Ce_xMn_(1-x)O_2复合氧化物的制备及催化湿式氧化降解高浓度有机酸的应用
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摘要
利用水热法制备CeO_2和一系列不同Ce/Mn原子比的Ce_xMn_(1-x)O_2复合氧化物的纳米球,对其进行XRD、XPS、SEM、H_2-TPR和N_2吸附-脱附的表征,并通过催化湿式氧化降解丁酸对催化活性进行测试,结果表明Ce_(0.2)Mn_(0.8)O_2对丁酸的降解呈现出优异的催化性能.该催化剂对高浓度的醋酸、丁酸以及两者混合酸的降解也具有高的催化活性,在185℃、0.9 MPa O_2条件下反应2 h,醋酸、丁酸以及两者混合酸COD(化学需氧量)的去除率分别高达89.8%、99.5%和99.4%.最后,对该催化剂催化湿式氧化降解丁酸、醋酸以及丁酸和醋酸的混合酸进行了动力学和稳定性方面的研究.
CeO_2 nanospheres and Ce_xMn_(1-x)O_2 nanospheres were prepared by PVP-assisted hydrothermal method and characterized by SEM, XPS, XRD, H_2-TPR and N_2 absorption-desorption. The catalytic wet air oxidation( CWAO) behavior of high concentration organic acids,including acetic acid,butyric acid and the mixture of acetic acid and butyric acid,is tested over the Ce_(0.2)Mn_(0.8)O_2 nanosphere,which turns out to be an efficient catalyst for the activation and degradation of high concentration organic acids. When the reaction operated at 0.9 MPa partial pressure of O_2,185 ℃ for 2 h,the chemical oxygen demand( COD) removal can reach up to 89.8%,99.5% and 99.4% for acetic acid,butyric acid and the mixture of acetic acid and butyric acid,respectively. Noticeably,the kinetic studies of CWAO for three kinds of organic acids over the Ce_(0.2)Mn_(0.8)O_2 reveal that the degradation of sole acid is easier than that of mixture acid. In addition,the Ce_(0.2)Mn_(0.8)O_2 oxides perform a good reusability during the cycle experiment even after six cycles.
CeO_2 nanospheres and Ce_xMn_(1-x)O_2 nanospheres were prepared by PVP-assisted hydrothermal method and characterized by SEM, XPS, XRD, H_2-TPR and N_2 absorption-desorption. The catalytic wet air oxidation( CWAO) behavior of high concentration organic acids,including acetic acid,butyric acid and the mixture of acetic acid and butyric acid,is tested over the Ce_(0.2)Mn_(0.8)O_2 nanosphere,which turns out to be an efficient catalyst for the activation and degradation of high concentration organic acids. When the reaction operated at 0.9 MPa partial pressure of O_2,185 ℃ for 2 h,the chemical oxygen demand( COD) removal can reach up to 89.8%,99.5% and 99.4% for acetic acid,butyric acid and the mixture of acetic acid and butyric acid,respectively. Noticeably,the kinetic studies of CWAO for three kinds of organic acids over the Ce_(0.2)Mn_(0.8)O_2 reveal that the degradation of sole acid is easier than that of mixture acid. In addition,the Ce_(0.2)Mn_(0.8)O_2 oxides perform a good reusability during the cycle experiment even after six cycles.
引文
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[30]Liao Y N,Fu M L,Chen L M,et al.Catalytic oxidation of toluene over nanorod-structured Mn-Cemixed oxides[J].Catal Today,2013,216(6):220-228.
[31]Tang W X,Wu X F,Liu G,et al.Preparation of hierarchical layer-stacking Mn-Ce composite oxide for catalytic total oxidation of VOCs[J].J Rare Earths,2015,33(1):62-69.
[32]Yu X H,Li J M,Wei Y C,et al.Three-dimensionally ordered macroporous MnxCe1-xOδand Pt/Mn0.5Ce0.5Oδcatalysts:Synthesis and catalytic performance for soot o xidation[J].Ind Eng Chem Res,2014,53(23):9653-9664.
[33]Tang X F,Li Y G,Huang X M,et al.Mn Ox-Ce O2mixed oxide catalysts for complete oxidation of formaldehyde:Effect of preparation method and calcination temperature[J].Appl Catal B:Environ,2006,62(3/4):265-273.
[34]Yu C Y,Zhao P Q,Chen G X,et al.Al2O3supported Ru catalysts prepared by thermolysis of Ru3(CO)12for catalytic wet air oxidation[J].Appl Surf Sci,2011,257(17):7727-7731.
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[2]Wang G W,Wang D,Xu X C,et al.Wet air oxidation of pretreatment of pharmaceutical wastewater by Cu2+and[PxWmOy]q-co-catalyst system[J].J Hazard Mater,2012,217/218(4):366-373.
[3]Rodríguez A,Ovejero G,Romero M D,et al.Catalytic wet air oxidation of textile industrial wastewater using metal supported on carbon nanofibers[J].J Supercrit Fluid,2008,46(2):163-172.
[4]a.Cassano A,Conidi C,Giorno L,et al.Fractionation of olive mill wastewaters by membrane separation techniques[J].J Hazard Mater,2013,248/249(1):185-193.b.Tang Chang-cun(唐长存),Li Yong-gang(李永刚),Huang Ying-ping(黄应平),et al.Effect of Na F soaking on photocatalytic degradation of organic dye Rh B over Bi OBr samples Na F(浸泡处理对Bi OBr光催化降解有机染料罗丹明B的影响)[J].J Mol Catal(China)(分子催化),2017,31(2):169-180.c.Lu Guang(陆光),Zhang Shuang(张爽),Lun Zishuai(伦子帅),et al.Effect of solvents on structural performance and photocatalytic degradation of Rh B over Bi OBr samples(溶剂对Bi OBr结构和光催化降解Rh B的影响)[J].J Mol Catal(China)(分子催化),2016,30(4):383-390.
[5]Song Jin-fu(宋敬伏),Yu Chao-ying(于超英),Zhao Pei-qing(赵培庆),et al.Research progress of catalytic wet air oxidation(湿式催化氧化技术研究进展)[J].J Mol Catal(China)(分子催化),2010,24(5):474-482.
[6]Bhargava S K,Tardio J,Prasad J,et al.Wet oxidation and catalytic wet oxidation[J].Ind Eng Chem Res,2006,45(4):1221-1258.
[7]Liu Jie(刘杰),Yu Chao-ying(于超英),Zhao Pei-qing(赵培庆),et al.Degradation ofβ-Naphthol by catalytic wet air oxidation(催化湿式氧化法降解水中的β-萘酚)[J].Environ Sci(环境科学),2012,33(11):3826-3832.
[8]Li N,Descorme C,Besson M.Catalytic wet air oxidation of2-chlorophenol over Ru loaded CexZr1-xO2solid solutions[J].Appl Catal B:Environ,2007,76(1/2):92-100.
[9]Gao P,Li N,Wang A Q,et al.Perovskite La Mn O3hollow nanospheres:the synthesis and the application in catalytic wet air oxidation of phenol[J].Mater Lett,2013,92(1):173-176.
[10]Garcia J,Gomes H T,Serp Ph,et al.Carbon nanotube supported ruthenium catalysts for the treatment of high strength wastewater with aniline using wet air oxidation[J].Carbon,2006,44(12):2384-2391.
[11]Barbier Jr J,Oliviero L,Renard B,et al.Catalytic wet air oxidation of ammonia over M/Ce O2catalysts in the treatment of nitrogen-containing pollutants[J].Catal Today,2002,75(1):29-34.
[12]Manole C C,Julcour L C,Wilhelm A M,et al.Catalytic oxidation of 4-hydroxybenzoic acid on activated carbon in batch autoclave and fixed-bed reactors[J].Ind Eng Chem Res,2007,46(25):8388-8396.
[13]Renarda B,Barbier Jr J,Dupreza D,et al.Catalytic wet air oxidation of stearic acid on cerium oxide supported noble metal catalysts[J].Appl Catal B:Environ,2005,55(1):1-10.
[14]Besson M,Kallel A,Gallezot P,et al.Gold catalysts supported on titanium oxide for catalytic wet air oxidation of succinic acid[J].Catal Commun,2003,4(9):471-476.
[15]Gomes H T,Figueiredo J L,Faria J L,et al.Carbonsupported iridium catalysts in the catalytic wet air oxidation of carboxylic acids:kinetics and mechanistic interpretation[J].J Mol Catal A:Chem,2002,182/183(1):47-60.
[16]DükancM,Gündüz G.Catalytic wet air oxidation of butyric acid and maleic acid solutions over noble metal catalysts prepared on Ti O2[J].Catal Commun,2009,10(6):913-919.
[17]MikulováJ,Barbier Jr J,Rossignol S,et al.Wet air o xidation of acetic acid over platinum catalysts supported on cerium-based materials:Influence of metal and oxide crystallite size[J].J Catal,2007,251(1):172-181.
[18]Gomes H T,Figueiredo J L,Faria J L.Catalytic wet air oxidation of low molecular weight carboxylic acids using a carbon supported platinum catalyst[J].Appl Catal B:Environ,2000,27(4):L217-L223.
[19]GaálováJ,Barbier Jr J,Rossignol S.Ruthenium versus platinum on cerium materials in wet air oxidation of acetic acid[J].J Hazard Mater,2010,181(1/3):633-639.
[20]Wang J B,Zhu W P,He X W,et al.Catalytic wet air oxidation of acetic acid over different ruthenium catalysts[J].Catal Commun,2008,9(13):2163-2167.
[21]Wang Wei(王伟),Wang Jian-bin(王建兵),Zhu Wan-peng(祝万鹏),et al.Catalytic wet air oxidation of acetic acid and phenol with Ru/Zr O2-Ce O2catalysts(Ru/Zr O2-Ce O2催化剂催化湿式氧化乙酸和苯酚的研究)[J].J Mol Catal(China)(分子催化),2007,21(5):401-405.
[22]Imamura S,Hlrano A,Kawabata N.Wet oxidation of acetic acid catalyzed by Co-Bi complex oxides[J].Ind Enp Chem Prd Res Dev,1982,21(4):570-575.
[23]Jiang Zhan-peng(蒋展鹏),Fu Hong-xiang(付宏祥),Tan Ya-jun(谭亚军).The catalytic wet air oxidation reaction of acetic acid with Ti-Ce series catalyst(Ti-Ce系列催化剂上乙酸的催化湿式氧化反应)[J].Environ Sci(环境科学),2002,23(1):54-57.
[24]Leitenburg C,Goi D,Primavera A,et al.Wet oxidation of acetic acid catalyzed by doped ceria[J].Appl Catal B:Environ,1996,11(1):L29-L35.
[25]Murugan B,Ramaswamy A V.Nature of manganese species in Ce1-xMnxO2-δsolid solutions synthesized by the solution combustion route[J].Chem Mater,2005,17(15):3983-3993.
[26]Mousavi S M,Niaei A,Gómez M J I,et al.Characterization and activity of alkaline earth metals loaded Ce O2-MOx(M=Mn,Fe)mixed oxides in catalytic reduction of NO[J].Mater Chem Phys,2014,143(3):921-928.
[27]Chen Y T,Zheng H J,Guo Z,et al.Pd catalysts supported on Mn Ce Oxmixed oxides and their catalytic application in solvent-free aerobic oxidation of benzyl alcohol:Support composition and structure sensitivity[J].J Catal,2011,283(1):34-44.
[28]Ma Z W,Zhao S L,Pei X P,et al.New insights into the support morphology dependent ammonia synthesis activity of Ru/Ce O2catalysts[J].Catal Sci Technol,2017,7(1):191-199.
[29]Yu D Q,Liu Y,Wu Z B.Low-temperature catalytic oxidation of toluene over mesoporous Mn Ox-Ce O2/Ti O2prepared by sol-gel method[J].Catal Commun,2010,11(8):788-791.
[30]Liao Y N,Fu M L,Chen L M,et al.Catalytic oxidation of toluene over nanorod-structured Mn-Cemixed oxides[J].Catal Today,2013,216(6):220-228.
[31]Tang W X,Wu X F,Liu G,et al.Preparation of hierarchical layer-stacking Mn-Ce composite oxide for catalytic total oxidation of VOCs[J].J Rare Earths,2015,33(1):62-69.
[32]Yu X H,Li J M,Wei Y C,et al.Three-dimensionally ordered macroporous MnxCe1-xOδand Pt/Mn0.5Ce0.5Oδcatalysts:Synthesis and catalytic performance for soot o xidation[J].Ind Eng Chem Res,2014,53(23):9653-9664.
[33]Tang X F,Li Y G,Huang X M,et al.Mn Ox-Ce O2mixed oxide catalysts for complete oxidation of formaldehyde:Effect of preparation method and calcination temperature[J].Appl Catal B:Environ,2006,62(3/4):265-273.
[34]Yu C Y,Zhao P Q,Chen G X,et al.Al2O3supported Ru catalysts prepared by thermolysis of Ru3(CO)12for catalytic wet air oxidation[J].Appl Surf Sci,2011,257(17):7727-7731.
[35]Wang Y M,Yu C Y,Meng X,et al.The ethanol mediated-Ce O2-supported low loading ruthenium catalysts for the catalytic wet air oxidation of butyric acid[J].RSC Adv,2017,7(63):39796-39802.