(181i) Hydrogen Solubility in Triolein and Oleic Acid for Estimation of Hydrodeoxygenation Reaction Rate At High Temperature and Pressure

Now, in Japan, hydrodeoxygenation reaction of fats has been paid much attention as a new method to produce biodiesel fuel (BDF) of the next generation. According to the method, triglyceride of fatty acid may be converted to propane, and some blanched alkanes by use of a desulfurization reactor in conventional petroleum refinery. In our previous study, we considered the utilization of trap grease as a carbon resources. The trap grease is free-floating grease in waste water reservoir of restaurant, food courts, food industry and so on, and mainly composed of triglyceride of fatty acids, and free fatty acid. Moreover, we have shown that the conventional hydrodesulfurization catalysts were effective for the hydrodeoxygenation reaction at 573.2 K. Though the phase equilibrium and the reaction rate are essential for designing the processes, there is few available data. So, in this study, a new apparatus was designed for a measurement of hydrogen solubility in triolein, and oleic acid up to 473.2 K. The apparatus was based on a recirculation method and the cell volume about 500 cm³. A cylinder, with the volume about 150 cm³, was connected with cell, and the inlet and the outlet of the cylinder have VCR assemblies. So, the liquid sample was picked up repeatedly. After weighing mass of the picked up sample, the dissolved hydrogen volume was measured by a flow meter.  The experimental data of hydrogen solubility showed a tendency like Henry's low up to 15 MPa and 473.2 K. The temperature dependence of Henry constant was correlated with a conventional relation. The next, by use of the extrapolated Henry constant at 573.2 K, the binary parameters, in mixing rule of Peng-Robinson (PR) equation of state, were determined. Finally the phase diagram and the reaction rate were evaluated by PR eq. at the desired reaction temperature, 573.2 K.