Biodiesel is a notable alternative to petroleum derived diesel fuel because it comes from natural domestic sources and thus reduces dependence on diminishing petroleum fuel from foreign sources, it likely lowers lifecycle greenhouse gas emissions, and it lowers an engine’s emission of most pollutants as compared to petroleum derived diesel. However, the use of biodiesel often slightly increases a diesel engine’s emission of smog forming nitrogen oxides (NOx) relative to petroleum diesel. In this paper, previously proposed theories for this slight NOx increase are reviewed, including theories based on biodiesel’s cetane number, which leads to differing amounts of charge preheating, and theories based on the fuel’s bulk modulus, which affects injection timing. This paper proposes an additional theory for the slight NOx increase of biodiesel. Biodiesel typically contains more double bonded molecules than petroleum derived diesel. These double bonded molecules have a slightly higher adiabatic flame temperature, which leads to the increase in NOx production for biodiesel. Our theory was verified using numerical simulations to show a NOx increase, due to the double bonded molecules, that is consistent with observation. Further, the details of these numerical simulations show that NOx is predominantly due to the Zeldovich mechanism.

Interest in the use of alternative fuels and engines is increasing as the price of petroleum climbs. The inherently higher efficiency of Diesel engines has led to increased adoption of Diesels in Europe, capturing approximately 40% of the new passenger car market. Unfortunately, lower CO2 emissions are countered with higher nitrogen oxides (NOx) and particulate matter (PM) emissions, and higher noise. Noise and PM have traditionally been the obstacles toward consumer acceptance of Diesel passenger cars in North America, while NOx (a key component in photochemical smog) has been more of an engineering challenge. Diesels have non-premixed combustion with excess oxygen; reducing NOx to N2 in an oxygen rich environment is difficult. Adding oxygenated compounds to the fuel helps reduce PM emissions. However, relying on fuel alone to reduce PM is unrealistic due to economic constraints and difficult due to the emerging PM standards. Keeping peak combustion temperature below 1700 K inhibits NOx formation. Altering the combustion regime to burn at temperatures below the NOx threshold and accept a wide variety of fuels seems like a promising alternative for future engines. Homogeneous Charge Compression Ignition (HCCI) is a possible solution. Fuel and air are well mixed prior to intake into a cylinder (homogeneous charge) and ignition occurs by compression of the fuel-air mixture by the piston. HCCI is rapid and relatively cool, producing little NOx and PM. Unfortunately, it is hard to control since HCCI is initiated by temperature and pressure instead of a spark or direct fuel injection. We investigate biofuel HCCI combustion, and use intrinsically labeled biofuels as tracers of HCCI combustion. Data from tracer experiments are used to improve our combustion modeling.

The influence of the small amounts (1-3%) of the additive di-tertiary butyl peroxide (DTBP) on the combustion event of Homogeneous Charge Compression Ignition (HCCI) engines was investigated using engine experiments, numerical modeling, and carbon-14 isotope tracing. DTBP was added to neat ethanol and diethyl ether (DEE) in ethanol fuel blends for a range of combustion timings and engine loads. The addition of DTBP to the fuel advanced combustion timing in each instance, with the DEE-in-ethanol mixture advancing more than the ethanol alone. A numerical model reproduced the experimental results. Carbon-14 isotope tracing showed that more ethanol burns to completion in DEE-in-ethanol blends with a DTBP additive when compared to results for DEE-in-ethanol without the additive. However, the addition of DTBP did not elongate the heat release in either case. The additive advances combustion timing for both pure ethanol and for DEE-in-ethanol mixtures, but the additive results in more of an advance in timing for the DEE-in-ethanol mixture. This suggests that although there are both thermal and kinetic influences from the addition of DTBP, the thermal effects are more important.

Despite the rapid combustion typically experienced in Homogeneous Charge Compression Ignition (HCCI), components in fuel mixtures do not ignite in unison or burn equally. In our experiments and modeling of blends of diethyl ether (DEE) and ethanol (EtOH), the DEE led combustion and proceeded further toward completion, as indicated by 14C isotope tracing. A numerical model of HCCI combustion of DEE and EtOH mixtures supports the isotopic findings. Although both approaches lacked information on incompletely combusted intermediates plentiful in HCCI emissions, the numerical model and 14C tracing data agreed within the limitations of the single zone model. Despite the fact that DEE is more reactive than EtOH in HCCI engines, they are sufficiently similar that we did not observe a large elongation of energy release or significant reduction in inlet temperature required for light-off, both desired effects for the combustion event. This finding suggests that, in general, HCCI combustion of fuel blends may have preferential combustion of some of the blend components.