徐思遥,李森,彭东辉,张雪洪

• 1:上海化工研究院有限公司
• 2:聚烯烃催化技术与高性能材料国家重点实验室
• 3:上海市聚烯烃催化技术重点实验室

摘要(Abstract)：

采用共沉淀法制备了系列MxCu1.5-xCo6-O复合氧化物催化剂(M=Ce,La;x=0.3～0.7)。借助N2吸脱附实验、X射线衍射(XRD)、扫描电子显微镜(SEM)、H2程序升温还原(H2-TPR)、O2程序升温脱附(O2-TPD)和X射线光电子能谱(XPS)对催化剂进行表征,并在反应体积空速15000 h-1,氧气体积分数10%,150～275℃温度范围内,以体积分数0.18%正庚烷为降解底物,于固定床连续反应器-气相色谱在线检测装置上考察了催化剂对正庚烷的催化燃烧降解活性。结果显示,适量Ce、La的添加能提高催化剂比表面积、氧化还原性能及吸附氧能力,进而提高催化剂的活性。其中Ce0.5Cu1Co6-O与La0.7Cu0.8Co6-O相对催化活性最优,正庚烷转化率达90%时的最低转化温度分别为180.80和184.73℃,相比于未改性Cu-Co催化剂分别降低15和10℃。稳定性考察结果表明,Ce0.5Cu1Co6-O与La0.7Cu0.8Co6-O具有一定的稳定性。

关键词(KeyWords)： 催化燃烧;正庚烷;铜-钴复合氧化物;铈;镧

Abstract:

Keywords:

基金项目(Foundation): 上海市自然科学基金(17ZR1413200);; 上海化工研究院有限公司自筹项目(N312-2017jszx-02)

作者(Author): 徐思遥,李森,彭东辉,张雪洪

参考文献(References)：

• [1]Kamal M S,Razzak S A,H M M.Catalytic oxidation of volatile organic compounds(VOCs)-a review[J].Atmospheric Environment,2016,140:117-134.
• [2]Carier W P L,Atkinson R.Atmospheric chemistry of alkanes[J].Journal of Atmospheric Chemistry,1985,3(3):377-405.
• [3]Kolade M A,Kogelbauer A,Alpay E.Adsorptive reactor technology for VOC abatement[J].Chemical Engineering Science,2009,64(6):1167-1177.
• [4]Zhou G,He X,Liu S,et al.Phenyl VOCs catalytic combustion on supported CoMn/AC oxide catalyst[J].Journal of Industrial and Engineering Chemistry,2015,21(1):932-941.
• [5]Bastos S S T,Carabineiro S A C,órf O J J M,et al.Total oxidation of ethyl acetate,ethanol and toluene catalyzed by exotemplated manganese and cerium oxides loaded with gold[J].Catalysis Today,2012,180(1):148-154.
• [6]Sp;spma B,Garcia T,Aul N E,et al.Promoting the activity and selectivity of high surface area Ni-Ce-O mixed oxides by gold deposition for VOC catalytic combustion[J].Chemical Engineering Journal,2011,175(1):271-278.
• [7]Kamiuchi N,Mitsui T,Yamaguchi N,et al.Activation of Pt/SnO2 catalyst for catalytic oxidation of volatile organic compounds[J].Catalysis Today,2010,157(1-4):415-419.
• [8]Lan H,Zhou G,Luo C,et al.High Efficiency CeCu composite oxide catalysts improved via preparation methods for propyl acetate catalytic combustion in air[J].International Journal of Chemical Reactor Engineering,2016,14(3):757-768.
• [9]Li X,Wang J,Liao C,et al.Catalytic combustion of ethyl acetate over CeMnOx and CeMnZrOx compounds synthesized by coprecipitation method[J].Journal of Energy Chemistry,2011,20(6):623-628.
• [10]He C,Xu B T,Shi J W,et al.Catalytic destruction of chlorobenzene over mesoporous ACeOx(A=Co,Cu,Fe,Mn or Zr)composites prepared by inorganic metal precursor spontaneous precipitation[J].Fuel Processing Technology,2015,130(1):179-187.
• [11]Tsoncheva T,Ivanova L,Rosnholm J,et al.Cobalt oxide species supported on SBA-15,KIT-5 and KIT-6 mesoporous silicas for ethyl acetate total oxidation[J].Applied Catalysis B Environmental,2009,89(3-4):365-374.
• [12]Rubio-Marcos F,Calvino-Casilda V,Ba ares M A,et al.Control of the interphases formation degree in Co3O4/ZnO catalysts[J].ChemCatChem,2013,5(6):1431-1440.
• [13]Wang C A,Li S,An L.Hierarchically porous Co3O4 hollow spheres with tunable pore structure and enhanced catalytic activity[J].Chemical communications,2013,49(67):7427-7429.
• [14]Wang C,Zhang C,Hua W,et al.Catalytic oxidation of vinyl chloride emissions over Co-Ce composite oxide catalysts[J].Chemical Engineering Journal,2017,315:392-402.
• [15]Carabineiro S A C,Chen X,Konsolakis M,et al.Catalytic oxidation of toluene on Ce-Co and La-Co mixed oxides synthesized by exotemplating and evaporation methods[J].Catalysis Today,2015,244:161-171.
• [16]Jia A P,Hu G S,Meng L,et al.CO oxidation over CuO/Ce1-xCuxO2-δand Ce1-xCuxO2-δcatalysts:synergetic effects and kinetic study[J].Journal of Catalysis,2012,289:199-209.
• [17]Mcfarland E W,Metiu H.Catalysis by doped oxides[J].Chemical Reviews,2013,113(6):4391-4427.
• [18]Metiu H,Chrtien S,Hu Z,et al.Chemistry of lewis acid-base pairs on oxide surfaces[J].The Journal of Physical Chemistry C,2012,116(19):10439-10450.
• [19]Hu Z,Li B,Sun X Y,et al.Chemistry of doped oxides:the activation of surface oxygen and the chemical compensation effect[J].The Journal of Physical Chemistry C,2011,115(7):3065-3074.
• [20]Delimaris D,Ioannides T.Voc oxidation over CuO-CeO2 catalysts prepared by a combustion method[J].Applied Catalysis B:Environmental,2009,89(1-2):295-302.
• [21]QIAN Ying(钱颖),MENG Ming(孟明),LUO Jin-yong(罗金勇),et al.Preparation,structures and properties of La-Co-Ce-Ocomplex oxides(La-Co-Ce-O复合氧化物催化剂的制备、结构与性能)[J].Journal of Molecular Catalysis(分子催化),2005,19(5):321-326.
• [22]Tan X,Lan H,Xie H,et al.Role of surface oxygen species of mesoporous CeCu oxide catalyst in OVOCs catalytic combustion[J].Journal of Environmental Chemical Engineering,2017,5(2):2068-2076.
• [23]He C,Yu Y,Chen C,et al.Facile preparation of 3D ordered mesoporous CuOx-CeO2 with notably enhanced efficiency for the low temperature oxidation of heteroatom-containing volatile organic compounds[J].RSC Advances,2013,3(42):19639-19656.
• [24]Luo J,Meng M,Li X,et al.Mesoporous Co3O4-CeO2 and Pd/Co3O4-CeO2 catalysts:Synthesis,characterization and mechanistic study of their catalytic properties for low-temperature CO oxidation[J].Journal of Catalysis,2008,254(2):310-324.
• [25]Tang C W,Wang C B,Chien S H.Characterization of cobalt oxides studied by FT-IR,Raman,TPR and TG-MS[J].Thermochimica Acta,2008,473(1-2):68-73.
• [26]Gao J,Guo J,Liang D,et al.Production of syngas via autothermal reforming of methane in a fluidized-bed reactor over the combined CeO2-ZrO2/SiO2 supported Ni catalysts[J].International Journal of Hydrogen Energy,2008,33(20):5493-5500.
• [27]Megarajan S K,Rayalu S,Teraoka Y,et al.High NO oxidation catalytic activity on non-noble metal based cobalt-ceria catalyst for diesel soot oxidation[J].Journal of Molecular Catalysis A Chemical,2014,385(4):112-118.
• [28]Michalis K,Zisis I.Surface/structure functionalization of Copper-based catalysts by metal-support and/or metal-metal interactions[J].Applied Surface Science,2014,320:244-255
• [29]Huang H,Dai Q,Wang X.Morphology effect of Ru/CeO2 catalysts for the catalytic combustion of chlorobenzene[J].Applied Catalysis B Environmental,2014,158-159(3):96-105.
• [30]Rivas B D,Lapez-Fonseca R,Jimenez-Gonzalez C,et al.Synthesis,characterisation and catalytic performance of nanocrystalline Co3O4 for gas-phase chlorinated VOC abatement[J].Journal of Catalysis,2011,281(1):88-97.
• [31]Solsona B,V Zquez I,Garcia T,et al.Complete oxidation of short chain alkanes using a nanocrystalline cobalt oxide catalyst[J].Catalysis Letters,2007,116(3-4):116-121.
• [32]Cai T,Huang H,Deng W,et al.Catalytic combustion of 1,2-dichlorobenzene at low temperature over Mn-modified Co3O4 catalysts[J].Applied Catalysis B:Environmental,2015,166-167:393-405.