Ni-Nb-O catalysts for ethane oxidative dehydrogenation

被引:118
作者
Savova, B. [2 ]
Loridant, S. [1 ]
Filkova, D. [2 ]
Millet, J. M. M. [1 ]
机构
[1] Univ Lyon 1, CNRS, UMR5256, Inst Rech Catalyse & Environm Lyon,IRCELYON, F-69626 Villeurbanne, France
[2] Bulgarian Acad Sci, Inst Catalysis, BU-1113 Sofia, Bulgaria
关键词
Ethane oxidative dehydrogenation; Ethylene; Ni-Nb-O mixed metal oxides; Active sites isolation; Oxygen over stoichiometry; O- electrophilic species; Catalyst deactivation; METAL-OXIDE CATALYSTS; SELECTIVE OXIDATION; MIXED OXIDES; ETHENE PRODUCTION; RAMAN-SCATTERING; NICKEL-OXIDE; ETHYLENE; OXYGEN; SPECTROSCOPY; PERFORMANCE;
D O I
10.1016/j.apcata.2010.10.004
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ni-Nb-O catalysts with various Nb contents (0-19%) have been studied as catalysts for the oxidative dehydrogenation of ethane An optimum ethane conversion of 33% with 78% of selectivity to ethylene was obtained for a Ni-Nb-O catalyst containing 15% of Nb at 350 degrees C with a weight to flow W/F ratio of 0 54gs mL(-1) The catalysts have been characterized using various techniques allowing to show that the efficiency of the catalysts was related to a surface interaction between the NiO active phase and an amorphous Nb2O5 phase Because ammonium oxalato niobate was used as niobium precursor oxalate ions were present concomitantly to the surface interaction described the thermal decomposition of these oxalate ions induced a reduction in NiO oxygen over-stoichiometry which also influences the catalytic properties It was demonstrated that only a small percent of Nb was necessary to have these effects and the optimal activity observed for 15% of Nb had to be related to another process which corresponds to the decrease in the active phase particle size induced by the amorphous Nb2O5 phase this phase prevents the sintering of the active phase particles during the thermal transformation of the catalysts precursors It was also shown that the thermal decomposition of oxalates limits NiO crystal growth Above 15% of Nb the amorphous phase reacted with the nickel oxide to form an inactive mixed niobium and nickel oxide phase NiNb2O6 The study of the catalytic properties over long periods of time showed that the Ni-Nb-O catalysts underwent a slow but systematic deactivation This deactivation has been attributed both to the continuous reduction of the NiO oxygen over-stoichiometry in the reaction conditions and to the formation of the NiNb2O6 phase thermodynamically stable at the catalytic reaction temperature Attempt to regenerate the catalysts has failed (C) 2010 Elsevier B V All rights reserved
引用
收藏
页码:148 / 157
页数:10
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