The industrialization of oxidative coupling of methane(OCM)is restricted by the low once through yield of C_(2)hydrocarbons.Recently,the halogen-assisted OCM process has been attempted to overcome this issue,but the r...The industrialization of oxidative coupling of methane(OCM)is restricted by the low once through yield of C_(2)hydrocarbons.Recently,the halogen-assisted OCM process has been attempted to overcome this issue,but the reaction stability was poor due to the rapid loss of gas-phase halides or molten alkali halides.In this work,the barium salts,particularly barium halides(BaCl_(2)and BaF_(2)),were demonstrated to be efficient promoters to improve the OCM reactivity of La_(2)O_(3)/CaO catalyst by increasing both C_(2)selectivity and C_(2)H_(4)/C_(2)H_(6)ratio,and simultaneously achieving outstanding reaction stability.The promoting mechanism can be understood in two aspects.On the one hand,the introduction of barium salts increased the amount of surface electrophilic oxygen species,serving as the alkaline active sites for selective methane activation.On the other hand,the barium halide additives induced the in-situ formation of methyl halide intermediates facilitating C_(2)H_(6)dehydrogenation,and their intimate contact with catalyst substrate restricted the rapid halogen loss and thereby improved the catalytic stability.This work not only provides a class of efficient OCM catalyst,but also offers a highly stable halogen-assisted reaction strategy.展开更多
基金financially supported by the National Natural Science Foundation of China(22178390,21961132026)the Key Research and Development Plan of Shandong Province(2018GGX107011)the Natural Science Foundation of Shandong Province(ZR2017BB020)。
文摘The industrialization of oxidative coupling of methane(OCM)is restricted by the low once through yield of C_(2)hydrocarbons.Recently,the halogen-assisted OCM process has been attempted to overcome this issue,but the reaction stability was poor due to the rapid loss of gas-phase halides or molten alkali halides.In this work,the barium salts,particularly barium halides(BaCl_(2)and BaF_(2)),were demonstrated to be efficient promoters to improve the OCM reactivity of La_(2)O_(3)/CaO catalyst by increasing both C_(2)selectivity and C_(2)H_(4)/C_(2)H_(6)ratio,and simultaneously achieving outstanding reaction stability.The promoting mechanism can be understood in two aspects.On the one hand,the introduction of barium salts increased the amount of surface electrophilic oxygen species,serving as the alkaline active sites for selective methane activation.On the other hand,the barium halide additives induced the in-situ formation of methyl halide intermediates facilitating C_(2)H_(6)dehydrogenation,and their intimate contact with catalyst substrate restricted the rapid halogen loss and thereby improved the catalytic stability.This work not only provides a class of efficient OCM catalyst,but also offers a highly stable halogen-assisted reaction strategy.
