Proposal of a new mechanism of ammonia on the coking inhibition of n-decane under supercritical conditions

Abstract

The coking problem of hydrocarbon fuel pyrolysis is the key factor affecting the application of active cooling technology for high-speed aircraft. The purpose of this work is to investigate the coking inhibition performance and coking mechanism of using ammonia as an additive during the thermal cracking. In this study, the pyrolysis and coking characteristics of supercritical n-decane were experimentally studied using an electrically heated tube. ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer), GC–MS (Gas Chromatograph Mass Spectrometer), SEM (Scanning Electron Microscope), EDS (Energy Dispersive Spectroscopy), TPO (Temperature Programmed Oxidation), and Raman spectroscopy are applied to characterize the anti-coking performance of the additives. The results show that the additive hardly affects the cracking of the fuel under high-temperature conditions, but the coke mass deposited on the inner surface of the tube is significantly reduced, and the coking inhibition rate can reach 80% at 750 °C. The addition of additives reduced the graphitization degree and oxidative activity of the coke. The maximum oxidation temperature of the coke obtained at 750 °C was reduced by 145 °C, and the ID/IG value of the Raman spectroscopy peak-fitting was 3.29. The new mechanism of the effect of additives on the formation of coking precursors and the deposition of coke on the surface of the tube wall is proposed. Ammonia can react with Ni of the inner metal tube and radicals generated by fuel cracking to form a carbonized film, achieving the effect of inhibiting metal catalytic coking. Meanwhile, the amino radicals generated by ammonia dehydrogenation can regulate the coking reaction path by forming a stable p-π conjugate structure with unsaturated radicals. Therefore, the research will contribute to a deeper comprehension of the coking inhibition mechanism and the development of more effective coking inhibitors, providing new technical support for active cooling technologies.