Formation mechanism of NOx precursors during the pyrolysis of 2,5-diketopiperazine based on experimental and theoretical study

Abstract

Incineration of food waste leads to the release of NO_x pollutants, whereas the formation mechanism of the NO_x precursors (HCN, NH₃, and HNCO) during the initial pyrolysis process is far from well-studied, limiting the source control on NO_x release. In this work, 2,5-diketopiperazine (DKP) was selected as the N-containing model compound to study the formation mechanism of NO_x precursors in food waste pyrolysis, by combining experiments and density functional theory (DFT) calculations. The C1-N2 bond broken via the N2-to-N5 H-transfer possesses the lowest energy barrier, together with the largest reaction rate constants in the range of 400-800 °C. NH₃ can be easily generated with low energy barriers and high rate constants at low temperatures (below 630 °C). Whereas, the rate constants of the pathways for HCN formation will exceed those for NH₃ generation in the range of 630-740 °C. In addition, the DKP pyrolysis can also lead to the formation of HNCO with a very low energy barrier, and it can convert into HCN and NH₃ through further hydrogenation and decomposition. These calculation results are exactly consistent with the experimental results that NH₃ was the main precursor in the range of 400-600 °C, and the yield of HCN exceeded that of NH₃ when the temperature was over 600 °C. Our current work on the formation mechanism of NO_x precursors during the pyrolysis of DKP can provide theoretical guidance for the development of NO_x control technology in the pyrolysis/combustion process of organic waste.

Keywords: 2,5-Diketopiperazine; Density functional theory; NO(x) precursors; Pyrolysis.