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Effect of hydrogen peroxide on the thermal characteristics in the decomposition of N–methylmorpholine–N–oxide

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Abstract

This paper is focused on the effect of hydrogen peroxide (H2O2) on the thermal decomposition of N–methylmorpholine–N–oxide (NMMO). First, accelerating rate calorimetry (ARC) was used to investigate the thermal characteristics of NMMO/H2O2 with different molar ratios. It was found that “onset” temperature was reduced to the minimum temperature with 391.67 K as the molar ratio of NMMO/H2O2 was 3:1. Second, the main decomposed products of NMMO and NMMO/H2O2 were 4–methylmorpholine (NMM) and morpholine (M) identified by liquid chromatography-mass spectrometry (LC–MS). The presence of H2O2 was beneficial to generate more M. Finally, microreactor calorimetry (C80) was employed to calculate the time to maximum rate (TMRad) and the temperature as TMRad is 24 h combined with Friedman and Flynn–Wall–Ozawa models during the decomposition of NMMO and NMMO/H2O2 (molar ratio of 3:1). The apparent activation energy (Ea,ARC) of pure NMMO with 274.99 kJ mol−1 was higher than that of NMMO in the mixture (NMMOmix) with 123.71 kJ mol−1. Besides, TMRad,s of NMMOmix decreased from 39.77 to 27.96 min, and no obvious decrease of TD24 was found compared with the pure NMMO. The results indicated that the presence of H2O2 increased the risk of thermal runaway of NMMOmix, and the mixture had the worst thermal stability as the molar ratio of NMMO/H2O2 was 3:1. It was worthy of mentioning that the most hazardous moment was not the dosing end, but the generated NMMO and H2O2 was reached to 3:1 in the synthesis of NMMO.

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Data availability

The data used to support the findings of this study are available from the corresponding author upon request.

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Authors and Affiliations

  1. School of Safety Engineering, Bei**g Institute of Petrochemical Technology, Bei**g, 102617, China

    Jiancun Gao, Yu**g Li, Wei Wang & Chenguang Shi

  2. Bei**g Academy of Safety Engineering and Technology, Bei**g, 102617, China

    Jiancun Gao & Wei Wang

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Gao, J., Li, Y., Wang, W. et al. Effect of hydrogen peroxide on the thermal characteristics in the decomposition of N–methylmorpholine–N–oxide. J Therm Anal Calorim 147, 13781–13792 (2022). https://doi.org/10.1007/s10973-022-11680-2

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