Technol ogy Overvi ew PIPELINES

An increasing number of offshore developments are

based on transporting unprocessed or partially
processed multiphase well streams from satellite wells
to main platforms, existing installations on
neighbouring fields or onshore processing facilities.
Corrosion, scale formation and salt accumulation
represent increasing challenges for the operation of
subsea multiphase pipelines. Corrosion-resistant
alloys such as 13% Cr steel and duplex stainless steel
are often used downhole and, recently, also for short
flowlines. For long-distance, large-diameter
pipelines, carbon steel is the only economically
feasible alternative and corrosion has to be controlled
by chemical additives to the transported fluids.
The presence of carbon dioxide (CO
2
), hydrogen-
sulphide (H
2
S) and free water can cause severe
corrosion problems in oil and gas pipelines. Internal
corrosion in wells and pipelines is influenced by
temperature, CO
2
and H
2
S content, water
chemistry, flow velocity, oil or water wetting and
composition and surface condition of the steel. A
small change in one of these parameters can change
the corrosion rate drastically due to changes in the
properties of the thin layer of corrosion products that
accumulates on the steel surface.
When corrosion products are not deposited on the
steel surface, very high corrosion rates of several
millimetres per year (mm/y) can occur. This worst
case corrosion is the easiest type to study and
reproduce in the laboratory. When CO
2
dominates
the corrosivity, the corrosion rate can be reduced
substantially under conditions where iron carbonate
can precipitate on the steel surface and form a dense
and protective corrosion product film. This occurs
more easily at high temperature or high pH value in
the water phase. When H
2
S is present in addition to
CO
2
, iron sulphide films are formed rather than iron
carbonate, and protective films can be formed at
lower temperature, since iron sulphide precipitates
much easier than iron carbonate.
Localised corrosion with very high corrosion rates can
occur when the corrosion product film does not give
sufficient protection, and this is the most feared type of
corrosion attack in oil and gas pipelines.
Pr e di c t i on of Pi pe l i ne Cor r os i on
Several prediction models have been developed for
CO
2
corrosion of oil and gas pipelines. The models
have very different approaches in accounting for oil
wetting and the effect of protective corrosion films,
and this can produce significant differences in
behaviour between the models. Some of the models
have a very strong effect of oil wetting for certain
flow conditions, while others do not consider oil
wetting effects at all. Some models include strong
effects of protective iron carbonate films, especially at
high pH value or high temperature. The models are
correlated to different laboratory data and, in some
cases, also to field data from the individual company.
It is important to understand how the corrosion
prediction models handle especially the effects of oil
wetting and protective corrosion films when the
models are used for corrosion evaluation of wells and
pipelines. Most of the models cannot be used in
situations where H
2
S or organic acids dominate the
corrosion process.
An important aspect in corrosion evaluation of oil
and gas wells and pipelines is to obtain a realistic
estimate of the actual pH value in the water phase.
When formation water is produced it is important to
obtain good water analysis data, especially with
respect to bicarbonate and organic acids. The actual
pH value must be calculated from the CO
2
and H
2
S
partial pressure, temperature, bicarbonate content in
the water and ionic strength. When only condensed
water is present the dissolved corrosion products may
increase the pH value significantly.
In a joint industry project at the Institute for Energy
Technology (IFE), the different CO
2
corrosion
prediction models were evaluated and compared with
actual field data gathered from the participating oil
companies. Figure 1 shows an example of measured
and predicted corrosion rates for an oil well where the
corrosion rate was relatively low except at a depth of
90 metres where a failure occurred. Model A takes
much account for effects of oil wetting and protective
corrosion films. This model predicts the low
corrosion rates downhole quite well, but it is unable
to predict the failure close to the wellhead. Model B
Rolf Nyborg is Deputy Department
Head in the Materials and Corrosion
Technology Department and Section
Head for Multiphase Corrosion at the
Institute for Energy Technology
(IFE) in Norway. He has been
working with corrosion research at
IFE for 20 years and, for the last
12 years, as Principal Research
Scientist. Mr Nyborg was appointed
Section Head and Deputy
Department Head in January 2003.
He has been project manager for
several international joint industry
projects on corrosion in oil and
gas wells and pipelines. Mr Nyborg
has an MSc degree in Physics from
the Norwegian University of Science
and Technology in Trondheim.
a report by
Rol f Ny bor g
Deputy Department Head, Materials and Corrosion Technology Department,
Institute for Energy Technology (IFE), Norway
Cor r os i on Cont r ol i n Oi l and Gas Pi pel i nes
B U S I N E S S B R I E F I N G : E X P L OR A T I ON & P R OD U C T I ON : T H E OI L & G A S R E V I E W 2 0 0 3 V OL U ME 2
79
nyborg_edit.qxd 10/28/03 16:38 Page 79
takes little account for effects of oil wetting and
protective corrosion films. This model is able to
predict the high corrosion rate leading to the failure,
but it does not predict the low corrosion rates further
down in the well. Model C takes more account for
protective corrosion films at high temperature and
predicts highest corrosion rate close to the wellhead
where the failure occurred. The models behaved
differently for other field cases, and none of them are
able to provide reliable predictions for all cases.
An example of corrosion rate prediction in a sub-sea
gas condensate pipeline is shown in Figure 2. Here,
two of the most commonly used corrosion prediction
models were combined with an oil and gas three-
phase fluid-flow model in order to be able to
calculate corrosion rate profiles along a pipeline. This
can help to identify locations where variation in flow
regime, flow velocity and water accumulation may
increase the risk for corrosion damage. For this
pipeline the temperature was 90C at the inlet and
20C at the outlet, and the decrease in predicted
corrosion rates towards the end of the pipeline is
mainly a result of the decreasing temperature. The
lower corrosion rates close to the pipeline inlet are
due to the effect of protective corrosion films at high
temperature, which is predicted differently by the
two corrosion models used. The peaks in predicted
corrosion rates result from variation in flow velocity
due to variations in elevation profile.
Us e of Cor r os i on I nhi bi t or s
Corrosion control of carbon steel pipelines is often
managed by the use of corrosion inhibitors. These are
organic molecules that are added in parts per million
(ppm) levels and form surface layers that reduce the
corrosion reaction on the steel. Different inhibitors are
used depending on the actual conditions in each
pipeline. Selection and qualification of inhibitors in
the laboratory prior to implementation in the field is
essential and, most often, dedicated laboratory
experiments will have to be performed with candidate
inhibitors for each field or pipeline.
A number of factors may influence inhibition in
multiphase pipelines. Factors such as temperature,
water-oil partitioning, water chemistry and flow
conditions have been widely studied. Less attention
has been paid to factors such as the composition and
microstructure of the steel, the type of corrosion
products formed on the steel surfaces, inhibitor
adsorption on suspended particles in the produced
water and inhibitor accumulation on gas bubbles,
oil/water droplets and emulsions. It has been
difficult to account for the effects of multiphase flow
Technol ogy Overvi ew PIPELINES
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nyborg_edit.qxd 10/28/03 16:40 Page 80
Cor r os i on Cont r ol i n Oi l and Gas Pi pel i nes
on corrosion inhibition in laboratory screening tests.
Laboratory experiments at IFE have shown that steel
microstructure, corrosion products on the steel
surface and presence of emulsions can affect
inhibitor perform-ance strongly. New test methods
and equipment are being developed in order to
account for the effect of multiphase flow and steel
surface conditions.
T he pH S t a bi l i s a t i on T e c hni que
The pH stabilisation technique can be used for
corrosion control in wet gas pipelines when no or
very little formation water is transported in the
pipeline. This technique is based on precipitation of
protective corrosion product films on the steel
surface by adding pH-stabilising agents to increase
the pH value of the water phase in the pipeline. The
pH-stabilisation technique has been taken into use in
several wet gas condensate pipelines and is currently
being considered for several new fields. This
technique is very well suited for use in pipelines
where glycol is used as hydrate preventer, as the pH
stabiliser will be regenerated together with the
glycol. This means that there is very little need for
replenishment of the pH stabiliser.
Experiments for qualification of the pH stabilisation
technique at the IFE have shown that protective
films form in a short time at temperatures between
40C and 100C, reducing the corrosion rate to less
than 0.1mm/y. At lower temperatures around
20C, the iron carbonate precipitation is very slow
and it may take several months to obtain protective
corrosion films. Since the initial corrosion rate is
low at 20C and with a high pH value, it is
acceptable to wait a few months for a protective
corrosion film to form.
A major application for the pH-stabilisation
technique has been the Troll pipelines. The Troll
field, originally developed by Shell and operated by
Statoil, is a large gas-condensate field in the
Norwegian sector of the North Sea. The field
commenced operation in 1996. The water depth is
about 300 metres and, in order to minimise the size
of the offshore production facilities, it was decided to
perform a simple processing with only removal of
free water offshore. This solution meant that wet gas
with CO
2
had to be transported in two 36-inch
pipelines over a distance of 65km from the platform
to shore. The Troll field is a sweet gasfield with a
CO
2
content of 0.3%. The pipeline inlet and outlet
temperature is 50C and 5C, respectively.
Monoethylene glycol is injected at the pipeline inlet
in order to control hydrate formation. It was
originally decided to use glycol as the only additive
with a rather large corrosion allowance, as the low
CO
2
pressure gave a low corrosivity in the system.
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nyborg_edit.qxd 10/28/03 16:45 Page 81
B U S I N E S S B R I E F I N G : E X P L OR A T I ON & P R OD U C T I ON : T H E OI L & G A S R E V I E W 2 0 0 3 V OL U ME 2
Technol ogy Overvi ew PIPELINES
The target was to reach a corrosion rate of less than
0.2mm/y. The amount of glycol had to be increased
above what was needed for hydrate control in order to
reach this corrosion rate. During the first year of
production, precipitation of corrosion products from
the pipeline started to present problems in the onshore
glycol regeneration units. The dissolved iron from the
pipeline formed scales on the surfaces in the heat
exchangers and boilers and some precipitated as
particles in the bulk phase. The estimated amount of
corrosion products was 20 tons in the first year of
operation. This was not regarded as a corrosion
problem in the pipelines, but as a process problem in
the onshore processing plant. In order to reduce the
amount of dissolved corrosion products in the pipeline
and avoid a costly rebuilding of the gas processing
plant, it was decided to reduce the corrosivity further
by applying the pH-stabilisation technique.
The pH value at the outlet of the pipeline prior to pH
stabilisation was close to six. Based on results from
laboratory testing and calculations at the IFE, it was
decided to increase the pH value in the pipeline to 7.4.
This was done by injecting a sodium-hydroxide
solution into the lean glycol tank that is operated at
ambient pressure. The concentration of dissolved iron,
which has the potential to form scale in the process
equipment was reduced from around 100ppm to less
than 5ppm after six weeks, as shown in Figure 4. This
corresponds to a corrosion rate far below 0.1mm/y.
Very little precipitation takes place in the process
system today and the system has been operated with
success since the treatment was carried out in 1997.
When glycol is used to prevent hydrate formation, it
is convenient to transport and inject the pH stabiliser
together with the glycol. The pH stabiliser is
regenerated together with the glycol and the
consumption is therefore very low. However, under
some conditions with high CO
2
partial pressure, the
demand for pH stabiliser can be so high that it is not
possible to dissolve enough pH stabiliser in the
glycol. The pH-stabilisation technique cannot be
used for pipelines carrying large quantities of
formation water due to formation of carbonate scale
at the elevated pH value. Replenishment of pH
stabiliser may become costly for systems where even
small amounts of formation water are carried over
from the offshore processing. When the glycol is
regenerated, the salts will be accumulated in the
regenerated glycol. When salts are removed, the pH
stabiliser will usually also be removed, and even a
small formation water carry-over may then require
considerable replenishment of the pH stabiliser.
The pH-stabilisation technique has been used mostly
for wet gas pipelines without any H
2
S in the gas, but
is now being taken into use also for pipelines with
considerable amounts of H
2
S in addition to CO
2
.
Here, the corrosion product depositing on the surface
will be iron sulphide instead of iron carbonate. These
sulphide films have different protective properties
than the iron carbonate films forming in sweet
systems. Localised corrosion in the form of pitting is
the critical factor in H
2
S-containing systems. The
application limits for the pH-stabilisation technique in
wet gas pipelines containing high amounts of H
2
S and
CO
2
are being studied in an on-going joint industry
project at the IFE.
Figure 3: Iron Content After pH Stabilisation of the Troll Pipelines
0
Injection of
NaOH started
Injection rate of
NaOH increased
Injection of
NaOH stopped
30 60 90 Time (days)
Dissolved iron Total iron
F
e
2
+
/
p
p
m
120 150
0
50
100
150
200
Figure 1: Example of Model Runs for an Oil Well
5
4
3
2
1
0
1,500
Depth (metres)
C
o
r
r
o
s
i
o
n

r
a
t
e

(
m
m
/
y
)
1,000 500 0
Model A
Model B
Model C
Measured
corrosion
Figure 2: Predicted Corrosion Rate in a Subsea Pipeline
10
8
6
4
2
0
0 5,000 Position (metres)
Norsok model de Waard model
C
o
r
r
o
s
i
o
n

r
a
t
e

(
m
m
/
y
)
10,000
82
nyborg_edit.qxd 10/28/03 16:56 Page 82
SINTEF Materials Technology
35 years of offshore experience
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Our laboratory facilities:
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CONTACT: Jack degrd
E-mail: jack.odegard@sintef.no
Phone: +47 73 59 52 26
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exprod_83.qxd 10/29/03 15:35 Page 83