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Adding oxygenates to diesel fuel has shown the potential for reducing particulate (PM) emissions in the exhaust. The objective of this study was to select the most promising oxygenate compounds as blending components in diesel fuel for advanced engine testing. A fuel matrix was designed to consider the effect of molecular structure and boiling point on the ability of oxygenates to reduce engine-out exhaust emissions from a modern diesel engine. Nine test fuels including a low-sulfur (∼1 ppm), low-aromatic hydrocracked base fuel and 8 oxygenate-base fuel blends were utilized. All oxygenated fuels were formulated to contain 7% wt. of oxygen. A DaimlerChrysler OM611 CIDI engine for light-duty vehicles was controlled with a SwRI Rapid Prototyping Electronic Control System. The base fuel was evaluated in four speed-load modes and oxygenated blends only in one mode. Each operating mode and fuel combination was run in triplicate.

Comparative emission measurements were made in two dynamometer-based diesel engines using protocol specified by the U.S. Environmental Protection Agency (EPA) and the California Air Resources Board (CARB). A single JP-8 fuel with a sulfur level of 0.06 weight percent (wt%) was adjusted to sulfur levels of 0.11 and 0.26 wt%. The emission characteristics of the three fuels were compared to the 1994 EPA certification low-sulfur diesel fuel (sulfur level equal to 0.035 wt%) in the Detroit Diesel Corporation (DDC) 1991 prototype Series 60 diesel engine and in the General Motors (GM) 6.2L diesel engine. Comparisons were made using the hot-start transient portion of the heavy-duty diesel engine Federal Test Procedure. Results from the Army study show that the gaseous emissions for the DDC Series 60 engine using kerosene-based JP-8 fuel are equivalent to values obtained with the 0.035 wt% sulfur EPA certification diesel fuel.

A second carbonyl round robin was conducted to enable participating laboratories doing routine analysis of carbonyls in vehicle exhaust emissions to assess their analytical capabilities. Three sets of solutions in acetonitrile containing varying number and amounts of standard DNPH-carbonyls were prepared. The parent carbonyls are known components of vehicle exhaust emissions. The samples were designed to challenge the capabilities of the participants to separate, identify and quantify all the components. The fourteen participating laboratories included automotive, contract, petroleum and regulatory organizations. All participants were able to separate and identify the C3 carbonyls; a few were not able to separate MEK from butyraldehyde and methacrolein from butyraldehyde; and many were not able to separate adequately the isomers of tolualdehyde. Inadequate separation and lack of appropriate standards resulted in a few misidentifications.

Previously we reported (SAE Paper 2005-01-0475) that emissions of toxicologically relevant compounds from an engine operating at low NOx conditions using Fischer-Tropsch fuel (FT100) were lower than those emissions from the engine using an ultra-low sulfur (15 PPM sulfur) diesel fuel (BP15). Those tests were performed at two operating modes: Mode 6 (4.2 bar BMEP, 2300 RPM) and Mode 11 (2.62 bar BMEP, 1500 RPM). We wanted to evaluate the effect on emissions of operating the engine at low power (near idle) in conjunction with the low NOx strategy. Specifically, we report on emissions of total hydrocarbon (HC), carbon monoxide (CO), NOx, particulates (PM), formaldehyde, acetaldehyde, benzene, 1,3-butadiene, gas phase polyaromatic hydrocarbons (PAH's) and particle phase PAH's from a DaimlerChrysler OM611 CIDI engine using a low NOx engine operating strategy at Mode 22 (1.0 bar BMEP and 1500 RPM).

A previous paper reported (SAE Paper 2002-01-2884) that it was possible to decrease mode-weighted NOx emissions compared to the OEM calibration with corresponding increases in particulate matter (PM) emissions. These PM emission increases were partially overcome with the use of oxygenated diesel fuel additives. We wanted to know if compounds of toxicological concern were emitted more or less using oxygenated diesel fuel additives that were used in conjunction with a modified engine operating strategy to lower engine-out NOx emissions. Emissions of toxicologically relevant compounds from fuels containing triproplyene glycol monomethyl ether and dibutyl maleate were the same or lower compared to a low sulfur fuel (15 ppm sulfur) even under engine operating conditions designed to lower engine-out NOx emissions.