Partial oxidation of methane to formaldehyde and methanol was studied at atmospheric pressure in the temperature range of 700-750 °C using heteropolycompound catalysts （NH4）6HSiMo11FeO40, （NH4）4PMo11FeO39, an...Partial oxidation of methane to formaldehyde and methanol was studied at atmospheric pressure in the temperature range of 700-750 °C using heteropolycompound catalysts （NH4）6HSiMo11FeO40, （NH4）4PMo11FeO39, and H4PMo11VO40, which were prepared and characterized by various analysis techniques such as infrared, visible UV, XRD and DTA. O2 or N2O was used as the oxidizing agent, and the principal products of the reaction were CH3OH, CH2O, CO, CO2, and water. The conversion and the selectivity of products depend strongly on the reaction temperature, the nature of oxidizing agent, and the composition of catalyst.展开更多
The catalytic dehydrocyclization of n-hexane was studied here for the first time using a number of compounds based on H3PMo12O40. The described catalysts were prepared by either replacing the acidic proton with counte...The catalytic dehydrocyclization of n-hexane was studied here for the first time using a number of compounds based on H3PMo12O40. The described catalysts were prepared by either replacing the acidic proton with counter-ions such as ammonium or transition metal cations (NH4+, Fe3+, K+), or by replacing Mo6+ with (Ni3+, Co3+, Mn3+) in the polyoxometalate framework, as reported earlier. For comparison purposes, the known (TBA)7PW11O39 catalyst system was used. All reactions were conducted at different temperatures in the range 200 - 450. The Keggin structure of these heteropolycompounds was ascertained by XRD, UV and IR measurements. 31P NMR measurements and thermal behaviour of the prepared catalysts were also studied. These modified polyoxometalates exhibited heterogeneous superacidic catalytic activities in dehydrocyclization of n-hexane into benzene, cyclohexane, cyclohexene and cyclohexadiene. The catalysts obtained by substituting the acidic proton or coordination atom exhibited higher selectivity and stability than the parent compound H3PMo12O40. Catalytic activity and selectivity were heavily dependent on the composition of the catalyst and on the reaction conditions. At higher temperatures, the catalyst exhibited higher conversion efficiency at the expense of selectivity. Using higher temperatures (>400) in the presence of hydrogen carrier gas, selectivity towards dehydrocyclization ceased and methane dominated. To explain the results, a plausible mechanism is presented, based on super-acidic nature of the catalyst systems.展开更多
文摘Partial oxidation of methane to formaldehyde and methanol was studied at atmospheric pressure in the temperature range of 700-750 °C using heteropolycompound catalysts （NH4）6HSiMo11FeO40, （NH4）4PMo11FeO39, and H4PMo11VO40, which were prepared and characterized by various analysis techniques such as infrared, visible UV, XRD and DTA. O2 or N2O was used as the oxidizing agent, and the principal products of the reaction were CH3OH, CH2O, CO, CO2, and water. The conversion and the selectivity of products depend strongly on the reaction temperature, the nature of oxidizing agent, and the composition of catalyst.
文摘The catalytic dehydrocyclization of n-hexane was studied here for the first time using a number of compounds based on H3PMo12O40. The described catalysts were prepared by either replacing the acidic proton with counter-ions such as ammonium or transition metal cations (NH4+, Fe3+, K+), or by replacing Mo6+ with (Ni3+, Co3+, Mn3+) in the polyoxometalate framework, as reported earlier. For comparison purposes, the known (TBA)7PW11O39 catalyst system was used. All reactions were conducted at different temperatures in the range 200 - 450. The Keggin structure of these heteropolycompounds was ascertained by XRD, UV and IR measurements. 31P NMR measurements and thermal behaviour of the prepared catalysts were also studied. These modified polyoxometalates exhibited heterogeneous superacidic catalytic activities in dehydrocyclization of n-hexane into benzene, cyclohexane, cyclohexene and cyclohexadiene. The catalysts obtained by substituting the acidic proton or coordination atom exhibited higher selectivity and stability than the parent compound H3PMo12O40. Catalytic activity and selectivity were heavily dependent on the composition of the catalyst and on the reaction conditions. At higher temperatures, the catalyst exhibited higher conversion efficiency at the expense of selectivity. Using higher temperatures (>400) in the presence of hydrogen carrier gas, selectivity towards dehydrocyclization ceased and methane dominated. To explain the results, a plausible mechanism is presented, based on super-acidic nature of the catalyst systems.
