SPE Updates Archive Corrosion inhibitor and cleaner, rolled into one Page 1 of 5

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Corrosion inhibitor and cleaner, rolled into one

Wednesday, 25 April 2007

While injecting corrosion inhibitors into production fluids can be an extremely cost-effective means of mitigating
corrosion in carbon steel pipelines, the inhibitors are worthless if they cannot reach the pipe wall. This is a particular
problem in production pipelines containing built-up oily solids that prevent even the best inhibitor from reaching the wall.
The Energy Services Division of Nalco Company claims to have developed a novel solution to this problem with the
introduction of Clean n Cor, a technology specifically developed to both remove oily sludge deposits and form a
protective barrier against corrosion.

Dr. David Horsup, R&D Manager for the Asset Integrity and Production Maximization group for Nalco, recently
explained the importance of keeping production equipment clean and the process used to develop Clean n Cor.

While the thickness of oily sludge in a pipeline may range from only a few millimeters to several centimeters, the
outcome is the same: the sludge may adsorb significant quantities of corrosion inhibitor, prevent the inhibitor from
reaching the pipe wall, and in addition may act as an ideal incubator for bacteria to grow, Horsup said. This bacteria
typically produces very corrosive byproducts during its metabolic cycle, causing the well known and potentially
aggressive process of microbiologically influenced corrosion (MIC).

Sludge buildup poses an additional challenge in those fields using water injection wells to maintain production. Sludge
may find its way through the separator and into the water injection line, where it may plug filters or collect down-hole in
the formation, resulting in lower water injection rates, and subsequent lower production rates as well.

Instead of investing a great deal of time and resources into developing a new cleaner/corrosion inhibitor package, why not
look at more conventional methods of keeping the line clean? Clearly the best approach would be to prevent the
problematic components in the production fluids from depositing within the pipe, says Horsup. While this can be
achieved to some extent through careful management of the production process, complete control can rarely be achieved.

The resulting deposits then have to be removed physically from the pipeline, typically through maintenance pigging
operations. However, in many fields with an older infrastructure, pig launchers and receivers may not be installed, and
even if they are, the pipe configuration may have changed such that youre faced with pipe of varying diameter along the
same line, Horsup says. It is often very difficult, if not impossible, to pig a line like that. Additionally, pigging
operations can result in process upsets, lost production, significant opex costs and EH&S challenges.

This reality forced Horsup and his colleagues at Nalco to initiate a thorough research effort aimed at understanding the
factors involved in successfully removing sludge by chemical means, and then developing a formulation that could
effectively remove this sludge while also mitigating aggressive corrosion.

A few field operators in North America with this specific problem of corrosion under sludge were more than happy to
provide assistance with the research effort. Says Horsup: We received a sample of sludge from one customers produced
water line following a maintenance pigging run and analyzed it compositionally. We discovered that the majority (40%)
of the sludge was hydrocarbon, which was essentially the glue holding the solids in the sludge together. These solids
included sand, clays, corrosion byproducts and biomass, all present on the order of 10-15% of the total mass.

http://updates.spe.org/index.php/2007/04/25/corrosion-inhibitor-and-cleaner-rolled-into-one/1/ 5/13/2007
SPE Updates Archive Corrosion inhibitor and cleaner, rolled into one Page 2 of 5
Product development starts at the fundamentals

By focusing on a way to desorb or remove the hydrocarbon glue, the remaining solids should be carried off the surface
as well, allowing the inhibitor to reach the pipe wall. To investigate this, Horsup drew upon his background in interfacial
phenomena and surfactants to look at the cleaning effect of different inhibitors. We solicited the help of Timothy
Dunstan and Professor John Clint in the Department of Chemistry at the University of Hull, UK to perform a series of
interfacial property studies on various inhibitor actives in the presence of field brines and crude oil samples. Most of the
inhibitor actives selected for study were well-established actives in Nalcos arsenal, as well as a new, patented modified
fatty amine.

One set of studies was a measurement of the interfacial tension between crude oil and water (ow), in the presence of the
inhibitor actives at various concentrations. Corrosion inhibitors are surface-active molecules, which means that they
adsorb at surfaces or interfaces, in this case the interface between the oil and water, explains Horsup. Once adsorbed,
the inhibitors will lower the tension between the oil and water, and as the inhibitor concentration is increased, a point is
reached where the interfacial tension plateaus. At this concentration, if the interfacial tension is low enough, the inhibitor
will allow oil droplets to easily be removed from a solid surface and dispersed in the water phase. The best actives reach
this minimum in interfacial tension at low dosages (low ppm range).

The results of these tests demonstrated that the modified fatty amine provided the lowest ow at the lowest dosage,
indicating that it would likely be the most cost-effective active for removing sludge from a pipe surface. This active was
combined with other proven inhibitor actives into a new formulation, which also demonstrated the ability to significantly
lower ow at very low dosages.

The interfacial property data was a useful starting point, and suggested that the formulation would be a cost-effective
inhibitor package for removing oily deposits from a pipeline. However, as Horsup pointed out, We then wanted to more
directly observe how effective this new formulation would be at removing sludge before we moved it to the field.

New lab test studies real-time sludge removal

Nalco and the University of Hull collaborated to build a test cell that would measure sludge removal in a way that
mimicked real-world conditions. This test loop incorporated a clear glass cell containing a freshly polished 1018 carbon
steel coupon at the base, explained Horsup. A known mass of sludge (obtained from a pigging operation) was applied to
the surface of the coupon, which was then placed in the glass test cell.

We then introduced a formulation at different dosages into the test loop to see how effective it would be at removing the
sludge, Horsup says. The flow rate through the loop was kept very low, on the order of 0.33 L/min (corresponding to a
linear velocity of 0.8 m/min), because we wanted to minimize turbulence effects and only study the effect of the inhibitor
package on sludge removal.

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SPE Updates Archive Corrosion inhibitor and cleaner, rolled into one Page 3 of 5
A video camera continuously monitored the sludge/coupon specimen to record how the sludge surface changed over time,
and online measurements of water turbidity over time were performed to determine how much oil was present in the
water. Each test ran for two hours, after which time the coupon was removed from the cell, dried and reweighed to
determine how much sludge was left.

In one set of tests, we compared the new formulation with a best-in-class corrosion inhibitor, both injected at 80 ppm.
With the new formulation, the sludge/water interface was extremely turbulent, and oil was continuously being removed
into the water, says Horsup. After 10 min, 99% of the sludge had been removed, and the test was essentially complete. In
contrast, the incumbent product removed sludge much more slowly, and after two hours, a maximum of only 30% of the
sludge had been removed.

A series of laboratory corrosion tests on this new formulation under a range of flow rates and shear stresses also indicated
promise. Our suite of lab tests suggests that the new formulation is one of our better inhibitors, said Horsup. It was at
least 10% better from a cost-performance standpoint than the same incumbent product run in the sludge removal flow
loop.

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http://updates.spe.org/index.php/2007/04/25/corrosion-inhibitor-and-cleaner-rolled-into-one/1/ 5/13/2007