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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.

The overall program objectives were three fold: assess the benefits and limitations of oxygenated diesel fuels on engine performance and emissions identify oxygenates most suitable for potential use in future diesel formulations based on physico-chemical properties (e.g. flash point), toxicity, biodegradability and estimated cost of production perform limited emissions and performance testing of the oxygenated diesel blends select at least two oxygenated compounds for advanced engine testing In Part 1 of this program which is described in this paper, an extensive literature review was conducted to identify potential oxygenates for blending into diesel fuels. As many as 71 oxygenates were identified for the initial screening process. Based on a set of physical and chemical properties, a screening methodology was developed to select the 8 oxygenates that will be eligible for engine testing.

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.