N_2O在Mg-Co和Mg-Mn-Co复合氧化物上的催化分解
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摘要
用溶胶-凝胶法制备了不同组成的Mg-Co和Mg-Mn-Co复合氧化物,用于催化分解N_2O。在较高活性的Mg-Mn-Co表面浸渍K_2CO_3溶液,制备K改性催化剂。用X射线衍射(XRD)、N_2物理吸附(BET)、扫描电镜(SEM)、H_2程序升温还原(H_2-TPR)、O_2程序升温脱附(O_2-TPD)等技术表征催化剂结构,考察了复合氧化物的组成、K负载量等制备参数对催化剂活性的影响。结果表明,加入助剂K显著提高了催化剂活性,其中,0.02 K/MgMn_(0.2)Co_(1.8)O_4活性较高,有氧无水、有氧有水气氛400℃连续反应50 h,N_2O转化率分别保持97%和60%。有水-无水气氛交替实验表明,有水反应后再进行无水实验,K改性催化剂的稳定性较好。
Mg-Co and Mg-Mn-Co composite oxides with different compositions were prepared by sol-gel method for N_2O catalytic decomposition in the presence of oxygen. Of Mg-Mn-Co catalysts,the one with higher activity was impregnated by K2CO_3 solution to make K-modified catalyst. These catalysts were characterized by X-ray diffraction( XRD),nitrogen physisorption( BET),scanning electron microscopy( SEM),temperatureprogrammed reduction of hydrogen( H_2-TPR),and temperature-programmed desorption of oxygen( O_2-TPD).The effect of preparation parameters such as compositions and potassium loadings on their catalytic activity has been investigated. The results show that K-modified catalysts exhibit better activity and higher resistance tow ards water in contrast to un-modified catalyst due to the weakness of surface metal-oxygen bonds. Among these catalysts,0.02 K/Mg Mn_(0.2)Co_(1.8)O_4 is the most active,over which 97% and 60% conversions of N_2O can be reached at 400 ℃ after continuous running for 50 h under the atmosphere of oxygen-alone and oxygen-steam together,respectively. When the steam is sw itched off,the catalytic activity of 0.02 K/MgMn_(0.2)Co_(1.8)O_4 can be restored to large extent,indicating the good water-resistance of K-modified catalyst.
Mg-Co and Mg-Mn-Co composite oxides with different compositions were prepared by sol-gel method for N_2O catalytic decomposition in the presence of oxygen. Of Mg-Mn-Co catalysts,the one with higher activity was impregnated by K2CO_3 solution to make K-modified catalyst. These catalysts were characterized by X-ray diffraction( XRD),nitrogen physisorption( BET),scanning electron microscopy( SEM),temperatureprogrammed reduction of hydrogen( H_2-TPR),and temperature-programmed desorption of oxygen( O_2-TPD).The effect of preparation parameters such as compositions and potassium loadings on their catalytic activity has been investigated. The results show that K-modified catalysts exhibit better activity and higher resistance tow ards water in contrast to un-modified catalyst due to the weakness of surface metal-oxygen bonds. Among these catalysts,0.02 K/Mg Mn_(0.2)Co_(1.8)O_4 is the most active,over which 97% and 60% conversions of N_2O can be reached at 400 ℃ after continuous running for 50 h under the atmosphere of oxygen-alone and oxygen-steam together,respectively. When the steam is sw itched off,the catalytic activity of 0.02 K/MgMn_(0.2)Co_(1.8)O_4 can be restored to large extent,indicating the good water-resistance of K-modified catalyst.
引文
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[25]PRRUTKO L V,CHERNYAVSKY V S,STAROKON E V,IVANOV A A,KHARITONOV A S,PANOV G.The role of a-sites in N2Odecomposition over FeZ SM-5.Comparison w ith the oxidation of benzene to phenol[J].Appl Catal B:Environ,2009,91(1/2):174-179.
[26]吴藏藏,张海杰,王建,郑丽,徐秀峰.N2O分解催化剂Co-Al尖晶石型复合氧化物制备参数的优化[J].分子催化,2016,30(1):62-71.(WU Cang-cang,ZHANG Hai-jie,WANG Jian,ZHENG Li,XU Xiu-feng.The preparation parameters screening of Co-Al spinel oxides for N2O catalytic decomposition[J].J M ol Catal(China),2016,30(1):62-71.)
[27]AMROUSSE R,TSUTSUMI A,BACHAR A,LAHCENE D.N2O catalytic decomposition over nano-sized particles of Co-substituted Fe3O4substrates[J].Appl Catal A:Gen,2013,450:253-260.
[28]FRANKEN T,PALKOVITS R.Investigation of potassium doped mixed spinels CuxCo3-xO4as catalysts for an efficient N2O decomposition in real reaction conditions[J].Appl Catal B:Environ,2015,176-177:298-305.
[2]ASANO K,OHNISHI C,IWAMOTO S,SHIOYA Y,INOUE M.Potassium-doped Co3O4catalyst for direct decomposition of N2O[J].Appl Catal B:Environ,2008,78(3/4):242-249.
[3]XUE L,ZHANG C B,HE H,TERAOKA Y.Promotion effect of residual K on the decomposition of N2O over cobalt-cerium mixed oxide catalyst[J].Catal Today,2007,126(3/4):449-455.
[4]HUSSAIN M,FINO D,RUSSO N.N2O decomposition by mesoporous silica supported Rh catalysts[J].J Hazard M ater,2012,211-212:255-265.
[5]KLYUSHINA A,PACULTOVAK,KREJCOVAS,SLOWIK G,JIRATOVAK,KOVANDA F,RYCZKOWSKI J,OBALOVAL.Advantages of stainless steel sieves as support for catalytic N2O decomposition over K-doped Co3O4[J].Catal Today,2015,257(1):2-10.
[6]ZABILSKIY M,DJINOVI'C P,ERJAVEC B,DRAZI'C G,PINTAR A.Small Cu O clusters on CeO 2nanospheres as active species for catalytic N2O decomposition[J].Appl Catal B:Environ,2015,163:113-122.
[7]AMROUSSE R,KATSUMI T.Substituted ferrite MxFe1-xFe2O4(M=Mn,Zn)catalysts for N2O catalytic decomposition processes[J].Catal Commun,2012,26:194-198.
[8]KUMAR S,VINU A,SUBBRT J,BAKARDJIEVA S,RAYALU S,TERAOKA Y,LABHSETWAR N.Catalytic N2O decomposition on Pr0.8Ba0.2M n O3type perovskite catalyst for industrial emission control[J].Catal Today,2012,198(1):125-132.
[9]XUE Z W,SHEN Y S,SHEN S B,LI C L,ZHU S M.Promotional effects of Ce4+,La3+and Nd3+incorporations on catalytic performance of Cu-Fe-Oxfor decomposition of N2O[J].J Ind Eng Chem,2015,30:98-105.
[10]LIN Y,MENG T,MA Z.Catalytic decomposition of N2O over Rh Oxsupported on metal phosphates[J].J Ind Eng Chem,2015,28:138-146.
[11]DACQUIN J P,DUJARDIN C,GRANGER P.Surface reconstruction of supported Pd on LaC o O3:Consequences on the catalytic properties in the decomposition of N2O[J].J Catal,2008,253(1):37-49.
[12]BEYER H,EMMERICH J,CHATZIAPOSTOLOU K,KHLER K.Decomposition of nitrous oxide by rhodium catalysts:Effect of rhodium particle size and metal oxide support[J].Appl Catal A:Gen,2011,391(1/2):411-416.
[13]PACHATOURIDOU E,PAPISTA E,DELIMITIS A,VASILIADES M A,EFSTATHIOU A M,AMIRIDIS M D,ALEXEEV O S,BLOOMD,MAMELLOS G E,KONSOLAKIS M,ILIOPOULOU E.N2O decomposition over ceria-promoted Ir/Al2O3catalysts:The role of ceria[J].Appl Catal B:Environ,2016,187:259-268.
[14]BERRIER E,OVSITSER O,KONDRATENKO E V,SCHWIDDER M,GRUNERT W,BRUCKNER A.Temperature-dependent N2Odecomposition over Fe-ZSM-5:Identification of sites w ith different activity[J].J Catal,2007,249(1):67-78.
[15]CURDANELI P E,ZKAR S.Ruthenium(III)ion-exchanged zeolite Y as highly active and reusable catalyst in decomposition of nitrous oxide to sole nitrogen and oxygen[J].M icroporous M esoporous M ater,2014,196:51-58.
[16]MENG T,REN N,MA Z.Silicalite-1@Cu-ZSM-5 core-shell catalyst for N2O decomposition[J].J M ol Catal A:Chem,2015,404-405:233-239.
[17]YAN L,REN T,WANG X L,GAO Q,JI D,SUO J S.Excellent catalytic performance of ZnxCo1-xCo2O4spinel catalysts for the decomposition of nitrous oxide[J].Catal Commun,2003,4(10):505-509.
[18]YAN L,REN T,WANG X L,JI D,SUO J S.Catalytic decomposition of N2O over MxCo1-xCo2O4(M=Ni,Mg)spinel oxides[J].Appl Catal B:Environ,2003,45(2):85-90.
[19]ABU-ZIED B M,SOLIMAN S A,ABDELLAH S E.Pure and Ni-substituted Co3O4spinel catalysts for direct N2O decomposition[J].Chin J Catal,2014,35(7):1105-1112.
[20]MANIAK G,STELMACHOWSKI P,STANEK J J,KOTARBA A,SOJKA Z.Catalytic properties in N2O decomposition of mixed cobaltiron spinels[J].Catal Commun,2011,15(1):127-131.
[21]窦喆,张海杰,潘燕飞,徐秀峰.N2O在钾改性Cu-Co尖晶石型复合氧化物上的催化分解[J].燃料化学学报,2014,42(2):238-245.(DOU Zhe,ZHANG Hai-jie,PAN Yan-fei,XU Xiu-feng.Catalytic decomposition of N2O over potassium-modified Cu-Co spinel oxides[J].J Fuel Chem Technol,2014,42(2):238-245.)
[22]王建,窦喆,潘燕飞,徐秀峰.MnxCo3-xO4复合氧化物及改性催化剂催化分解N2O[J].分子催化,2015,29(3):246-255.(WANG Jian,DOU Zhe,PAN Yan-fei,XU Xiu-feng.MnxCo3-xO4composite oxide and modified catalyst catalytic decomposition of N2O[J].J Mol Catal(China),2015,29(3):246-255.)
[23]CHELLAM U,XU Z P,ZENG H C.Low-temperature synthesis of MgxCo1-xCo2O4spinel catalysts for N2O decomposition[J].Chem M ater,2000,12:650-658.
[24]KUBO NOVAL,FRIDRICHOVAD,WACH A,KU'S TROWSKR P,OBALOVAL,COOL P.Catalytic activity of rhodium grafted on ordered mesoporous silicamaterials modified w ith aluminum in N2O decomposition[J].Catal Today,2015,257:51-58.
[25]PRRUTKO L V,CHERNYAVSKY V S,STAROKON E V,IVANOV A A,KHARITONOV A S,PANOV G.The role of a-sites in N2Odecomposition over FeZ SM-5.Comparison w ith the oxidation of benzene to phenol[J].Appl Catal B:Environ,2009,91(1/2):174-179.
[26]吴藏藏,张海杰,王建,郑丽,徐秀峰.N2O分解催化剂Co-Al尖晶石型复合氧化物制备参数的优化[J].分子催化,2016,30(1):62-71.(WU Cang-cang,ZHANG Hai-jie,WANG Jian,ZHENG Li,XU Xiu-feng.The preparation parameters screening of Co-Al spinel oxides for N2O catalytic decomposition[J].J M ol Catal(China),2016,30(1):62-71.)
[27]AMROUSSE R,TSUTSUMI A,BACHAR A,LAHCENE D.N2O catalytic decomposition over nano-sized particles of Co-substituted Fe3O4substrates[J].Appl Catal A:Gen,2013,450:253-260.
[28]FRANKEN T,PALKOVITS R.Investigation of potassium doped mixed spinels CuxCo3-xO4as catalysts for an efficient N2O decomposition in real reaction conditions[J].Appl Catal B:Environ,2015,176-177:298-305.