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. shu

Performance of oxidative coupling of methane on LiMn₂O₄/TiO₂ catalysts

Department of Energy Reaction Engineerig, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Corresponding author: ZHANG Ze-kai, zzk@zjut.edu.cn CHEN Yin-fei, yfchen@zjtu.edu.cn
Received Date: 21 December 2015
Revised Date: 23 March 2016

Figures(4)

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.
- oxidative coupling of methane,
- spinel,
- LiMn₂O₄,
- TiO₂,
- synergistic effect
1. [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. [2]
  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. [3]
  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.
4. [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. [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. [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. [7]
  CHEN Hong-shan, NIU Jian-zhong, ZHAGN Bing, LI Shu-ben. The synergistic effect over the components of Na-W-Mn/SiO₂ catalyst[J]. Chin J Catal, 2000,21(1):55-58.
8. [8]
  SONG Guo-hua, MIU Jian-wen, FAN Yi-ning, ZHOU Jing. In situ ESR and TPSR measurements of SrTi_0.975Li_0.025O_3-δ nanocatalysts for oxidative coupling of methane at low-temperature[J]. J Fuel Chem Technol, 2010,38(4):490-495.
9. [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. [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. [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. [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. [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. [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. [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. [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. [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. [18]
  MALEKZADEH A, KHODADADI A, ABEDINI M, AMINI M, BAHRAMIAN A, DALAI A K. Correlation of electrical properties and performance of OCM MO_x/Na₂WO₄/SiO₂ catalysts[J]. Catal Commun, 2001,2(8):241-247. doi: 10.1016/S1566-7367(01)00034-6
19. [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. [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. [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. [22]
  ZHAO Q, BAO X H, WANG Y, LIN L W, LI G, GUO X W, WANG X S. Studies on superoxide O^2- species on the interaction of TS-1 zeolite with H₂O₂[J]. J Mol Catal A:Chem, 2000,157(1/2):265-268.
23. [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. [24]
  SHEN Hong-fu, WANG Xin-ping, LIU Qin. Li₂SO₄-Mn_xO_y/TiO₂ catalyst for the oxidative coupling of methane[J]. Chin J Catal, 1990,11(1):60-65.
25. [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. [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. [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. [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. [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. [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. [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. [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.
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Performance of oxidative coupling of methane on LiMn₂O₄/TiO₂ catalysts