On the Dynamic Measurement of Dissolved Oxygen Concentration during Liquid Phase Glycerol Catalytic Oxidation R. Ducoulombier, P. Fongarland*, M. Capron and F. Dumeignil Unité de catalyse et de chimie du solide, bâtiment C3, cité scientifique, 59655 Villeneuve d’Ascq, France *pascal.fongarland@ec-lille.fr Normalized Pressure or Dissolved Concentration Introduction. The progressive rarefaction of fossil resources has increased the interest on renewable raw resources. Glycerol is a by-product of the reaction of transesterification of triglycerides used for producing biodiesels. It can be valorized by liquid phase oxidation, which yields added value compounds such as dihydroxyaceton or hydroxypyruvic acid. The aim of this work is to enable more reliable kinetics studies of the liquid phase catalytic oxidation of glycerol. In situ direct determination of the concentration in dissolved oxygen using a specific probe at the reaction practical temperature (60-80 °C) and pressure (0.5 – 5 MPa of O2) is very useful for kinetic and external mass transfer coupling studies. This paper deals with the interest of using a unique commercial probe for studying the liquid phase glycerol oxidation reaction. Experimental. The measurements were performed in a 300 mL stirred tank reactor in batch mode. The gas-liquid mass transfer coefficient (kLa) of oxygen in glycerol-water mixture as well as the Henry coefficient (He) in the absence of chemical reaction were first determined using the conventional physical absorption method (dynamic pressure steps). The influence of liquid composition, temperature and pressure on the value of kLa was studied. Subsequently, a Fugatron® probe (OXY-100 from LPD company) was adapted to the reactor and successfully used for measuring the quantity of dissolved oxygen with a calibrated mass spectrometer. Results. The Henry coefficient obtained for the O2-water system (101.8 kPa at 25 °C and 0.5 MPa) was in good agreement with Gourich et al. (101.6 kPa).1 He varied from 101 to 1,0 196 kPa with the water-glycerol mixture 0,8 composition. The kLa in the absence of a chemical reaction was measured for 0,6 several mixture compositions, impeller O2 Pressure Response rotation rates, temperatures and 0,4 + O2 Fugatron Response pressures, which led values within the 0,2 range of 10-4 to 0.39 s-1. The Fugatron® probe efficiency for measuring the T90% = 38 s 0,0 oxygen dissolution extent was then 0 10 20 30 40 50 60 70 validated. Indeed, the results were similar Time (s) to those obtained by the dynamic pressure method, even if the response time t90% (corresponding to 90 % of the saturation) for the probe was delayed at 38 s compared to 6 s for the pressure response (Figure 1). However, this is much less than previous studies on H2 solubilization2,3 with a similar probe. Note that the presence of a slurry and gas bubbles had no influence on the oxygen liquid concentration measurement. Conclusion. Direct in-situ measurement of oxygen concentration in the liquid phase during glycerol oxidation reaction in a slurry reactor containing gas bubbles is made possible by the use of the Fugatron® probe. However, response time can be a limit especially for dynamic systems when the characteristic time is lower than 30 s (typical reaction startup or kLa > 0.03 s-1). 1 Gourich, B; Vial, Ch.; El Azher, N.; Soulami, M.B.; Ziyad, M.; Biochemical Engineering J. 39, 1-14 (2008). Meyberg, M.; Roessler, F.;. Ind. Eng. Chem. Res. 44, 9705-9711 (2005). 3 Schärringer, P.; Müller, T.E.; Kaltner, W.; Lercher, J.A;. Ind. Eng. Chem. Res. 44, 9770-9775 (2005). 2