Emission reduction by targeted transient <delta> operations in three-way catalysts for heavy-duty natural gas applications

To curb the severe effects of climate change, our society needs to radically reduce its CO2 footprint. For the heavy-duty sector, where electrification is difficult, alternative fuels can be the solution. Methane-fueled engines have lower energy-specific CO2 emissions than conventional Diesel-fueled engines. Furthermore, they have the potential of becoming carbon-neutral, when combined with bio-methane/synthetic methane. However, oxidation of unburnt methane in the exhaust gas poses a challenge for aftertreatment systems. The aim of this thesis is to investigate the mechanism of methane abatement and to reveal methods to reduce methane and other hazardous gas emissions. The majority of the experiments were conducted directly on an engine test bench, which is rarely seen in studies focusing on catalytic reaction pathways. Initial investigations focused on methane abatement under steady state and λ-step transitions. Under steady state, the presence of oxygen was identified as a prerequisite for methane conversion. Reacting with oxygen is the only methane conversion pathway. However, after step transition from oxygen excess conditions (slightly lean) to oxygen-poor conditions (slightly rich), high methane conversion was observed under rich conditions with no oxygen available. This high conversion was attributed to steam reforming (SR), which was activated by the step transition. The SR reaction rate decreased over time when staying at rich conditions, until full deactivation. Investigations in the lab-scale model gas reactor confirmed this analysis. In addition, the reason for SR deactivation was identified by DRIFTS measurements as the accumulation of carbonates on the catalytic surface, blocking the active sites. Based on the identified importance of the SR reaction, targeted λ oscillations across stoichiometry were introduced, in order to repeatably activate SR and achieve sustainable high methane conversion. During the rich parts of the oscillations, methane was converted via SR, while, during lean parts, the carbonates were periodically removed from the catalyst surface. With these oscillations, methane conversion has been significantly improved, in comparison to steady state. In parallel, a numerical model has been developed in order to simulate the catalyst behavior under oscillating conditions. The model provided insights on the reaction pathways and their distribution along the catalyst axis. The catalytic activity of the different Platinum-group metals has been investigated for the identified reactions. Various catalysts of different compositions were tested under cold start, λ oscillations and quasi-steady state conditions. Both Pt and Pd activated SR reactions, however SR attenuation was faster in Pt catalysts. In lean conditions, Pt exhibited higher methane oxidation. Rh was identified as important for enhancing NOx reduction and lowering NH3 emissions. The combination of all three metals has improved the overall catalyst performances. In the final part of the thesis, a special aftertreatment system was investigated. It combines a Pd/Rh catalyst subject to stoichiometric conditions with a Pt oxidation catalyst subject to lean conditions. In the Pd/Rh catalyst, methane was removed via λ oscillations. In the Pt catalyst, the remaining CO, H2 and NH3 were oxidized. The setup provided a novel perspective in reducing the overall environmental impacts.