Abstract

ABSTRACT In petroleum storage tanks, sulfur-containing crude oil continues to corrode equipment, generating sulfur corrosion products such as FeS. These products exhibit rapid exothermic reactions upon contact with air, thereby increasing the risk of fires and explosions. Additionally, sulfur monomers precipitated from sulfur or other compounds present in crude oil can adhere to FeS, consequently altering its spontaneous combustion characteristics. To explore the impact of associated sulfur content on the spontaneous combustion characteristics of FeS during its formation, this research synthesized FeS and its sulfur mixtures with sulfur concentrations of 5%, 10%, 15%, and 20%. These mixtures were prepared using a liquid-phase method, which involved the synthesis of self-made active FeS followed by the addition of different sulfur components. Differences in the spontaneous combustion characteristics of the five groups of samples were investigated in stages by simultaneous thermal analysis. The trends of the characteristic parameters of spontaneous combustion of FeS with different percentages of sulfur-containing components were analyzed. Finally, the apparent activation energy values of FeS with FeS and its associated sulfur were calculated by using thermodynamic analysis in the room-temperature spontaneous combustion stage (RT-75℃) and high temperature combustion stage (160–250℃). The findings indicate that the presence of sulfur components enhances the reactivity of FeS, yet reduces its oxygen absorption saturation threshold, thus advancing the oxygen absorption endpoint and facilitating entry into the high-temperature combustion stage. Moreover, FeS and its associated sulfur exhibit prolonged sustained combustion times when the sulfur component percentage is below 10%, favorably influencing the combustion behavior of FeS. As the percentage of sulfur component increases (from 10% to 20%), the combustion duration temperature rises from 60°C to 95°C. Additionally, an increase in the percentage of sulfur component (from 10% to 20%) leads to a higher combustion temperature. The activation energies of the five samples were determined using the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) kinetic methods. During the room temperature spontaneous combustion stage, the activation energy increases from 65.05 kJ/mol to 112.44 kJ/mol as the percentage of sulfur component rises from 0% to 20%. During the high temperature combustion stage, the activation energy increased from 108.32 kJ/mol to 214.49 kJ/mol with the increase in the percentage of sulfur component. FeS and its associated sulfur necessitate energy to propel the process due to heat absorption from the melting of sulfur monomers. As the reaction progresses into the high temperature stage, the required activation energy escalates accordingly.

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