Interactions in Ammonia and Hydrogen Oxidation Examined in a Flow Reactor and a Shock Tube

Denghao Zhu; Lena Ruwe; Steffen Schmitt; Bo Shu; Katharina Kohse-Höinghaus; Arnas Lucassen

doi:10.1021/acs.jpca.2c07784

Interactions in Ammonia and Hydrogen Oxidation Examined in a Flow Reactor and a Shock Tube

J Phys Chem A. 2023 Mar 16;127(10):2351-2366. doi: 10.1021/acs.jpca.2c07784. Epub 2023 Mar 6.

Authors

Denghao Zhu¹, Lena Ruwe², Steffen Schmitt³, Bo Shu¹, Katharina Kohse-Höinghaus³, Arnas Lucassen²

Affiliations

¹ Department of Physical Chemistry, Physikalisch-Technische Bundesanstalt (PTB), 38116 Braunschweig, Germany.
² Department of Fundamentals of Explosion Protection, Physikalisch-Technische Bundesanstalt (PTB), 38116 Braunschweig, Germany.
³ Department of Chemistry, Bielefeld University, Universitätsstraße 25, 33615 Bielefeld, Germany.

PMID: 36877868
DOI: 10.1021/acs.jpca.2c07784

Abstract

Ammonia (NH₃) is a promising fuel, because it is carbon-free and easier to store and transport than hydrogen (H₂). However, an ignition enhancer such as H₂ might be needed for technical applications, because of the rather poor ignition properties of NH₃. The combustion of pure NH₃ and H₂ has been explored widely. However, for mixtures of both gases, mostly only global parameters such as ignition delay times or flame speeds were reported. Studies with extensive experimental species profiles are scarce. Therefore, we experimentally investigated the interactions in the oxidation of different NH₃/H₂ mixtures in the temperature range of 750-1173 K at 0.97 bar in a plug-flow reactor (PFR), as well as in the temperature range of 1615-2358 K with an average pressure of 3.16 bar in a shock tube. In the PFR, temperature-dependent mole fraction profiles of the main species were obtained via electron ionization molecular-beam mass spectrometry (EI-MBMS). Additionally, for the first time, tunable diode laser absorption spectroscopy (TDLAS) with a scanned-wavelength method was adapted to the PFR for the quantification of nitric oxide (NO). In the shock tube, time-resolved NO profiles were also measured by TDLAS using a fixed-wavelength approach. The experimental results both in PFR and shock tube reveal the reactivity enhancement by H₂ on ammonia oxidation. The extensive sets of results were compared with predictions by four NH₃-related reaction mechanisms. None of the mechanisms can well predict all experimental results, but the Stagni et al. [React. Chem. Eng. 2020, 5, 696-711] and Zhu et al. [Combust. Flame 2022, 246, 115389] mechanisms perform best for the PFR and shock tube conditions, respectively. Exploratory kinetic analysis was conducted to identify the effect of H₂ addition on ammonia oxidation and NO formation, as well as sensitive reactions in different temperature regimes. The results presented in this study can provide valuable information for further model development and highlight relevant properties of H₂-assisted NH₃ combustion.