Properties That Potentially Limit High-Level Blends of Biomass-Based Diesel Fuel.

While today's biomass-based diesel fuels are used at relatively low blend levels in petroleum diesel, decarbonization of the heavy-duty trucking and off-road sectors is driving increasing use of higher level blends and the combination of hydroprocessing-derived renewable diesel (RD) with biodiesel (fatty acid methyl esters) to create a 100% renewable fuel. However, little data are available on the properties of biodiesel blends over 20 vol % into RD or conventional diesel, despite the potential for properties to fall well outside the normal range for diesel fuels. Here, we evaluate the properties of 20-80% blends of a soy-derived biodiesel into RD and petroleum diesel. Properties measured were flash point, cloud point, cetane number, surface tension, density, kinematic viscosity, distillation curve, lower heating value, water content, water solubility in the fuel, lubricity, and oxidation stability. Density and viscosity were measured over a wide temperature range. A key objective was to reveal properties that might limit blending of biodiesel and any differences between biodiesel blends into RD versus petroleum diesel and to understand research needed to advance the use of high-level blends and 100% renewable fuel. Properties that may limit blending include the cloud point, viscosity, distillation curve, and oxidation stability. Meeting cloud point requirements can be an issue for all distillate fuels. For biodiesel, reducing the blend level and use of lower cloud point hydrocarbon blendstocks, such as No. 1 diesel or kerosene, can be used in winter months. Alternatively, a heated fuel system that allows for starting the vehicle on conventional diesel before switching to pure biodiesel (B100) or a high-level blend has been successfully demonstrated in the literature. Some biodiesels can have kinematic viscosity above the upper limit for diesel fuels (4.1 mm2/s), which will limit the amount that can be blended. Biodiesel boils in a narrow range at the very high end of the No. 2 diesel range. Additional research is needed to understand how the high T90 of B100 and high-level blends and the very low distillation range of B100, some RD samples, and high-level biodiesel blends impact lube oil dilution, engine deposits, and diesel oxidation catalyst light-off. Blending with No. 1 diesel or kerosene or biodiesel-specific engine calibrations may mitigate these issues. Oxidation stability of higher level blends is poorly understood but may be addressed through the increased use of antioxidant additives. Finally, high-level biodiesel blends and B100 will have significantly higher density, viscosity, and surface tension compared to conventional diesel. In combination with the high boiling point, these properties may impact fuel spray atomization and evaporation, and additional research is needed in this area.

Screening and evaluation of biomass upgrading strategies for sustainable transportation fuel production with biomass-derived volatile fatty acids.

Biomass conversion to fuels and chemicals is crucial to decarbonization, but choosing an advantageous upgrading pathway out of many options is challenging. Rigorously evaluating all candidate pathways (process simulation, product property testing) requires a prohibitive amount of research effort; even simple upgrading schemes have hundreds of possible permutations. We present a method enabling high-throughput screening by approximating upgrading unit operations and drop-in compatibility of products (e.g., fuel properties) and apply it to volatile fatty acid (VFA) conversion to liquid transportation fuels via a MATLAB script, VFA Upgrading to Liquid Transportation fUels Refinery Estimation (VULTURE). VULTURE selects upgrading configurations that maximize fuel blend bio-derived content. We validate VULTURE's approximations through surrogate fuel property testing and process simulation. Techno-economic and life cycle analyses suggest that VFA upgrading processes down-selected by VULTURE are profitable and have low carbon intensities, demonstrating the potential for the strategy to accelerate process development timelines at decreased costs.

Impact of higher alcohols blended in gasoline on light-duty vehicle exhaust emissions.

Certification gasoline was splash blended with alcohols to produce four blends: ethanol (16 vol%), n-butanol (17 vol%), i-butanol (21 vol%), and an i-butanol (12 vol%)/ethanol (7 vol%) mixture; these fuels were tested in a 2009 Honda Odyssey (a Tier 2 Bin 5 vehicle) over triplicate LA92 cycles. Emissions of oxides of nitrogen, carbon monoxide, non-methane organic gases (NMOG), unburned alcohols, carbonyls, and C1-C8 hydrocarbons (particularly 1,3-butadiene and benzene) were determined. Large, statistically significant fuel effects on regulated emissions were a 29% reduction in CO from E16 and a 60% increase in formaldehyde emissions from i-butanol, compared to certification gasoline. Ethanol produced the highest unburned alcohol emissions of 1.38 mg/mile ethanol, while butanols produced much lower unburned alcohol emissions (0.17 mg/mile n-butanol, and 0.30 mg/mile i-butanol); these reductions were offset by higher emissions of carbonyls. Formaldehyde, acetaldehyde, and butyraldehyde were the most significant carbonyls from the n-butanol blend, while formaldehyde, acetone, and 2-methylpropanal were the most significant from the i-butanol blend. The 12% i-butanol/7% ethanol blend was designed to produce no increase in gasoline vapor pressure. This fuel's exhaust emissions contained the lowest total oxygenates among the alcohol blends and the lowest NMOG of all fuels tested.

Impact of adaptation on flex-fuel vehicle emissions when fueled with E40.

Nine flex-fuel vehicles meeting Tier 1, light duty vehicle-low emission vehicle (LDV-LEV), light duty truck 2-LEV (LDT2-LEV), and Tier 2 emission standards were tested over hot-start and cold-start three-phase LA92 cycles for nonmethane organic gases, ethanol, acetaldehyde, formaldehyde, acetone, nitrous oxide, nitrogen oxides (NO(x)), carbon monoxide (CO), and carbon dioxide (CO(2)), as well as fuel economy. Emissions were measured immediately after refueling with E40. The vehicles had previously been adapted to either E10 or E76. An overall comparison of emissions and fuel economy behavior of vehicles running on E40 showed results generally consistent with adaptation to the blend after the length of the three-phase hot-start LA92 test procedure (1735 s, 11 miles). However, the single LDT2-LEV vehicle, a Dodge Caravan, continued to exhibit statistically significant differences in emissions for most pollutants when tested on E40 depending on whether the vehicle had been previously adapted to E10 or E76. The results were consistent with an overestimate of the amount of ethanol in the fuel when E40 was added immediately after the use of E76. Increasing ethanol concentration in fuel led to reductions in fuel economy, NO(x), CO, CO(2), and acetone emissions as well as increases in emissions of ethanol, acetaldehyde, and formaldehyde.

Diesel particle filter and fuel effects on heavy-duty diesel engine emissions.

The impacts of biodiesel and a continuously regenerated (catalyzed) diesel particle filter (DPF) on the emissions of volatile unburned hydrocarbons, carbonyls, and particle associated polycyclic aromatic hydrocarbons (PAH) and nitro-PAH, were investigated. Experiments were conducted on a 5.9 L Cummins ISB, heavy-duty diesel engine using certification ultra-low-sulfur diesel (ULSD, S ≤ 15 ppm), soy biodiesel (B100), and a 20% blend thereof (B20). Against the ULSD baseline, B20 and B100 reduced engine-out emissions of measured unburned volatile hydrocarbons and PM associated PAH and nitro-PAH by significant percentages (40% or more for B20 and higher percentage for B100). However, emissions of benzene were unaffected by the presence of biodiesel and emissions of naphthalene actually increased for B100. This suggests that the unsaturated FAME in soy-biodiesel can react to form aromatic rings in the diesel combustion environment. Methyl acrylate and methyl 3-butanoate were observed as significant species in the exhaust for B20 and B100 and may serve as markers of the presence of biodiesel in the fuel. The DPF was highly effective at converting gaseous hydrocarbons and PM associated PAH and total nitro-PAH. However, conversion of 1-nitropyrene by the DPF was less than 50% for all fuels. Blending of biodiesel caused a slight reduction in engine-out emissions of acrolein, but otherwise had little effect on carbonyl emissions. The DPF was highly effective for conversion of carbonyls, with the exception of formaldehyde. Formaldehyde emissions were increased by the DPF for ULSD and B20.