Abstract
The effects of hydrogen sources (hydrogen gas as an ex-situ hydrogen source and formic acid as an in-situ hydrogen source) on upgrading of pyrolysis oil by hydrodeoxygenation (HDO) in supercritical ethanol were comparatively investigated in this study for the first time. Effects of catalysts (5%Ru/C and 10%Ni-6%Mo-5%W/Al2O3), time and temperature on the product yields and quality of upgraded oil were investigated comparatively with different hydrogen sources. An interesting result was obtained, demonstrating that the in-situ hydrogen (formic acid) showed better HDO performance at mild temperatures (260, 300 ℃), while the HDO of pyrolysis oil with ex-situ hydrogen (H2 gas) at higher temperatures (325 or 350 ℃) with respects to degree of deoxygenation and the quality of the produced upgraded oils. HDO of the woody derived pyrolysis oil with total acid number (TAN) of 136.0 mgKOH/g at 350 ℃ for 2 h over Ru/C catalyst with formic acid or hydrogen gas resulted in 74% and 85% degree of de-oxygenation, respectively, producing high quality upgraded oils with TAN of 35.3 mgKOH/g and 50.1 mgKOH/g and HHV of 39.5 MJ/kg and 43.0 MJ/kg, respectively.
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