RESUMEN
A series of bifunctional catalysts, MoS2/Al2O3 (70 wt.%), zeolite (30 wt.%) (zeolite-ZSM-5, ZSM-12, and ZSM-22), and silica aluminophosphate SAPO-11, were synthesized for hydroconversion of methyl palmitate (10 wt.% in dodecane) in a trickle-bed reactor. Mo loading was about 7 wt.%. Catalysts and supports were characterized by different physical-chemical methods (HRTEM-EDX, SEM-EDX, XRD, N2 physisorption, and FTIR spectroscopy). Hydroprocessing was performed at a temperature of 250-350 °C, hydrogen pressure of 3.0-5.0 MPa, liquid hourly space velocity (LHSV) of 36 h-1, and an H2/feed ratio of 600 Nm3/m3. Complete conversion of oxygen-containing compounds was achieved at 310 °C in the presence of MoS2/Al2O3-zeolite catalysts; the selectivity for the conversion of methyl palmitate via the 'direct' hydrodeoxygenation (HDO) route was over 85%. The yield of iso-alkanes gradually increases in order: MoS2/Al2O3 < MoS2/Al2O3-ZSM-12 < MoS2/Al2O3-ZSM-5 < MoS2/Al2O3-SAPO-11 < MoS2/Al2O3-ZSM-22. The sample MoS2/Al2O3-ZSM-22 demonstrated the highest yield of iso-alkanes (40%). The hydroisomerization activity of the catalysts was in good correlation with the concentration of Brønsted acid sites in the synthesized supports.
Asunto(s)
Molibdeno , Zeolitas , Zeolitas/química , Alcanos/química , Dióxido de SilicioRESUMEN
A π-conjugated oligomer bearing two 15-crown-5-containing styryl moieties connected at the inner ß positions of the terminal thiophene nuclei can adopt either a U or a Z shape depending on the structures of its complexes with magnesium and barium ions. We show that barium cations lead to the formation of a mononuclear complex in solution, which causes the system to fold into the U shape. Magnesium ions lead to the same effect at low concentration, but force the ligand to adopt the Z-shaped geometry at high concentrations favoring formation of a binuclear complex. These geometrical reorganizations in solution are accompanied by profound changes in spectroscopic properties, which can be rationalized in terms of variations in the extent of electron delocalization along the oligothiophene backbone. The effects are analyzed by mass spectrometry and (1)H NMR, UV/Vis absorption, and fluorescence spectroscopy in the steady-state and time-resolved regimes. The experimental results are compared to data calculated by using MOPAC2007 with the PM6 Hamiltonian including the COSMO solvation model.