| Due to the law of supply and demand, the last decade has witnessed a skyrocketing in the price of light sweet crude oil. Therefore, refineries are increasingly interested in "opportunity crudes", characterized by their discounted price and relative ease of procurement. However, the attractive economics of opportunity crudes come with the disadvantage of high acid/organosulfur compound content, which could lead to corrosion and even failure of facilities in refineries. However, it is generally accepted that organosulfur compounds may form protective iron sulfide layers on the metal surface and decrease the corrosion rate. Therefore, it is necessary to investigate the corrosive property of crudes at high temperatures, the mechanism of corrosion by acids (naphthenic acids) in the presence of organosulfur compounds, and methods to mitigate its corrosive effect.;In 2004, an industrial project was initiated at the Institute for Corrosion and Multiphase Technology to investigate the corrosion by naphthenic acids and organosulfur compounds. In this project, for each experiment there were two experimentation phases: pretreatment and challenge. In the first pretreatment phase, a stirred autoclave was filled with a real crude oil fraction or model oil of different acidity and organosulfur compound concentration. Then, the stirred autoclave was heated to high temperatures to examine the corrosivity of the oil to different materials (specimens made from CS and 5% Cr containing steel were used). During the pretreatment, corrosion product layers were formed on the metal surface.;In the second challenge phase, the steel specimens pretreated in the first phase were inserted into a rotating cylinder autoclave, called High Velocity Rig (HVR). The HVR was fed with a high-temperature oil solution of naphthenic acids to attack the iron sulfide layers. Based on the difference of specimen weight loss between the two steps, the net corrosion rate could be calculated and the protectiveness of corrosion product layer against naphthenic acid corrosion could be assessed.;Routinely, the layers generated in pretreatment and challenge phases were investigated with SEM/EDS (Scanning Electron Microscopy/Energy Dispersive Spectroscopy). Selectively, some thin layers formed in the first or second phase were analyzed with FIB-TEM (Focused Ion Beam - Transmission Electron Microscopy).;FIB-TEM analysis revealed that there was an iron oxide layer beneath the iron sulfide layer. Experimental results showed that the iron oxide layer was closely related to the layer protectiveness against naphthenic acid corrosion and its formation was due to the presence of naphthenic acids in the fluid.;Finally, a new mechanism of naphthenic acid/organosulfur compound corrosion was proposed based on properties of crudes, results of corrosion experimentation, and microscopic analysis of developed surface layers. |
