RESUMO
Lignocellulosic biomass offers a renewable carbon source which can be anaerobically digested to produce short-chain carboxylic acids. Here, we assess fuel properties of oxygenates accessible from catalytic upgrading of these acids a priori for their potential to serve as diesel bioblendstocks. Ethers derived from C2 and C4 carboxylic acids are identified as advantaged fuel candidates with significantly improved ignition quality (>56% cetane number increase) and reduced sooting (>86% yield sooting index reduction) when compared to commercial petrodiesel. The prescreening process informed conversion pathway selection toward a C11 branched ether, 4-butoxyheptane, which showed promise for fuel performance and health- and safety-related attributes. A continuous, solvent-free production process was then developed using metal oxide acidic catalysts to provide improved thermal stability, water tolerance, and yields. Liter-scale production of 4-butoxyheptane enabled fuel property testing to confirm predicted fuel properties, while incorporation into petrodiesel at 20 vol % demonstrated 10% improvement in ignition quality and 20% reduction in intrinsic sooting tendency. Storage stability of the pure bioblendstock and 20 vol % blend was confirmed with a common fuel antioxidant, as was compatibility with elastomeric components within existing engine and fueling infrastructure. Technoeconomic analysis of the conversion process identified major cost drivers to guide further research and development. Life-cycle analysis determined the potential to reduce greenhouse gas emissions by 50 to 271% relative to petrodiesel, depending on treatment of coproducts.
