Since 1920, certain crude oils have been found to be corrosive in refineries. At
temperatures between 428 and 752°F (220 and 400°C), sulfur-containing and organic acid
species in crude oils are known to promote corrosion. Elemental sulfur, mercaptan, sulfide
and polysulfide species convert to hydrogen sulfide which attacks carbon and low-alloy steels.
Organic acids, such as naphthenic acids consisting of cycloalkane ring(s) with an attached
aliphatic chain having a terminal carboxylic acid group, have been implicated. However,
neither total sulfur content measured by elemental analyses, nor total acid content, measured
by total acid number (TAN), have been found to correlate well with corrosivity of engineering
alloys.
A fundamental study of the relationships between the molecular structure of organic acid
compounds to elevated temperature corrosion of refinery alloys has been performed. In
particular, the corrosion rates of steel exposed to a series of homologous organic acids with
respect to temperature has been assessed in a test unit that simulates corrosion found in
refinery vacuum distillation towers. As well, organic acids from Athabasca bitumen have been
isolated and characterized. The corrosivity of the model compounds and how they compare to
the corrosivity of Athabasca bitumen will be discussed in terms of the molecular structure of the
different organic acids. This work is partially supported by the Alberta Energy Research
Institute and the Canadian Association of Petroleum Producers.
Keywords: naphthenic acid, molecular structure, refinery, corrosion, Athabasca bitumen