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International Journal of Emerging Technology and Advanced Engineering

Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 4, April 2014)
471

Characteristics of Corrosion Scales on Pipeline Steel in CO
2
-
Saturated NaCl Brine Solution
G. S. DAS
Material Science and Metallurgical Engineering, National Institute of Foundry and Forge Technology, Hatia, Ranchi-834003
Abstract-- The present study is aimed to conduct the
experiments in various corrosive environments at various
temperatures and constant partial pressures of carbon dioxide
(CO
2
) under dynamic condition to understand the basic
mechanism and corrosion resistance of carbon steel. Usually,
API grade steels are used in the pipeline for carrying the
crude oil and gas.
Corrosion problems constitute the major operating
difficulty in the oil and gas industry particularly in the
transportation system from refinery to the different source
station and have caused unscheduled downtime, production
losses and reduced equipment life. The presence of CO
2
and
addition of H
2
S in the solution is an important parameter
which affects the severity of corrosion in steel. Thus it is a
challenging and most important task to study the corrosion of
steel in most affected corrosive environment. Few experiments
on API X-52 grade steel have been carried out at different
temperature range (30-120
o
) at a constant partial pressure of
carbon dioxide i.e 100 psi to know the severity of corrosion.
The exposed sample has been analyzed using x-ray diffraction
and scanning electron microscope.
Keywords-- API X-52 grade steel, partial pressure of CO
2
,
crude oil
I. INTRODUCTION
Pipeline steels are the primary materials of construction
in just about every sphere of petroleum industry
particularly in production, transmission and refining
systems. One of the most significant tasks in current-day
corrosion engineering is the accurate assessment and
prediction of severity of corrosion in aggressive
environment. Many literatures reported that the parameters
that contribute to corrosiveness are dissolved CO
2
,
dissolved O
2
, type of solvents, degradation products,
temperature, and solution velocity. One inherent limitation
of the use of carbon steel is their susceptibility to corrosion
damage in environments that contain significant amounts of
carbon dioxide (CO
2
), hydrogen sulfide (H
2
S) and
chlorides (Cl
-
) in combination with produced water. While
metallurgical, manufacturing and economic considerations
promote the utilization of American Petroleum Institute
(API) grade steel for use in petroleum industry especially
for production, transmission and refining systems.

These steels have the tendency to resistance of corrosion
even in severe corrosive condition at high temperature and
pressure. However, CO
2
corrosion of carbon steel is one of
the most important problems in the oil and gas industry
because of high corrosion rate and severe localized
corrosion. The CO
2
corrosion affects the materials which
are used in production, transportation and processing
systems. Generally, pipeline steels are made of low alloy
steel which is susceptible to corrosion in CO
2
environments. The susceptibility of their corrosion depends
on various parameters such as temperature, CO
2
partial
pressure, pH, oxygen solubility, chloride concentration,
flow rate and characteristics of the materials [1]. The
corrosion of carbon steel is related to the formation
behavior of iron carbonate (FeCO
3
) which is a corrosion
product and precipitates out of the solution due to its low
solubility and settles on the metal surface [2]. When this
product increases on the metal surface uniform corrosion
decreases and localized corrosion increases [3].
The presence of H
2
S is also another most important
factor responsible for the severe localized corrosion in the
carbon steel. In presence of small amount of H
2
S in the
solution the corrosivity of the metal affect severely because
it can easily dissolves in water and reacts with the metal
surface. At low concentration of H
2
S and higher
temperature above 80
o
C the formations of iron sulphide
(FeS) favours that may stable on the metal surface and thus
prevent the metal for further corrosion. In absence of iron
sulphide region, dip pit may forms on the surface results in
crack formation called sulphide stress corrosion cracking
(SSCC). However, this type of corrosion is not significant
unless the H
2
S level exceed 200 ppm [4]. The partial
pressure of CO
2
has strong influence role on corrosion
process of carbon steel in compare to any strong acid of
same concentration [5]. Hence the study of CO
2
/H
2
S
corrosion is essential for the safe utilization of carbon steel
in oil and gas industries which are cheaper in compare to
all new developed corrosion resistance steels. Very few
literatures are available under static condition on CO
2
/H
2
S
corrosion at high temperature and pressures but the open
literature are rarely found in CO
2
/H
2
S environment under
dynamic condition.


International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 4, April 2014)
472

II. EXPERIMENTAL
The material used in the current study was obtained from
ONGC pipeline group Juhu Helibase in pipe.form. The as-
received materials was cut into the rectangular specimen of
dimension 20 mm x 12 mm x 2.5 mm with a center hole of
diameter 1.5 mm at the top edge of each specimen to
facilitate the suspension inside of the autoclave of capacity
2.2 liter. The faces of the sample were initially coarse
grounded on a SiC belt grinder machine then consequently
machine polished in the successive grades of emery papers
(220, 400, 600 800 and 1000). The initial weight and area
of the sample was measured using digital weighing
machine upto an accuracy of four digit. Four different
experiments were carried out at different temperature (30
o
C, 60
o
C, 90
o
C and 120
o
C) in a multiphase dynamic loop
machine at constant partial pressure of 100 psi. The
velocity of fluid was maintained at a constant speed of 1.5
m/s for 96 hours. The oxygen solubility of the system was
maintained below 40 ppm using the Ar gas. In the
beginning of the test, the actual temperature of the machine
was set as 30
o
C, 60
o
C, 90
o
C and 120
o
C separately and
respectively and then created the actual partial pressure of
carbon dioxide by releasing the carbon dioxide gas inside
the autoclave. After 96 hrs. of exposure the sample was
taken out from the autoclave washed in distilled water,
rinsed in acetone and then dried in air. After cleaning, the
coupon weighed again and finally the corrosion rate of the
sample was measured in mills per year using the formula;
Corrosion rate = Weight loss (g) X Constant (K)/Metal
density (gm/cm3) X Metal Area (A) X Exposure time (hrs.)
The constant value (K) is 5.34 x 10
5
.
The surface morphology of corroded sample was
observed using environmental scanning electron
microscope (ESEM) at an operating voltage of 15 kV. The
phases of the sample were analyzed using XRD systems.
Table 1
Chemical composition of the as received material (in wt %) was
obtained using (ICP) method
Elements Wt %
C 0.19
Mn 1.22
Si 0.36
S 0.003
P 0.004
Cr 0.07
Mo -
Cu 0.16


III. RESULTS AND DISCUSSION
The physical appearances of exposed sample at
aggressive and protective temperature are shown in Fig. 1.
The sample after 96 hours of exposure at 90
o
C shown
higher and depth pits while at 120
o
C the appearance of
depth of the pit is comparatively less. The weight loss data
as a function of temperature at a constant partial pressure of
carbon dioxide are shown in Fig. 2. The results showed that
corrosion rate of the sample increases with increasing
temperature. The highest corrosion rate has been observed
at a temperature of 90
o
C due to formation of porous layer
of oxides and sulphides on the metal surface as shown in
Fig. 3. This causes faster reaction and dissolution of the
film in the solution results in higher corrosion rate. Also,
the results indicated that the corrosion rate decreases at
higher temperature near about 100-120
o
C due to formation
of adherent and dense layer of protective film that protects
from further reaction of corrosion as shown in Fig. 4. X-ray
diffraction analysis shows that the FeCO
3
phase is
predominantly form over the surface which is protective in
nature. The other phases observed are Fe
3
O
4
, Fe
2
O
3
and
Fe
3
C respectively as shown in Fig. 5.


International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 4, April 2014)
473


Fig. 2: Weight loss data as a function of temperature at constant
partial pressure of CO2 (100psi)

Fig. 3: Surface morphology of exposed sample @ 5000X at 90
o
C



Fig. 4: Surface morphology of exposed sample @ 5000X at 120
o
C

Fig. 5: XRD analysis of phases formed in exposed sample
IV. CONCLUSIONS
The corrosion rate of pipeline steel increases with
increasing temperature upto 90
o
C due to formation of
porous layer results in spallation of the film in the solution.
Beyond this temperature the corrosion rate again fall down
due to formation of dense and adhered layer of oxide film
on the metal surface. At aggressive temperature the layer
formed on the surface dissolving continuously and the
reaction rate becomes faster and shown higher corrosion
rate while at higher temperature the iron carbonate film
form which very dense and compact on the surface results
in slower corrosion rate.

API X-52 steel
0
50
100
150
200
250
300
350
400
450
0 30 60 90 120 150
Temperature (
o
C)
C
o
r
r
o
s
i
o
n

r
a
t
e

(
m
p
y
)

International Journal of Emerging Technology and Advanced Engineering
Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 4, Issue 4, April 2014)
474

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[7] K.D. Efird, E.J. Wright, J.A. Boros, T.G. Hailey, Wall shear stress
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[8] G.I. Ogundele and W.E. White, Some observations on corrosion of
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