Influence of film formers on magnetite properties under water-steam cycle conditions

Abstract

Corrosion and fouling are considered major factors affecting the performance of water-steam cycles (WSC). Flow-accelerated corrosion (FAC), present in feed and condensate systems, is a well known corrosion mechanism, eroding and dissolving the protective magnetite layers. Fouling of the boiler, by suspended magnetite particles, is partly controlled by forces arising due to surface charging. Film forming amines (FFA) are gaining acceptance as means to control FAC. However, its performance in low pH regions is unknown. In addition, despite FFA being a surfactant, its effect on the colloidal magnetite surface charge and point of zero charge (pzc) are unknown. This research set out to determine the effect
of FFAs on the formation of a protective magnetite layer and its resistance against acidic FAC, and to determine the effect of FFAs on the surface charge of colloidal magnetite. This study focused on two FFAs, Octadecylamine (ODA) and Oleyl Propylenediamine (OLDA). In 48h 230-250 ºC immersion corrosion tests magnetite layers were formed on C1010 coupons, inside a high pressure high temperature autoclave under different treatments: untreated (blank), 2ppm ODA and 2ppm Ammonia, 2ppm OLDA and 2ppm Ammonia, and only 2ppm Ammonia. 48h 150 ºC re-immersion corrosion tests were performed to test the magnetite layer performance under acidic (acetate 0.08ppm) FAC. After the corrosion tests, the layers were verified using XRD, EDS + SEM and Weigh-loss measurements. Potentiometric titrations were employed to measure the proton induced surface charge of magnetite particles (10g/L) at an ionic strength of 0.01, and 0.1 mol/kg (KNO3) in the presence or absence of ODA, or OLDA (2ppm) over a wide pH range, at 25, and 150 ºC. This gave the magnetite surface charge density curves. The pzc was determined using the inflection point of titrations (pHinfl) and common intersection point (pHcip). XRD confirmed the presence of magnetite layers on all coupons after the immersion and re-immersion tests. The SEM measured magnetite layer decrease after the re-immersion tests was: 19.1%, 14.5%, 8.6%, and 23.3% for blank, ODA, OLDA, and ammonia treatment respectively. Weight loss determined corrosion rates taken over both immersion and re-immersion tests were: 0.070, 0.057, 0.060, and 0.073 mm/y for blank, ODA, OLDA, and ammonia treatment respectively. All magnetite surface charge density curves were unaffected by the presence of ODA, and OLDA, except for ODA at 0.1 mol/kg KNO3 and 25 ºC, which resulted in a raised/neutralized surface charge density curve in the alkaline pH region. Magnetite layers formed under ODA, and OLDA additions were smoother, thinner, and more uniform compared to layers formed under an ammonia only chemistry, and blank chemistry. Layers formed under the ODA, and OLDA chemistries were better resistant against acidic FAC and offered better protection, in terms of corrosion rate. At the applied concentration ratio, and ionic strength of 0.01M, ODA, and OLDA did not affect the magnetite colloid surface charge over pH. However, both caused magnetite particles to agglomerate. At higher ionic strengths of 0.1M, ODA neutralized the magnetite surface charge in the alkaline region.