Experimental study of the methane/hydrogen/ammonia and ethylene/ammonia oxidation: Multi-parameter measurements using a shock tube combined with laser absorption spectroscopy

Abstract

Ammonia (NH3) is a promising hydrogen carrier and carbon-free fuel, which can be synthesized using renewable energy and has attracted increasing attention from both academic and industrial communities. This study selected six absorption lines and developed a laser absorption diagnostics system that can simultaneously measure the temperature, CO, CO2, H2O, NH3, and NO time-histories during the oxidation of CH4/H2/NH3 and C2H4/NH3 mixtures (equivalence ratio ϕ ≈ 1.2) behind reflected shock waves. Since the fuels were highly diluted to reduce the nonideal effects and heat release behind reflected shock waves, the maximum NO mole fraction was only ∼0.2% and led to a small absorption (< 2.0%). Therefore. the wavelength modulation spectroscopy (WMS-2f/1f) was used for the NO time-history measurements while the other species were measured using fixed-wavelength absorption spectroscopy. A total of thirteen kinetics models were used to interpret the measurements. The main differences between the model predictions and measured data lie in two aspects: the mixture reactivities and the NO production. Generally speaking, for both CH4/H2/NH3 and C2H4/NH3 mixtures, the Glarborg model performs the best in predicting the temperature and species time-histories but the differences still exist. The high-quality experimental data support further analyses and improvements. Detailed kinetics analyses based on the Glarborg 2018 model were performed. It indicates that H + O2 = O + OH is the most sensitive and promoting reaction for both mixtures, followed by the H-abstraction reactions of H2 and C2H4. Conversely, the H-abstraction reactions of CH4 and NH3 impede oxidation due to competition with promoting reactions for reactants (H, OH, or O). Moreover, subsequent reactions involving the produced CH3 or C2H3 radicals also have significant effects on oxidation. The reactions affecting the NO plateau were also selected as the basis to optimize the predicted NO plateau. Although updating the rate constants of some key reactions improved model performance for both mixtures, discrepancies still exist, particularly for the C2H4/NH3 mixture.