Volume 44 Issue 6
Jun.  2016
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LIU Yu-lan, ZHANG Ze-kai, NI Guang, LIU Hua-yan, CHEN Yin-fei. Performance of oxidative coupling of methane on LiMn2O4/TiO2 catalysts[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 703-709.
Citation: LIU Yu-lan, ZHANG Ze-kai, NI Guang, LIU Hua-yan, CHEN Yin-fei. Performance of oxidative coupling of methane on LiMn2O4/TiO2 catalysts[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 703-709.

Performance of oxidative coupling of methane on LiMn2O4/TiO2 catalysts

  • Received Date: 2015-12-21
  • Rev Recd Date: 2016-03-23
  • Available Online: 2021-01-23
  • Publish Date: 2016-06-10
  • A series of LiMn2O4/TiO2 catalysts with spinel crystal structure were prepared by solid state reaction method, and the catalytic performance of oxidative coupling of methane on the different catalysts, such as TiO2, Li/TiO2, Mn/TiO2, LiMn2O4 as well as LiMn2O4/TiO2, was evaluated. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, CO2 temperature programmed desorption and H2 temperature programmed reduction. It is found that LiMn2O4 with spinel structure has high catalytic activity in oxidative coupling of methane reaction. 25.8% of CH4 conversion, 43.2% of C2 selectivity was obtained under the reaction conditions of 775℃, 0.1MPa, 7200mL·h-1·g-1, CH4:O2(volume ratio)=2.5. The introduction of TiO2 support can not only improve CH4 conversion and C2 selectivity, but also restrain the deep oxidation of methane to CO2. The LiMn2O4/TiO2 with 8% loading amount showed the best activity, on which 31.6% of CH4 conversion, 52.4% of C2 selectivity were obtained and CO2 selectivity was decreased to 26.3%. The effect of calcination temperature on the activity of LiMn2O4/TiO2 catalysts was investigated. 850℃ is the optimal calcination temperature.
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  • [1]
    KELLER G E, BHASIN M M. Synthesis of ethylene via oxidative coupling of methane:I. Determination of active catalysts[J]. J Catal, 1982, 73(1):9-19. doi: 10.1016/0021-9517(82)90075-6
    [2]
    张志翔, 王凤荣, 苑慧敏, 王斯晗, 张宝军, 孟素凤.甲烷氧化偶联反应制乙烯的研究进展[J].现代化工, 2007, 27(3):20-25.

    ZHANG Zhi-xiang, WANG Feng-rong, YUAN Hui-min, WANG Si-han, ZHANG Bao-jun, MENG Su-feng. The research progress of the oxidative coupling of methane to ethylene[J]. Mod Chem Ind, 2007, 27(3):20-25.
    [3]
    王凡, 郑丹星.甲烷氧化偶联制烯烃的热力学平衡限度[J].燃料化学学报, 2006, 34(1):71-74. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract16951.shtml

    WANG Fan, ZHENG Dan-xing. The thermodynamic equilibrium limit for the oxidative coupling of methane[J]. J Fuel Chem Technol, 2006, 34(1):71-74. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract16951.shtml
    [4]
    KORF S J, ROOS J A, DERKSEN J W H C, VREEMAN J A, VAN OMMEN J G, ROSS J R H. Oxidative coupling of methane over Ba/CaO catalysts:A comparison with Li/MgO[J]. Appl Catal, 1990, 59(1):291-309. doi: 10.1016/S0166-9834(00)82205-8
    [5]
    JI S F, XIAO T C, LI S B, CHOU L J, ZHANG B, XU C Z, HOU R I, YORK A P E, GREEN M L H. Surface WO4 tetrahedron:The essence of the oxidative coupling of methane over M-W-Mn/SiO2 catalysts[J]. J Catal, 2003, 220(1):47-56. doi: 10.1016/S0021-9517(03)00248-3
    [6]
    IVANOV D V, ISUPOVA L A, GERASIMOV E Y, DOVLITOVA L S, GLAZNEVA T S, PROSVIRIN I P. Oxidative methane coupling over Mg, Al, Ca, Ba, Pb-promoted SrTiO3 and Sr2TiO4:Influence of surface composition and microstructure[J]. Appl Catal A:Gen, 2014, 485:10-19. doi: 10.1016/j.apcata.2014.07.024
    [7]
    陈宏善, 牛建中, 张兵, 李树本. Na-W-Mn/SiO2催化剂中的组分协同效应[J].催化学报, 2000, 21(1):55-58.

    CHEN Hong-shan, NIU Jian-zhong, ZHAGN Bing, LI Shu-ben. The synergistic effect over the components of Na-W-Mn/SiO2 catalyst. Chin J Catal, 2000, 21(1):55-58.
    [8]
    宋国华, 缪建文, 范以宁, 周静.低温甲烷氧化偶联纳米SrTi0.975Li0.025O3-δ催化剂的原位ESR和TPSR表征[J].燃料化学学报, 2010, 38(4):490-495. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17613.shtml

    SONG Guo-hua, MIU Jian-wen, FAN Yi-ning, ZHOU Jing. In situ ESR and TPSR measurements of SrTi0.975Li0.025O3-δ nanocatalysts for oxidative coupling of methane at low-temperature[J]. J Fuel Chem Technol, 2010, 38(4):490-495. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17613.shtml
    [9]
    HARGREAVES J S J, HUTCHINGS G J, JOYNER R W, KIELY C J. Structural aspects of magnesium oxide catalysts for the oxidative coupling of methane[J]. Catal Today, 1991, 10(3):259-266. doi: 10.1016/0920-5861(91)80005-T
    [10]
    WANG D J, ROSYNEK M P, LUNSFORD J H. The effect of chloride Ions on a Li+-MgO catalyst for the oxidative dehydrogenation of ethane[J]. J Catal, 1995, 151(1):155-167. doi: 10.1006/jcat.1995.1018
    [11]
    XU M, LUNSFORD J. Effect of temperature on methyl radical generation over Sr/La2O3 catalysts[J]. Catal Lett, 1991, 11(3/6):295-300.
    [12]
    MAHMOODI S, EHSANI M R, GHOREISHI S M. Effect of promoter in the oxidative coupling of methane over synthesized Mn/SiO2 nanocatalysts via incipient wetness impregnation[J]. J Ind Eng Chem, 2010, 16(6):923-928. doi: 10.1016/j.jiec.2010.09.007
    [13]
    ARNDT S, OTREMBA T, SIMON U, YILDIZ M, SCHUBERT H, SCHOMÄCKER R. Mn-Na2WO4/SiO2 as catalyst for the oxidative coupling of methane. What is really known?[J]. Appl Catal A:Gen, 2012, 425-426:53-61. doi: 10.1016/j.apcata.2012.02.046
    [14]
    TIEMERSMA T P, TUINIER M J, GALLUCCI F, KUIPERS J A M, ANNALAND M V S. A kinetics study for the oxidative coupling of methane on a Mn/Na2WO4/SiO2 catalyst[J]. Appl Catal A:Gen, 2012, 433-434:96-108. doi: 10.1016/j.apcata.2012.05.002
    [15]
    BECK B, FLEISCHER V, ARNDT S, HEVIA M G, URAKAWA A, HUGO P, SCHOMÄCKER R. Oxidative coupling of methane-A complex surface/gas phase mechanism with strong impact on the reaction engineering[J]. Catal Today, 2014, 228:212-218. doi: 10.1016/j.cattod.2013.11.059
    [16]
    KOIRALA R, BVCHEL R, PRATSINIS S E, BAIKER A. Oxidative coupling of methane on flame-made Mn-Na2WO4/SiO2:Influence of catalyst composition and reaction conditions[J]. Appl Catal A:Gen, 2014, 484:97-107. doi: 10.1016/j.apcata.2014.07.013
    [17]
    KOU Y, WANG H, ZHANG H, YANG X. Amorphous features of working catalysts[J]. Catal Today, 1999, 51(1):47-57. doi: 10.1016/S0920-5861(99)00007-3
    [18]
    MALEKZADEH A, KHODADADI A, ABEDINI M, AMINI M, BAHRAMIAN A, DALAI A K. Correlation of electrical properties and performance of OCM MOx/Na2WO4/SiO2 catalysts[J]. Catal Commun, 2001, 2(8):241-247. doi: 10.1016/S1566-7367(01)00034-6
    [19]
    WANG D J, ROSYNEK M P, LUNSFORD J H. Oxidative coupling of methane over oxide-supported sodium-manganese catalysts[J]. J Catal, 1995, 155(2):390-402. doi: 10.1006/jcat.1995.1221
    [20]
    MALEKZADEH A, KHODADADI A, DALAI A K, ABEDINI M. Oxidative coupling of methane over lithium doped (Mn+W)/SiO2 catalysts[J]. J Nat Gas Chem, 2007, 16(2):121-129. doi: 10.1016/S1003-9953(07)60037-1
    [21]
    ZHONG W, DAI H X, NG C F, AU C T. A comparison of nanoscale and large-size BaCl2-modified Er2O3 catalysts for the selective oxidation of ethane to ethylene[J]. Appl Catal A:Gen, 2000, 203(2):239-250. doi: 10.1016/S0926-860X(00)00486-5
    [22]
    ZHAO Q, BAO X H, WANG Y, LIN L W, LI G, GUO X W, WANG X S. Studies on superoxide O2- species on the interaction of TS-1 zeolite with H2O2[J]. J Mol Catal A:Chem, 2000, 157(1/2):265-268.
    [23]
    WANG Z, ZOU G, LUO X, LIU H, GAO R, CHOU L, WANG X. Oxidative coupling of methane over BaCl2-TiO2-SnO2 catalyst[J]. J Nat Gas Chem, 2012, 21(1):49-55. doi: 10.1016/S1003-9953(11)60332-0
    [24]
    沈鸿福, 王新平, 刘勤.甲烷氧化合成乙烯的Li2SO4-MnxOy/TiO2催化剂[J].催化学报, 1990, 11(1):60-65.

    SHEN Hong-fu, WANG Xin-ping, LIU Qin. Li2SO4-MnxOy/TiO2 catalyst for the oxidative coupling of methane[J]. Chin J Catal, 1990, 11(1):60-65.
    [25]
    KONDRATENKO E V, WOLF D, BAERNS M. Influence of electronic properties of Na2O/CaO catalysts on their catalytic characteristics for the oxidative coupling of methane[J]. Catal Lett, 1999, 58:217-223. doi: 10.1023/A:1019058724099
    [26]
    MALEKZADEH A, ABEDINI M, KHODADADI A A, AMINI M, MISHRA H K, DALAI A K. Critical influence of Mn on low-temperature catalytic activity of Mn/Na2WO4/SiO2 catalyst for oxidative coupling of methane[J]. Catal Lett, 2002, 84:45-51. doi: 10.1023/A:1021020516674
    [27]
    YANG T L, FENG L B, SHEN S K. Oxygen species on the surface of La2O3/CaO and its role in the oxidative coupling of methane[J]. J Catal, 1994, 145:384-389. doi: 10.1006/jcat.1994.1048
    [28]
    GOPINATH C S, HEGDE S G, RAMASWAMY A V, MAHAPATRA S. Photoemission studies of polymorphic CaCO3 materials[J]. Mater Res Bull, 2002, 37(7):1323-1332. doi: 10.1016/S0025-5408(02)00763-8
    [29]
    FERREIRA V J, TAVARES P, FIGUEIREDO J L, FARIA J L. Ce-doped La2O3 based catalyst for the oxidative coupling of methane[J]. Catal Commun, 2013, 42:50-53. doi: 10.1016/j.catcom.2013.07.035
    [30]
    JONES C A, LEONARD J J, SOFRANKO J A. The oxidative conversion of methane to higher hydrocarbons over alkali-promoted Mn-SiO2[J]. J Catal, 1987, 103:311-319. doi: 10.1016/0021-9517(87)90123-0
    [31]
    LI H, VRINAT M, BERHAULT G, LI D, NIE H, AFANASIEV P. Hydrothermal synthesis and acidity characterization of TiO2 polymorphs[J]. Mater Res Bull, 2013, 48(9):3374-3382. doi: 10.1016/j.materresbull.2013.05.017
    [32]
    KAPTEIJN F, SINGOREDJO L, ANDREINI A, MOULIJN J A. Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia[J]. Appl Catal B:Environ, 1994, 3(2):173-189. https://www.researchgate.net/publication/222491231_Activity_and_selectivity_of_pure_manganese_oxides_in_the_selective_catalytic_reduction_of_nitric_oxide_with_ammonia
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