With phenanthrene and hydrogen as raw materials, the hydrogenation of phenanthrene was tested over CoMo/ Al 2 O 3 catalyst in a fixed-bed microreactor. Effects of temperature, pressure and space velocity on the reactions were systematically investigated. On the basis of the equilibrium constants calculated by thermodynamic method and kinetic equation derived by the adsorption theory of Langmuir−Hinshelwood−Hougen−Watson, the rate constants, activation energy, and adsorption constants were estimated by the Broyden−Fletcher−Goldfarb−Shanno optimization method, and the different reaction networks were compared and screened. In this study, the result showed the path from 9,10-dihydrophenathrene to tetrahydrophenathrene could be neglected, and the path from 9,10-dihydrophenathrene to 1,10-octahydrophenanthrene could not be excluded.
Direct coal liquefaction in the heating stage of Shenhua Shendong bituminous coal was carried out in a 0.01 t/d continuous tubular facility with iron catalyst and hydrogenated anthracene and wash oil as solvent at a residence time (t) of 3.5− 6.5 min and a reaction temperature (T) of 340−450 °C. The results show that when t = 3.5 min and T = 340 °C, a cracking reaction of coal occurs, while the oil yield was almost zero. As the residence time and temperature each increase, coal conversion and product yield exhibit different change patterns. Especially when t = 6.5 min and T = 450 °C: under these conditions, the coal conversion and oil yield reached 83.67 and 52.27 wt %, respectively. To investigate the liquefaction kinetics, a 8-lump reaction kinetic model which follow first-order irreversible reactions (r = k i dC/dt) was developed to estimate the rate constants. The results indicated that the model is perfectly valid for the heating stage, and the yield of oil and gas were mainly from coal other than preasphaltene (PAA).
The kinetics of hydrodenitrogenation
(HDN) were systematically
studied in an isothermally high-throughput reactor over three kinds
of catalysts (CoMo, NiMo, and NiMoW) to produce clean diesel meeting
the latest national standard of China. The influences of reaction
temperature, reaction pressure, volume ratio of H2 to oil,
and space time on hydrodenitrogenation were investigated to obtain
kinetic parameters. Two kinetic models considering the influence of
self-inhibition were proposed for the HDN reaction of diesel oil.
The results of both models are satisfactory. Taking the two-lump model
as an example, it could well predict the evolution of nitrogen-containing
compounds’ concentration along the axial length of the reactor,
and the simulation on the HDN activity of various catalyst stacking
schemes is close to the experimental data, which proves that the model
is applicable for the simulation of a catalyst stacking system. In
addition, the concentration of nitrogen-containing compounds was predicted
for the catalyst gradation model of different loading sequences.
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