催化湿式氧化丙烯酸废水Ru/La_xCe_(1-x)O_δ催化剂的制备与表征
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摘要
采用燃烧法制备了不同含量La掺杂的CeO_2载体,并采用等体积浸渍法将Ru负载于载体上,得到了一系列Ru/La_xCe_(1-x)O_δ催化剂。采用X-射线衍射(XRD)、N2物理吸脱附以及拉曼光谱(Raman)、扫描电子显微镜(SEM)、ICP等表征手段分析了催化剂的结构组成与表面性质,并研究了其催化湿式氧化丙烯酸废水的性能。结果表明:Ru/La_(0.2)Ce_(0.8)O_δ催化剂具有优异的催化湿式氧化降解丙烯酸活性,在260℃、P(O_2)=7 MPa、催化剂用量为4g/L时,反应30min后废水CODCr去除率可达96%,TOC转化率为93%,并且催化剂重复利用10次后仍然保持良好的活性和稳定性。这与催化剂大比表面积、高分散Ru纳米颗粒以及氧缺位数量有着密切的关系。
La doped CeO_2 support with different La contents La_xCe_(1-x)O_δ were prepared via combustion method,and then a series of Ru loaded catalysts were obtained by incipient wetness impregnation method.The structure and surface properties of catalysts were characterized by various techniques,including X-ray diffraction,N_2 adsorption-desorption,SEM,Raman and ICP.The results showed that the catalyst Ru/La_(0.2)Ce_(0.8)O_δ had good catalytic activity and stability for wet oxidation of waste water from acrylic acid production plant.At 260℃,and 7 MPa of pure oxygen,the amount of catalyst was 1 g/L,reaction time for30 minutes,the COD of the waste water could be removed up to 96%,the TOC conversion rate was 93%,the activity still maintained even after 10 cycles.The high surface area highly-dispersed Ru nanoparticles and the amounts of oxygen vacancy generatednin reaction were responsible for the good catalytic performance of Ru/La_(0.2)Ce_(0.8)O_δ catalyst.
La doped CeO_2 support with different La contents La_xCe_(1-x)O_δ were prepared via combustion method,and then a series of Ru loaded catalysts were obtained by incipient wetness impregnation method.The structure and surface properties of catalysts were characterized by various techniques,including X-ray diffraction,N_2 adsorption-desorption,SEM,Raman and ICP.The results showed that the catalyst Ru/La_(0.2)Ce_(0.8)O_δ had good catalytic activity and stability for wet oxidation of waste water from acrylic acid production plant.At 260℃,and 7 MPa of pure oxygen,the amount of catalyst was 1 g/L,reaction time for30 minutes,the COD of the waste water could be removed up to 96%,the TOC conversion rate was 93%,the activity still maintained even after 10 cycles.The high surface area highly-dispersed Ru nanoparticles and the amounts of oxygen vacancy generatednin reaction were responsible for the good catalytic performance of Ru/La_(0.2)Ce_(0.8)O_δ catalyst.
引文
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[3]王子丹,Hameeds S,张诺伟,等.PdNi/C低温高效催化湿式氧化无害化处理氨氮废水[J].厦门大学学报,2018,57(1):32-37.DOI:10.6043/j.issn.0438-0479.201703025.
[4] Dietrich M J.Wet Air Oxidation of Hazardous Organics in Wastewater[J].Environ Prog,1985,4(3):171-177.DOI:10.1002/ep.670040312.
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[7] Pintar A,Besson M,Gallezot P.Catalytic Wet Air Oxidation of Kraft Bleaching Plant Effluents in the Presence of Titania and Zirconia Supported Ruthenium[J].Appl Catal B:Environ,2001,30(1-2):123-139.DOI:10.1016/S0926-3373(00)00228-9.
[8]王建兵,祝万鹏,王伟,等.催化剂Ru/ZrO2-CeO2催化湿式氧化苯酚[J].环境科学,2007,28(7):1460-1465.DOI:10.3321/j.issn:0250-3301.2007.07.009.
[9]杜鸿章,房廉清,江义,等.难降解高浓度有机废水催化湿式氧化净化技术Ⅰ.高活性、高稳定性的湿式氧化催化剂的研制[J].水处理技术,1997,23(2):83-87.DOI:10.16796/j.cnki.1000-3770.1997.02.005.
[10] Perret N,Wang X,Delgado J J,et al,Selective Hydrogenation of Benzoic Acid over Au Supported on CeO2and Ce0.62Zr0.38O2:Formation of Benzyl Alcohol[J].J Catal,2014,317:114-125.DOI:10.1016/j.jcat.2014.06.010.
[11] Bueno-López A,Such-Bas1ez I,de Lecea C S.Stabilization of Active Rh2O3Species for Catalytic Decomposition of N2O on La-,Pr-doped CeO2[J].J Catal,2006,244(1):102.DOI:10.1016/j.jcat.2006.08.021.
[12] Ndifor E N,Garcia T,Solsona B,et al.Influence of Preparation Conditions of Nano-crystalline Ceria Catalysts on the Total Oxidation of Naphthalene,a Model Polycyclic Aromatic Hydrocarbon[J].Appl Catal B,2007,76(3):248.DOI:10.1016/j.apcatb.2007.05.027.
[13] Anjaneya K C,Nayaka G P,Manjanna J,et al.Studies on Structural,Morphological and Electrical Properties of Ce0.8Ln0.2O2-(Ln=Y3+,Gd3+,Sm3+,Nd3+and La3+)Solid Solutions Prepared by Citrate Complexation Method[J].J Alloys Compd,2014,585:594.DOI:10.1016/j.jallcom.2013.09.101.
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[17]杨少霞,冯玉杰,蔡伟民,等.负载型湿式氧化催化剂RuO2/-Al2O3活性与稳定性[J].化工学报,2003,54(9):1240-1245.DOI:10.3321/j.issn:0438-1157.2003.09.012.
[18]杨少霞,冯玉杰,万家峰,等.CeO2掺杂RuO2/γ-Al2O3催化剂结构与湿式氧化降解苯酚的活性研究[J].高等学校化学学报,2005,26(5):897-901.DOI:10.3321/j.issn:0251-0790.2005.05.016.