combination of adsorption and catalysis oxidation[J].Applied Catalysis B:Environmental,2016,199:447-457.
[23]SHENG Y Y,SUN Y,XU J,et al.Fenton-like degradation of rhodamine B over highly durable Cu-embedded alumina:kinetics and mechanism[J].AIChE Journal,2018,64:538-549.
[24]ZHANG X,DING Y,TANG H,et al.Degradation of bisphenol A by hydrogen peroxide activated with CuFeO2 microparticles as a heterogeneous Fenton-like catalyst:efficiency,stability and mechanism[J].Chemical Engineering Journal,2014,236:251-262.
[25]LAI L,ZHANG L,HU C,et al.Enhanced Fenton-catalytic efficiency by highly accessible active sites on dandelion-like copper-aluminumsilica nanospheres for water purification[J].Journal of Materials Chemistry A,2016,4(22):8610-8619.
[26]FU L,LI X,LIU M,et al.Insights into the nature of Cu doping in amorphous mesoporous alumina[J].Journal of Materials Chemistry A,2013,1(46):14592-14605.
[27]EISENBERG G.Colorimetric determination of hydrogen peroxide[J].Industrial&Engineering Chemistry Analytical Edition,1943,15(5):327-328.
[28]LINDSEY M E,TARR M A.Quantitation of hydroxyl radical during Fenton oxidation following a single addition of iron and peroxide[J].Chemosphere,2000,41(3):409-417.
[29]JENSEN M C R,VENKATARAMANI K,HELVEG S,et al.Morphology,dispersion,and stability of Cu nanoclusters on clean and hydroxylatedα-Al2O3(0001)substrates[J].The Journal of Physical Chemistry C,2008,112(43):16953-16960.
[30]TIAN P F,OUYANG L K,XU X Y,et al.The origin of palladium particle size effects in the direct synthesis of H2O2:is smaller better?[J].Journal of Catalysis,2017,349:30-40.
[31]张国臣.过氧化氢生产技术[M].北京:化学工业出版社,2012:54-72.ZHANG G C.Production Technology of H2O2[M].Beijing:Chemical Industry Press,2012:54-72.
[32]GOOR G,GLENNEBERG J,JACOBI S.Hydrogen Peroxide[M].Weinheim:Wiley-VCH Verlag GmbH&Co.KGaA,2007:396-397
[33]YANG X J,XU X M,XU X C,et al.Modeling and kinetics study of Bisphenol A(BPA)degradation over an FeOCl/SiO2 Fenton-like catalyst[J].Catalysis Today,2016,276:85-96.
[34]ARSLAN-ALATON I,TURELI G,OLMEZ-HANCI T.Treatment of azo dye production wastewaters using photo-Fenton-like advanced oxidation processes:optimization by response surface methodology[J].Journal of Photochemistry and Photobiology A:Chemistry,2009,202(2):142-153.
[35]WU Y,ZHOU S,QIN F,et al.Modeling physical and oxidative removal properties of Fenton process for treatment of landfill leachate using response surface methodology(RSM)[J].Journal of Hazardous Materials,2010,180(1):456-465.
[36]MITSIKA E E,CHRISTOPHORIDIS C,FYTIANOS K.Fenton and Fenton-like oxidation of pesticide acetamiprid in water samples:kinetic study of the degradation and optimization using response surface methodology[J].Chemosphere,2013,93(9):1818-1825.
[37]CRUZ-GONZáLEZ K,TORRES-LóPEZ O,GARCíA-LEóN A,et al.Determination of optimum operating parameters for acid yellow36 decolorization by electro-Fenton process using BDD cathode[J].Chemical Engineering Journal,2010,160(1):199-206.
[38]LI H,GONG Y,HUANG Q,et al.Degradation of orange II by UV-assisted advanced Fenton process:response surface approach,degradation pathway,and biodegradability[J].Industrial&Engineering Chemistry Research,2013,52(44):15560-15567.
[39]ZHU X,TIAN J,LIU R,et al.Optimization of Fenton and electroFenton oxidation of biologically treated coking wastewater using response surface methodology[J].Separation and Purification Technology,2011,81(3):444-450.
[40]王欣,王金翠,殷晓梅,等.乙酰甲胺磷UV-TiO2/类Fenton光催化降解过程的响应面法优化[J].应用化工,2013,42(1):33-40.WANG X,WANG J C,YIN X M,et al.Optimization of photocatalytic degradation of acephate by UV-TiO2/Fenton-like process using response surface methodology[J].Applied Chemical Industry,2013,42(1):33-40.
[41]ZHANG P,YUAN S,LIAO P.Mechanisms of hydroxyl radical production from abiotic oxidation of pyrite under acidic conditions[J].Geochimicaet Cosmochimica Acta,2016,172:444-457.
[42]HE J,YANG X,MEN B,et al.Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials:a review[J].Journal of Environmental Sciences,2016,39:97-109.
[2]HUANG C,DONG C,TANG Z.Advanced chemical oxidation:its present role and potential future in hazardous waste treatment[J].Waste Management,1993,13(5):361-377.
[3]KUZNETSOVA E V,SAVINOV E N,VOSTRIKOVA L A,et al.Heterogeneous catalysis in the Fenton-type system FeZSM-5/H2O2[J].Applied Catalysis B Environmental,2004,51(3):165-170.
[4]HERMANEK M,ZBORIL R,MEDRIK I,et al.Catalytic efficiency of iron(Ⅲ)oxides in decomposition of hydrogen peroxide:?competition between the surface area and crystallinity of nanoparticles[J].Journal of the American Chemical Society,2007,129(35):10929-10936.
[5]POURAN S R,AZIZ A,WAN M,et al.Estimation of the effect of catalyst physical characteristics on Fenton-like oxidation efficiency using adaptive neuro-fuzzy computing technique[J].Measurement,2015,59:314-328.
[6]HE J,MA W,HE J,et al.Photooxidation of azo dye in aqueous dispersions of H2O2/α-FeOOH[J].Applied Catalysis BEnvironmental,2002,39(3):211-220.
[7]ZHONG X,ROYER S,ZHANG H,et al.Mesoporous silica irondoped as stable and efficient heterogeneous catalyst for the degradation of C.I.Acid Orange 7 using sono-photo-Fenton process[J].Separation&Purification Technology,2011,80(1):163-171.
[8]YANG X J,XU X M,XU J,et al.Iron oxychloride(Fe OCl):an efficient Fenton-like catalyst for producing hydroxyl radicals in degradation of organic contaminants[J].Journal of the American Chemical Society,2013,135:16058-16061.
[9]YANG X J,TIAN P F,ZHANG X M,et al.The generation of hydroxyl radicals by hydrogen peroxide decomposition on FeOCl/SBA-15catalysts for phenol degradation[J].AIChE Journal,2015,61:166-176.
[10]BOKARE A D,CHOI W.Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes[J].Journal of Hazardous Materials,2014,275:121-135.
[11]ZHANG L,XU D,HU C,et al.Framework Cu-doped Al PO4 as an effective Fenton-like catalyst for bisphenol A degradation[J].Applied Catalysis B:Environmental,2017,207:9-16.
[12]GRANATO T,KATOVIC A,VALKAJ K M,et al.Cu-silicalite-1catalyst for the wet hydrogen peroxide oxidation of phenol[J].Journal of Porous Materials,2009,16(2):227-232.
[13]GUZMAN-VARGAS A,DE LA ROSA-PINEDA J E,OLIVER-TOLENTINO M A,et al.Stability of Cu species and zeolite structure on ecological heterogeneous Fenton discoloration-degradation of yellow 5 dye:efficiency on reusable Cu-Y catalysts[J].Environmental Progress&Sustainable Energy,2015,34(4):990-998.
[14]PAN W,ZHANG G,ZHENG T,et al.Degradation of p-nitrophenol using CuO/Al2O3 as a Fenton-like catalyst under microwave irradiation[J].RSC Advances,2015,5(34):27043-27051.
[15]SUBBARAMAIAH V,SRIVASTAVA V C,MALL I D.Catalytic activity of Cu/SBA-15 for peroxidation of pyridine bearing wastewater at atmospheric condition[J].AIChE Journal,2013,59(7):2577-2586.
[16]TARAN O P,ZAGORUIKO A N,AYUSHEEV A B,et al.Wet peroxide oxidation of phenol over Cu-ZSM-5 catalyst in a flow reactor.Kinetics and diffusion study[J].Chemical Engineering Journal,2015,282:108-115.
[17]BJ?RKBACKA?,YANG M,GASPARRINI C,et al.Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides[J].Dalton Transactions,2015,44(36):16045-16051.
[18]LYU L,ZHANG L,HU C.Enhanced Fenton-like degradation of pharmaceuticals over framework copper species in copper-doped mesoporous silica microspheres[J].Chemical Engineering Journal,2015,274:298-306.
[19]LYU L,ZHANG L,HU C,et al.Enhanced Fenton-catalytic efficiency by highly accessible active sites on dandelion-like copper-aluminumsilica nanospheres for water purification[J].Journal of Materials Chemistry A,2016,4(22):8610-8619.
[20]LYU L,ZHANG L,WANG Q,et al.Enhanced Fenton catalytic efficiency ofγ-Cu-Al2O3 byσ-Cu2+-ligand complexes from aromatic pollutant degradation[J].Environmental Science&Technology,2015,49(14):8639-8647.
[21]WANG H,ZHANG L,HU C,et al.Enhanced degradation of organic pollutants over Cu-doped La AlO3 perovskite through heterogeneous Fenton-like reactions[J].Chemical Engineering Journal,2018,332:572-581.
[22]ZHANG Y,LIU C,XU B,et al.Degradation of benzotriazole by a novel Fenton-like reaction with mesoporous Cu/MnO2:combination of adsorption and catalysis oxidation[J].Applied Catalysis B:Environmental,2016,199:447-457.
[23]SHENG Y Y,SUN Y,XU J,et al.Fenton-like degradation of rhodamine B over highly durable Cu-embedded alumina:kinetics and mechanism[J].AIChE Journal,2018,64:538-549.
[24]ZHANG X,DING Y,TANG H,et al.Degradation of bisphenol A by hydrogen peroxide activated with CuFeO2 microparticles as a heterogeneous Fenton-like catalyst:efficiency,stability and mechanism[J].Chemical Engineering Journal,2014,236:251-262.
[25]LAI L,ZHANG L,HU C,et al.Enhanced Fenton-catalytic efficiency by highly accessible active sites on dandelion-like copper-aluminumsilica nanospheres for water purification[J].Journal of Materials Chemistry A,2016,4(22):8610-8619.
[26]FU L,LI X,LIU M,et al.Insights into the nature of Cu doping in amorphous mesoporous alumina[J].Journal of Materials Chemistry A,2013,1(46):14592-14605.
[27]EISENBERG G.Colorimetric determination of hydrogen peroxide[J].Industrial&Engineering Chemistry Analytical Edition,1943,15(5):327-328.
[28]LINDSEY M E,TARR M A.Quantitation of hydroxyl radical during Fenton oxidation following a single addition of iron and peroxide[J].Chemosphere,2000,41(3):409-417.
[29]JENSEN M C R,VENKATARAMANI K,HELVEG S,et al.Morphology,dispersion,and stability of Cu nanoclusters on clean and hydroxylatedα-Al2O3(0001)substrates[J].The Journal of Physical Chemistry C,2008,112(43):16953-16960.
[30]TIAN P F,OUYANG L K,XU X Y,et al.The origin of palladium particle size effects in the direct synthesis of H2O2:is smaller better?[J].Journal of Catalysis,2017,349:30-40.
[31]张国臣.过氧化氢生产技术[M].北京:化学工业出版社,2012:54-72.ZHANG G C.Production Technology of H2O2[M].Beijing:Chemical Industry Press,2012:54-72.
[32]GOOR G,GLENNEBERG J,JACOBI S.Hydrogen Peroxide[M].Weinheim:Wiley-VCH Verlag GmbH&Co.KGaA,2007:396-397
[33]YANG X J,XU X M,XU X C,et al.Modeling and kinetics study of Bisphenol A(BPA)degradation over an FeOCl/SiO2 Fenton-like catalyst[J].Catalysis Today,2016,276:85-96.
[34]ARSLAN-ALATON I,TURELI G,OLMEZ-HANCI T.Treatment of azo dye production wastewaters using photo-Fenton-like advanced oxidation processes:optimization by response surface methodology[J].Journal of Photochemistry and Photobiology A:Chemistry,2009,202(2):142-153.
[35]WU Y,ZHOU S,QIN F,et al.Modeling physical and oxidative removal properties of Fenton process for treatment of landfill leachate using response surface methodology(RSM)[J].Journal of Hazardous Materials,2010,180(1):456-465.
[36]MITSIKA E E,CHRISTOPHORIDIS C,FYTIANOS K.Fenton and Fenton-like oxidation of pesticide acetamiprid in water samples:kinetic study of the degradation and optimization using response surface methodology[J].Chemosphere,2013,93(9):1818-1825.
[37]CRUZ-GONZáLEZ K,TORRES-LóPEZ O,GARCíA-LEóN A,et al.Determination of optimum operating parameters for acid yellow36 decolorization by electro-Fenton process using BDD cathode[J].Chemical Engineering Journal,2010,160(1):199-206.
[38]LI H,GONG Y,HUANG Q,et al.Degradation of orange II by UV-assisted advanced Fenton process:response surface approach,degradation pathway,and biodegradability[J].Industrial&Engineering Chemistry Research,2013,52(44):15560-15567.
[39]ZHU X,TIAN J,LIU R,et al.Optimization of Fenton and electroFenton oxidation of biologically treated coking wastewater using response surface methodology[J].Separation and Purification Technology,2011,81(3):444-450.
[40]王欣,王金翠,殷晓梅,等.乙酰甲胺磷UV-TiO2/类Fenton光催化降解过程的响应面法优化[J].应用化工,2013,42(1):33-40.WANG X,WANG J C,YIN X M,et al.Optimization of photocatalytic degradation of acephate by UV-TiO2/Fenton-like process using response surface methodology[J].Applied Chemical Industry,2013,42(1):33-40.
[41]ZHANG P,YUAN S,LIAO P.Mechanisms of hydroxyl radical production from abiotic oxidation of pyrite under acidic conditions[J].Geochimicaet Cosmochimica Acta,2016,172:444-457.
[42]HE J,YANG X,MEN B,et al.Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials:a review[J].Journal of Environmental Sciences,2016,39:97-109.