ABSTRACT
The dependence of the C-C hydrogenolysis activity on reaction parameters and the structure of the substrate alkanes was investigated for Ru/CeO2 catalyst with very small (dispersion: H/Ru=0.89) Ru particles. The substrate concentration and reaction temperature did not have a significant effect on the selectivity pattern, except that methane production was promoted at high temperatures. However, the hydrogen pressure had a marked effect on the selectivity pattern. Ctertiary -C bond dissociation, terminal Csecondary -Cprimary bond dissociation, and fragmentation to form excess methane had negative reaction order with respect to hydrogen partial pressure, whereas Csecondary -Csecondary bond dissociation had an approximately zero reaction order. Therefore, a high hydrogen pressure is essential for the regioselective hydrogenolysis of Csecondary -Csecondary bonds in squalane. Ru/SiO2 catalyst with larger Ru particles showed similar changes in the product distribution during the change in hydrogen pressure. The reaction mechanism for each type of C-C bond dissociation is proposed based on reactivity trends and DFT calculations. The proposed intermediate species for the internal Csecondary -Csecondary dissociation, terminal Csecondary -Cprimary dissociation, and Ctertiary -C dissociation is alkyls, alkylidynes, and alkenes, respectively.
Subject(s)
Alkanes/chemistry , Hydrogen/chemistry , Ruthenium/chemistry , Squalene/analogs & derivatives , Catalysis , Models, Molecular , Molecular Conformation , Pressure , Silicon Dioxide/chemistry , Squalene/chemistry , Stereoisomerism , Substrate Specificity , Surface Properties , TemperatureABSTRACT
In tomographic adaptive-optics (AO) systems, errors due to tomographic wavefront reconstruction limit the performance and angular size of the scientific field of view (FoV), where AO correction is effective. We propose a multi time-step tomographic wavefront reconstruction method to reduce the tomographic error by using measurements from both the current and previous time steps simultaneously. We further outline the method to feed the reconstructor with both wind speed and direction of each turbulence layer. An end-to-end numerical simulation, assuming a multi-object AO (MOAO) system on a 30 m aperture telescope, shows that the multi time-step reconstruction increases the Strehl ratio (SR) over a scientific FoV of 10 arc min in diameter by a factor of 1.5-1.8 when compared to the classical tomographic reconstructor, depending on the guide star asterism and with perfect knowledge of wind speeds and directions. We also evaluate the multi time-step reconstruction method and the wind estimation method on the RAVEN demonstrator under laboratory setting conditions. The wind speeds and directions at multiple atmospheric layers are measured successfully in the laboratory experiment by our wind estimation method with errors below 2 ms-1. With these wind estimates, the multi time-step reconstructor increases the SR value by a factor of 1.2-1.5, which is consistent with a prediction from the end-to-end numerical simulation.
ABSTRACT
Squalane, C30 algae-derived branched hydrocarbon, was successfully converted to smaller hydrocarbons without skeletal isomerization and aromatization over ruthenium on ceria (Ru/CeO2 ). The internal CH2 CH2 bonds located between branches are preferably dissociated to give branched alkanes with very simple distribution as compared with conventional methods using metal-acid bifunctional catalysts.
