Semi-Batch Deoxygenation of Canola- and Lard-Derived Fatty Acids to Diesel-Range Hydrocarbons

Fatty acids (FAs) derived via thermal hydrolysis of food-grade lard and canola oil were deoxygenated in the liquid phase using a commercially available 5 wt % Pd/C catalyst. Online quadrupole mass spectrometry and gas chromatography were used to monitor the effluent gases from the semi-batch stirred autoclave reactors. Stearic, oleic, and palmitic acids were employed as model compounds. A catalyst lifetime exceeding 2200 turnovers for oleic acid deoxygenation was demonstrated at 300 °C and 15 atm under 10% H2. The initial decarboxylation rate of palmitic acid under 5% H2 decreases sharply with increasing initial concentration; in contrast, the initial decarbonylation rate increases linearly, indicative of first-order kinetics. Scale-up of diesel-range hydrocarbon production was investigated by increasing the reactor vessel size, initial FA concentration, and FA/catalyst mass ratio. Lower CO2 selectivity and batch productivity were observed at the larger scales (600 and 5000 mL), primarily because of the higher initial FA concentration (67 wt %) employed. Because unsaturated FAs must be hydrogenated before deoxygenation can proceed at an appreciable rate, the additional batch time required for FA hydrogenation reduces the batch productivity for unsaturated feedstocks. Low-temperature hydrogenation of unsaturated feedstocks (using Pd/C or another less-expensive catalyst) prior to deoxygenation is recommended.