The oxidative coupling of methane to C2 hydrocarbons has been studied over a series of La-promoted CaO （La/Ca = 0.05） catalysts, prepared using different precursor salts for CaO and La2O3 （viz. acetates, carbonates...The oxidative coupling of methane to C2 hydrocarbons has been studied over a series of La-promoted CaO （La/Ca = 0.05） catalysts, prepared using different precursor salts for CaO and La2O3 （viz. acetates, carbonates, nitrates and hydroxides） and catalyst preparation methods （viz. physical mixing of precursors, co-precipitation using ammonium carbonate/sodium carbonate as a precipitating agent）, under different reaction conditions （temperature： 700-850 ℃, CH4/O2 ratio： 4.0 and 8.0, and GHSV： 51360 cm^3·g^-1·h^- 1）. The surface area and surface basicity/base strength distribution of the catalysts have also been investigated. The surface properties and catalytic activity/selectivity of the La-promoted CaO catalysts vary from catalyst to catalyst depending on the catalyst precursors used and catalyst preparation method. The basicity/base strength distribution is strongly influenced by the precursors （for CaO and La2O3） and catalyst preparation method. Basicity （total and strong basic sites measured in terms of CO2 chemisorbed at 50℃ and 500 ℃, respectively） observed for the catalyst prepared by co-precipitation method is higher than that of the catalysts prepared by physical mixing method. The catalysts prepared by the nitrates of La- and Ca- and co- precipitated by the solution of sodium carbonate and ammonium carbonate exhibit different catalytic performance in OCM. The finding that no direct relationship between the surface basicity and catalytic activity/selectivity in OCM exists indicates that basicity is not solely responsible for obtaining high selectivity to C2 hydrocarbons.展开更多
The oxidative coupling of methane over La203/CaO type-catalyst in a fixed-bed reactor is studied under a wide range of operating conditions （973〈T〈 1103 K, 55〈 Ptotal 〈220 kPa, and 3.7〈 mcat/VTp 〈50 kg.s/m^3）....The oxidative coupling of methane over La203/CaO type-catalyst in a fixed-bed reactor is studied under a wide range of operating conditions （973〈T〈 1103 K, 55〈 Ptotal 〈220 kPa, and 3.7〈 mcat/VTp 〈50 kg.s/m^3）. A ten-step kinetic model incorporating all main products was used to predict the behavior of the system. Methane conversions and C2 selectivities were calculated by varying methane to oxygen ratios in the feed under different operating conditions which were also compared with the rule of 100. The results show that deviation from this rule depends on the operating conditions. Within the range studied, an increase in pressure, temperature and contact time results in smaller deviation from the rule. This rule is best approximated when the catalyst operates near its optimal performance. For negative deviations, common to the most catalysts, it is found that the optimal performance should occur at methane conversion levels lower than 50%. A plot of selectivity versus conversion for high-yield reported performance data of a large variety of catalysts shows that data points concentrated roughly in 20%-50% methane conversion region, confirming the generality and prediction of modeling.展开更多
文摘The oxidative coupling of methane to C2 hydrocarbons has been studied over a series of La-promoted CaO （La/Ca = 0.05） catalysts, prepared using different precursor salts for CaO and La2O3 （viz. acetates, carbonates, nitrates and hydroxides） and catalyst preparation methods （viz. physical mixing of precursors, co-precipitation using ammonium carbonate/sodium carbonate as a precipitating agent）, under different reaction conditions （temperature： 700-850 ℃, CH4/O2 ratio： 4.0 and 8.0, and GHSV： 51360 cm^3·g^-1·h^- 1）. The surface area and surface basicity/base strength distribution of the catalysts have also been investigated. The surface properties and catalytic activity/selectivity of the La-promoted CaO catalysts vary from catalyst to catalyst depending on the catalyst precursors used and catalyst preparation method. The basicity/base strength distribution is strongly influenced by the precursors （for CaO and La2O3） and catalyst preparation method. Basicity （total and strong basic sites measured in terms of CO2 chemisorbed at 50℃ and 500 ℃, respectively） observed for the catalyst prepared by co-precipitation method is higher than that of the catalysts prepared by physical mixing method. The catalysts prepared by the nitrates of La- and Ca- and co- precipitated by the solution of sodium carbonate and ammonium carbonate exhibit different catalytic performance in OCM. The finding that no direct relationship between the surface basicity and catalytic activity/selectivity in OCM exists indicates that basicity is not solely responsible for obtaining high selectivity to C2 hydrocarbons.
文摘The oxidative coupling of methane over La203/CaO type-catalyst in a fixed-bed reactor is studied under a wide range of operating conditions （973〈T〈 1103 K, 55〈 Ptotal 〈220 kPa, and 3.7〈 mcat/VTp 〈50 kg.s/m^3）. A ten-step kinetic model incorporating all main products was used to predict the behavior of the system. Methane conversions and C2 selectivities were calculated by varying methane to oxygen ratios in the feed under different operating conditions which were also compared with the rule of 100. The results show that deviation from this rule depends on the operating conditions. Within the range studied, an increase in pressure, temperature and contact time results in smaller deviation from the rule. This rule is best approximated when the catalyst operates near its optimal performance. For negative deviations, common to the most catalysts, it is found that the optimal performance should occur at methane conversion levels lower than 50%. A plot of selectivity versus conversion for high-yield reported performance data of a large variety of catalysts shows that data points concentrated roughly in 20%-50% methane conversion region, confirming the generality and prediction of modeling.
