Evaluation of Minimum NOx Emission From Ammonia Combustion

Abstract

Ammonia (NH3) is being explored as a hydrogen carrier with no carbon emissions. However, if burned directly as NH3, rather than being completely decomposed back to N2/H2, the fuel-bound nitrogen comes with a potentially significant NOx emissions penalty. Indeed, several existing studies are showing ammonia combustion NOx emissions that exceed current natural gas fueled, DLN technologies by one to two orders of magnitude. Therefore, it is important to establish the theoretical minimum NOx emissions for an ammonia combustor, to determine how much NOx levels can be reduced via further technology development. In other words, the purpose of this work is not to analyze the performance of a specific combustor but, rather, the fundamental limits of what is achievable. This study quantifies this minimum NOx level for a two-stage combustor system for a given combustor exit temperature and residence time, with a constraint on unburned fuel levels. As expected, the optimum configuration is a rich front end combustor to burn and crack ammonia with significant H2 production, followed by an NO relaxation reactor, followed by a lean stage that consumes the remaining H2. The optimum residence time and stoichiometry of each zone are determined in the fast mixing limit, which essentially balances between NOx production in the primary and secondary zones. These results show minimum NOx levels are in 200–400 ppm range at 1 bar, but drop to levels of ∼25 ppm at 20 bar. These NOx emissions are dominated by NOx production in the primary stage which relaxes to equilibrium levels quite slowly. As processes controlling NOx relaxation to equilibrium in the primary stage dominate overall NO emission levels, combustor NOx sensitivities are essentially opposite that of natural gas fired, DLN systems. Specifically, NOx values drop with increased combustor residence time, increased pressure, and increased combustor exit temperature. These results also suggest that the most important strategy for NOx minimization is to provide sufficient relaxation time after the primary zone for NOx to approach equilibrium—this can be done via kinetic means to accelerate this relaxation rate, such as enhancing pressure or temperature, or increasing residence times. Indeed, this work shows that low pressure combustors specifically optimized for ammonia will have residence times that are one to two orders of magnitude larger than current natural gas systems. By doing so, NOx levels below 10 ppm may be achievable. Finally, we discuss the sensitivity of these values to uncertainties in ammonia kinetics.