Carl Justin Kamp

While biodiesel is one of many necessary steps forward in a cleaner transportation future, alkali metal residuals, including Na and K (in the form of oxides, sulfates, hydroxides, and carbonates) originating from fuel production catalysts were found to be detrimental to emissions control components. Na + K and Ca + Mg (also biodiesel production byproducts) are regulated by ASTM-D6751 standards (American Society for Testing and Materials) to be less than 5 ppm for B100; however, the literature gives examples of physical and chemical degradation of automotive emissions catalysts and their substrates with these Na and K residuals. The purpose of this study is to investigate the impacts of ash from Na-doped biodiesel fuel (B20) on a diesel particulate filter (DPF). Investigations found that the Na-ash accumulated in the DPF has several unique properties which help to fundamentally explain some of the interactions and impacts of biodiesel on the particle filter. The biodiesel-related Na-ash was found to (1) have a significantly lower melting temperature than typical ash from inorganic lubricant additives and Ultra Low Sulfur Diesel (ULSD) fuel resulting in ash particles sintered to the DPF catalyst/substrate, (2) have a primary particle size which is about an order of magnitude larger than typical ash, (3) produce a larger amount of ash resulting in significantly thick wall ash layers and (4) penetrate the DPF substrate about 3× deeper than typical ULSD and lubricant-related ash. This study utilizes numerous characterization techniques to investigate the interactions between biodiesel-related ash and a DPF, ranging from visualization to composition to thermal analysis methods. The findings suggest the need for tighter control of the thermal environment in the DPF when using biodiesel, additional/improved DPF cleaning efforts, and avoidance of unregulated biodiesel with high Na/K levels.

The catalytic oxidation of carbon by molecular oxygen was studied using C/Pt, Pt/C, Pt/Al₂O₃/C, Pt/CeO₂/C, Al₂O₃/C, and CeO₂/C model samples prepared by hole-mask colloidal lithography. By this technique, the degree of contact between platinum and carbon was controlled with high precision. The oxidation of carbon was monitored using atomic force microscopy and scanning electron microscopy. The results show that Pt in direct contact with carbon catalyzes the oxidation of carbon by spillover of dissociated oxygen from Pt to carbon. By physically separating Pt and carbon with a 10 nm thin spacer layer of Al₂O₃, the oxygen spillover was entirely blocked. However, through a corresponding spacer layer of CeO₂, carbon oxidation was still observed, either by oxygen spillover from Pt to carbon or directly dissociated on the ceria, although at a slower rate compared to the case with no spacer layer between Pt and carbon.