Thermochemical valorization of camelina straw waste via fast pyrolysis

The present work investigates the thermochemical valorization of camelina straw, which is a waste generated during the harvesting of Camelina sativa, an oilseed crop for the production of biodiesel or hydrotreated vegetable oil (HVO). In particular, it is focused on obtaining bio-oil via thermal or catalytic fast pyrolysis, which would be the first stage on a sequence of chemical processes for biofuel production. The catalytic interference of the inorganic matter present in the biomass was studied by preparing a batch of de-ashed camelina straw by washing with diluted nitric acid. Chemical analysis revealed this treatment effectively removed alkaline (K and Na) and alkaline earth (Ca and Mg) metals. Pyrolysis of de-ashed camelina straw led to higher mass and energy yields of bio-oil in water-free basis (bio-oil*), but with higher oxygen concentration. Catalytic pyrolysis over HZSM-5 was also studied in both raw and de-ashed feedstocks. This catalyst promoted mainly decarbonylation and decarboxylation reactions of the pyrolysis vapors, leading to much higher gas yields and lower of bio-oil*, but with better quality. Catalytic pyrolysis of untreated camelina straw exhibited a synergetic effect between both the inorganic matter and the external HZSM-5 catalyst, so that bio-oil* yield was the lowest (20 wt%) due to an extensive deoxygenation (18 wt% oxygen content), which resulted in the highest HHV obtained (37.3 MJ/kg(db)). Significant differences were also found on the molecular composition of the bio-oils* with larger proportion of anhydro sugars when the biomass was de-ashed, while HZSM-5 strongly promoted the formation of oxygenated aromatics and aromatic hydrocarbons.