Adsorption Characteristics between Ti Atoms of TiO2(100) and Corrosive Species of CO2-H2S-Cl− System in Oil and Gas Fields

Abstract

The service environment of OCTG (Oil Country Tubular Goods) in oil and gas fields is becoming more and more severe due to the strong affinity between ions or atoms of corrosive species coming from solutions and metal ions or atoms on metals. While it is difficult for traditional technologies to accurately analyze the corrosion characteristics of OCTG in CO2-H2S-Cl− systems, it is necessary to study the corrosion-resistant behavior of TC4 (Ti-6Al-4V) alloys based on an atomic or molecular scale. In this paper, the thermodynamic characteristics of the TiO2(100) surface of TC4 alloys in the CO2-H2S-Cl− system were simulated and analyzed by first principles, and the corrosion electrochemical technologies were used to verify the simulation results. The results indicated that all of the best adsorption positions of corrosive ions (Cl−, HS−, S2−, HCO3−, and CO32−) on TiO2(100) surfaces were bridge sites. A forceful charge interaction existed between Cl, S, and O atoms in Cl−, HS−, S2−, HCO3−, CO32−, and Ti atoms in TiO2(100) surfaces after adsorption in a stable state. The charge was transferred from near Ti atoms in TiO2 to near Cl, S, and O atoms in Cl−, HS−, S2−, HCO3−, and CO32−. Electronic orbital hybridization occurred between 3p5 of Cl, 3p4 of S, 2p4 of O, and 3d2 of Ti, which was chemical adsorption. The effect strength of five corrosive ions on the stability of TiO2 passivation film was S2− > CO32− > Cl− > HS− > HCO3−. In addition, the corrosion current density of TC4 alloy in different solutions containing saturated CO2 was as follows: NaCl + Na2S + Na2CO3 > NaCl + Na2S > NaCl + Na2CO3 > NaCl. At the same time, the trends of Rs (solution transfer resistance), Rct (charge transfer resistance), and Rc (ion adsorption double layer resistance) were opposite to the corrosion current density. The corrosion resistance of TiO2 passivation film to corrosive species was weakened owing to the synergistic effect of corrosive species. Severe corrosion resulted, especially pitting corrosion, which further proved the simulation results mentioned above. Thus, this outcome provides the theoretical support to reveal the corrosion resistance mechanism of OCTG and to develop novel corrosion inhibitors in CO2-H2S-Cl− environments.

Localized Corrosion of Stainless Steel Triggered by Typical Inclusions in NaCl Solution: Oxy-Sulfide and MnS

“…The microelectrochemical behavior for both inclusions needs to be further investigated to make precise conclusions. In future work, not only should the complete localized corrosion mechanism in stainless steel be refined by more precise instruments or simulation/calculations, such as high-resolution transmission electron microscopy and DFT calculations [ 47 ], but corresponding corrosion protection methods should also be explored, such as the application of corrosion inhibitors on stainless steel [ 48 , 49 ].…”

“…The microelectrochemical behavior for both inclusions needs to be further investigated to make precise conclusions. In future work, not only should the complete localized corrosion mechanism in stainless steel be refined by more precise instruments or simulation/calculations, such as high-resolution transmission electron microscopy and DFT calculations [47], but corresponding corrosion protection methods should also be explored, such as the application of corrosion inhibitors on stainless steel [48,49]. Moreover, it is worth mentioning that the current density of the matrix containing both inclusions increase faster than that of the matrix only after 0.3 V (area enclosed by yellow dotted lines in Figure 9), which may be due to the propagation of metastable pitting induced by inclusions.…”