Sweet Corrosion

Oil and gas production and drilling that is often conducted off shore, as well as this it often involves
more mature wells. The consequence of this is multiphase mixtures that can contain water cuts
that make up to 90% of the mixture. The mixture contains oil, gas and water and within that gas is
CO
2
which is the initiator for sweet corrosion. Carbon dioxide is a highly soluble gas that produces
acidity in solution. The acid formed can discharge electrons on the metal surface in several ways due
to this carbon dioxide is more corrosive than mineral acids of the same molarity. It is found in
natural gas, crude oil, and condensate and produced water. The carbon dioxide dissolves in water to
form carbonic acid, which then dissociates to hydrogen ions and bicarbonate anion. The hydrogen
ions remove electrons from the metal surface and the carbonic anion may also discharge an electron
to form carbonate. At higher pH values (>6) the HCO
3
-
dissociates further to H
+
+ CO
3
2-
.

Figure 1 Sweet Corrosion Reactions (Uhlig, 2011)
The carbon steel corrodes in the water contain CO
2
under the reaction:
Fe Fe
2+
+ 2e
-

The overall reaction is:
Fe + H
2
CO
3
FeCO
3
+H
2
Where the FeCO
3
is iron carbonate/siderite. The iron carbonate precipitates out of solution and
deposits of the wall of the pipe creating a film. The film that forms due to sweet corrosion is called
siderite or iron carbonate. This is formed due to the reaction of the corroding steel with the
bicarbonate ions. This film may also include hydroxides and oxides. The iron carbonate has poor
solubility in water and the solubility decreases with an increase in temperature.


Figure 2 Illustration of Sweet Corrosion Mechanism (Javeherdashti, et al., 2013)
In the oil/gas system the rate of corrosion is affected by multiple variables. Temperature, pressure,
pH and flow as well as others. The partial pressure of CO
2
equals the mol fraction of CO
2
in the gas
multiplied by the total pressure. The precipitated water phase dissolves the CO
2
up to a
concentration proportional to the partial pressure of the CO
2
in the gas phase. The solubility also
depends on the temperature (Bardal, 2004). The rate of the reaction is limited by the pH of the
system, with a more acid solution having a greater rate of reaction (Laws, 2000). The initial rate of
corrosion is high, by declines rapidly over a 24-48 hour period due to the formation of a film of
corrosive products forming on the surface of the metal.


Figure 3 Effect of CO2 partial pressure on corrosion rates
(Uhlig, 2011)
Figure 4 Effect of pH on sweet corrosion rate (Uhlig, 2011)

Sweet corrosion presents itself as general and localised corrosion of which, pitting, mesa and flow
induced localised corrosion are the main forms depending on the conditions within the tube. The
general mechanism for the corrosion will be described and then the variation after that. . If the flow
in the pipe is not strong enough to disturb the film, it will grow overtime and slow the rate of the
reaction. If the flow is strong it can wear away the protective film which leads to increases corrosion.
The damage is mostly found at the bottom 6 oclock position of the pipe where water
preferentially lies. This layer of water causes a layer of the ion carbonate or siderite to form, this
layer however breaks down over time. This break down is more profound on areas of the pipeline
that have morphology anomalies, such as weld splatters, mill scale/ oxidation films, turbulence at
weld defects or within pits, places along the pipe which could inhibit the formation/adherence of
siderite. This causes the corrosion to be higher at these points. The loss of metal at these points
increases turbulence and therefore increases the corrosion.

Figure 5 Illustration of MESA corrosion (Palmer & King, 2008)

Pitting can occur over the full range of operating temperatures under stagnant to moderate flow
conditions. An increase in temperature and CO2 partial pressure increases the susceptibility to
pitting, though it generally occurs between 80-90C (Kermani & Smith, n.d.). The most feared type
of corrosion in practice (Dugstad, et al., 1994) is mesa corrosion. Mesa corrosion is usually
associated with medium flow rates. The mechanism is based on a fine balance between film growth
and film dissolution or mechanical film removal (Kermani & Smith, n.d.). Mesa corrosion is found
when the protective film does not cover the whole surface of the pipeline. The Corrosion spreads as
an even band down the length of the pipe from the initiation point which can be seen in figure XX.
The metal appears as if it has been selectively milled in bands with sharp step edges. The final
manifestation of sweet corrosion that is usually seen is flow induced localised corrosion that
occurs at high liquid flow rates. This corrosion is propagated by the pits and wells of pitting and mesa
corrosion which cause areas of highly turbulent flow (Kermani, et al., 2006). The turbulence destroys
existing scale and prevents reformation. (Kermani & Smith, n.d.)


Prevention
CO
2
(sweet) corrosion is influenced by many process factors including: temperature, increase in the pH value,
composition of aqueous solution, the presence of non-aqueous solution, flow conditions and/or metal
characteristics (Popoola, LT. & Grema, AS. 2013). The first line of defence to avoid or reduce corrosion rate(s)
is technical. Cathodic and anodic protection, material selection of equipment, chemical dosing and application
of internal/external coatings are some of the options that are available. Nevertheless, the choices between the
possibilities are usually based on economically-feasible conditions (Popoola, LT. & Grema, AS. 2013). For that
reason, alternative methods have been developed. Use of inhibitors/protective coatings along with adequate
corrosion monitoring and inspection is observed to be successful.
A protective layer/coating on a material is painted on to avoid direct contact with the process medium, and
to extend the material/equipment life (CAPP, 2009). Examples of coatings generally consist of metallic-lining,
or non-metallic, such as, fiberglass, glass-flakes, and epoxy. However, a protective coating is not sufficient. In
the oil and gas industry there are mediums which can bypass the barrier and still erode the apparatus. When
carbonic acid comes into contact with the metal, the material coating is disrupted, resulting in corrosion (CAPP,
2009). Essentially other mitigation techniques are required. One way is to introduce corrosion inhibitors.
Corrosion inhibitors are chemicals that are utilised to protect the surface of materials used in the oil and gas
industries to prevent corrosion. An inhibitor can operate in 2 different ways. Merging the metal with inhibitor
or reacting the inhibitor with the impurities in the environment in which cause the pollution in the first place.
When reacted with the surface, the inhibitor restricts the rate of the anodic/cathodic process by simply
blocking the active sites on the metal surface. Furthermore, it can also increase the potential of the metal
surface and passivation arises, triggering a natural oxide film to form (Abbasov, V.M. & El-Lateef, M.E. 2012).
Yet, when considering an inhibitor, toxicity, environmental friendliness, availability and cost must be
considered.
Traditionally, inorganic inhibitors were commonly used in the petroleum and petrochemical industries. They
were observed to provide higher inhibition performance. Crystallised salts of heavy metals such as, chromate,
cerate and borate were some of the inhibitors exercised. These caused the induction of dense-soluble oxide
barriers of corrosion products on the metal surface that prevent the surface from participating in further
corrosion activities. Nevertheless, environmental conditions are of high priority, therefore some of the heavy
metals caused limitations as they carried high levels of toxicity. Organic inhibitors were proposed. Unlike
inorganic compounds, organic compounds presented no harm on either the environment or human health.
Modern organic corrosion inhibitors used nitrogen-containing compounds. Various amines display stability,
high degree of protection in corrosive mediums and further improved the operational characteristics. The
imidazoline (IM) compound is the most frequently used, compromising of 3 different substrates (Abbasov, V.M.
& El-Lateef, M.E. 2012). The structure composed of N-containing five member ring, pendant-side chain with
hydrophilic active functional group (R1), and a long hydrophobic hydrocarbon chain (R2). The presence of the
hydrophilic-group greatly improved the corrosion performance (Popoola, LT. & Grema, AS. 2013). When in
contact with water, the hydrophilic group does not react with the solution, instead, repelling the aqueous
medium. Since, the medium is adsorbed onto the surface rather than absorbed, accumulation of product is
apparent. However, the effectiveness of the organic layer heavily depends on the chemical composition,
molecular structure and the affinity of the metal surface (Abbasov, V.M. & El-Lateef, M.E. 2012).
Similarly, preventing corrosion can also be further managed via monitoring and controlling the problem.
Assessing the useful life of the equipment can influence the operation(s). When corrosion conditions change,
controls must also be altered (Brondel, D. & Edwards, R. 1994). Once these modifications have been
established, effectiveness of the controls can be concluded. It will determine if the measurements have been
successful or not. Ineffective measures are rectified and re-implemented. However, all techniques are
dependent on: what equipment, what it is used for and where? Ultimately, protection of CO
2
(sweet) corrosion
occurring in the petroleum and gas industries is most effective when both organic and management is used in
conjunction.
References:
1. Abbasov, V.M. & El-Lateef, M.E. 2012. Corrosion Protection of Steel Pipelines against CO2 Corrosion-
A Review. Chemistry Journal. Vol. 02, Issue 02, pp. 52-63. Nottinghamshire, UK.
2. Brondel, D. & Edwards, R. 1994. Corrosion in the oil industry. Schlumberger. Texas, USA.
3. Canadian Association of Petroleum Producers (CAPP). 2009. Mitigation of Internal Corrosion in Sweet
Gas Gathering Systems. Ontario, Canada.
4. Popoola, L.T. & Grema, A.S. 2013. Corrosion problems during oil and gas production and its
mitigation. International Journal of Industrial chemistry. Vol.4, No. 35. Babalola University, Nigeria.