With the increasing demand for net-zero sustainable aviation fuels (SAF), new conversion technologies are needed to process waste feedstocks and meet carbon reduction and cost targets. Wet waste is a low-cost, prevalent feedstock with the energy potential to displace over 20% of US jet fuel consumption; however, its complexity and high moisture typically relegates its use to methane production from anaerobic digestion. To overcome this, methanogenesis can be arrested during fermentation to instead produce C2 to C8 volatile fatty acids (VFA) for catalytic upgrading to SAF. Here, we evaluate the catalytic conversion of food waste–derived VFAs to produce n-paraffin SAF for near-term use as a 10 vol% blend for ASTM “Fast Track” qualification and produce a highly branched, isoparaffin VFA-SAF to increase the renewable blend limit. VFA ketonization models assessed the carbon chain length distributions suitable for each VFA-SAF conversion pathway, and food waste–derived VFA ketonization was demonstrated for >100 h of time on stream at approximately theoretical yield. Fuel property blending models and experimental testing determined normal paraffin VFA-SAF meets 10 vol% fuel specifications for “Fast Track.” Synergistic blending with isoparaffin VFA-SAF increased the blend limit to 70 vol% by addressing flashpoint and viscosity constraints, with sooting 34% lower than fossil jet. Techno-economic analysis evaluated the major catalytic process cost-drivers, determining the minimum fuel selling price as a function of VFA production costs. Life cycle analysis determined that if food waste is diverted from landfills to avoid methane emissions, VFA-SAF could enable up to 165% reduction in greenhouse gas emissions relative to fossil jet.
Bio-oil derived by fast pyrolysis of biomass represents a potentially attractive source of hydrocarbon transportation fuels. Raw bio-oil however is completely unsuitable for application as a fuel due primarily to high organic oxygen content, which imparts a number of undesirable properties including high acidity and low stability. These problems can be overcome by catalytic hydrodeoxygenation (HDO); however, removing oxygen to very low levels by hydrotreating carries a strong economic penalty. Mild hydrotreating (where moderate levels of deoxygenation take place) coupled with coprocessing in a petroleum refinery represents an alternative to deep hydrotreating, which may help improve the economics of manufacture of hydrocarbon transportation fuels from biomass. This study reports on the effect of reaction severity on the quality of bio-oil produced via mild hydrotreating in a semibatch reactor using conventional hydroprocessing catalysts. Detailed speciation of oxygen functional groups in distillate and bottoms products has been carried out, and the fate of organic oxygen as a function of reaction severity has been determined. The results indicate that acceptable refinery blendstocks and perhaps final fuels can be produced by mild hydrotreating.
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 C2and C4carboxylic 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 C11branched 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.
Applying a rational design approach to produce a high-quality, low-sooting hydrocarbon diesel blendstock from lignocellulosic biomass-derived short-chain carboxylic acids.
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