The photoionization and dissociation of 2-methyl-2-propen-1-ol(MPO)have been investigated by using molecular beam experimental apparatus with tunable vacuum ultraviolet synchrotron radiation in the photon energy regio...The photoionization and dissociation of 2-methyl-2-propen-1-ol(MPO)have been investigated by using molecular beam experimental apparatus with tunable vacuum ultraviolet synchrotron radiation in the photon energy region of 8.0-15.5 eV.The photoionization efficiency(PIE)curves for molecule ion and fragment ions:C4H8O^+,C4H7O^+,C3H5O^+,C4H7^+,C4H6^+,C4H5^+,C2H4O^+,C2H3O+,C3H6^+,C3H5^+,C3H3^+,CH3O^+,CHO^+have been measured,and the ionization energy(IE)and the appearance energies(AEs)of the fragment ions have been obtained.The stable species and the first order saddle points have been calculated on the CCSD(T)/cc-pvTZ//B3LYP/6-31+G(d,p)level.With combination of theoretical and experimental results,the dissociative photoionization pathways of 2-methyl-2-propen-1-ol are proposed.Hydrogen migrations within the molecule are the dominant processes in most of the fragmentation pathways of MPO.展开更多
This paper describes the hydrogenation of impurities in the methanol-containing effluent from the propylene epoxidation process with hydrogen peroxide. The effects of reaction temperature, pressure, weight hourly spac...This paper describes the hydrogenation of impurities in the methanol-containing effluent from the propylene epoxidation process with hydrogen peroxide. The effects of reaction temperature, pressure, weight hourly space velocity(WHSV) and H2/methanol ratio on the concentration of various impurities in methanol solvent were investigated. It was found out that the aldehyde, hydrogen peroxide and nitro compounds in the methanol solvent could be completely hydrogenated over the Ni catalyst under proper reaction conditions. 90% of acetone and up to 50% of acetals(ketals) existing in the methanol solvent could be hydrogenated. No significant change was observed for the rest of the impurities that were present in the methanol solvent(i. e., 1-methoxy-2-propanol, 2-methoxy-1-propanol and 1,2-propanediol). The H2O2 decomposition reaction was enhanced using Ni catalyst, through the formation of NioOH, but no oxygen was found in the off-gas of hydrogenation reaction since NioH could react on NioOH formed via dissociative adsorption of hydrogen peroxide, or on NioO formed via adsorption of oxygen.展开更多
基金supported by the National Natural Science Foundation of China(No.91544105,No.U1532137,No.275127,No.U1232130,No.U1232209,and No.U11575178)the Supercomputing Center of USTC is also acknowledged
文摘The photoionization and dissociation of 2-methyl-2-propen-1-ol(MPO)have been investigated by using molecular beam experimental apparatus with tunable vacuum ultraviolet synchrotron radiation in the photon energy region of 8.0-15.5 eV.The photoionization efficiency(PIE)curves for molecule ion and fragment ions:C4H8O^+,C4H7O^+,C3H5O^+,C4H7^+,C4H6^+,C4H5^+,C2H4O^+,C2H3O+,C3H6^+,C3H5^+,C3H3^+,CH3O^+,CHO^+have been measured,and the ionization energy(IE)and the appearance energies(AEs)of the fragment ions have been obtained.The stable species and the first order saddle points have been calculated on the CCSD(T)/cc-pvTZ//B3LYP/6-31+G(d,p)level.With combination of theoretical and experimental results,the dissociative photoionization pathways of 2-methyl-2-propen-1-ol are proposed.Hydrogen migrations within the molecule are the dominant processes in most of the fragmentation pathways of MPO.
文摘This paper describes the hydrogenation of impurities in the methanol-containing effluent from the propylene epoxidation process with hydrogen peroxide. The effects of reaction temperature, pressure, weight hourly space velocity(WHSV) and H2/methanol ratio on the concentration of various impurities in methanol solvent were investigated. It was found out that the aldehyde, hydrogen peroxide and nitro compounds in the methanol solvent could be completely hydrogenated over the Ni catalyst under proper reaction conditions. 90% of acetone and up to 50% of acetals(ketals) existing in the methanol solvent could be hydrogenated. No significant change was observed for the rest of the impurities that were present in the methanol solvent(i. e., 1-methoxy-2-propanol, 2-methoxy-1-propanol and 1,2-propanediol). The H2O2 decomposition reaction was enhanced using Ni catalyst, through the formation of NioOH, but no oxygen was found in the off-gas of hydrogenation reaction since NioH could react on NioOH formed via dissociative adsorption of hydrogen peroxide, or on NioO formed via adsorption of oxygen.
