Corrosion Science 44 (2002) 101112

www.elsevier.com/locate/corsci

Study on corrosion inhibitor in large

pipelines under multiphase ow using EIS
T. Hong *, Y.H. Sun, W.P. Jepson
NSF I/UCRC Corrosion in Multiphase System Center, Institute for Corrosion and Multiphase
Technology, Ohio University, Athens, OH 45701, USA
Received 4 July 2000; accepted 26 February 2001

Abstract

An imidazoline based inhibitor behavior in carbon dioxide environment has been studied in
large pipelines under dierent slug ow conditions by electrochemical impedance method. It is
found that, for each of the slug ow condition, charge transfer resistance, Rt , and Warburg
impedance coecient, r, increase with increasing exposure time. It is suggested that the per-
formance of the corrosion inhibitor is dependent on exposure time. The corrosion inhibitor
has a good performance of corrosion protection by forming more compact inhibitor lms on
the metal surface at longer exposure time. Experimental results also show that, at a given time,
both Rt and r decrease with increasing the Froude number of slug ow. This fact implies that
the inhibitor lm is damaged and washed away from the metal surface by high turbulence and
the higher frequency of bubble pulse in high Froude number of slug ow, thus leading to low
corrosion resistance. 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Low alloy steel; Acid inhibitor; EIS

1. Introduction

Organic corrosion inhibition is the most eective means of protecting the severe
internal corrosion of carbon steel pipelines in oil product transportation. Since imi-
dazoline based inhibitors have a high inhibition ability in acidic media, they are
widely used to minimize carbon dioxide induced corrosion in the oil and gas in-
dustry.

*
Corresponding author. Tel.: +1-740-593-9947; fax: +1-740-593-9949.
E-mail addresses: thong@bobcat.ent.ohiou.edu (T. Hong), sun@bobcat.ent.ohiou.edu (Y.H. Sun).

0010-938X/02/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 0 1 ) 0 0 0 5 2 - X
102 T. Hong et al. / Corrosion Science 44 (2002) 101112

It is well known that the corrosion rate in pipelines is strongly related to ow

condition. Slug ow, an intermittent ow regime, is observed at higher gas velocities.
The front of the slug is a highly turbulent mixing zone where gas is entrained. Jepson
and his workers indicate [1] that high wall shear stress at the bottom of the pipe in
slug ow results in high levels of corrosion there. Slug ow can be characterized by a
dimensionless Froude number calculated by the following equation [2]:
1=2
Fr Vt Vf =gheff 1

where Fr is the Froude number, Vt the translational velocities of the slug front, m/s,
Vf the average velocity of the liquid lm, m/s, g the acceleration due to gravity, m/s2 ,
heff the eective height of the liquid lm, m.
Most of the studies on the inhibition mechanisms of imidazoline based inhibitors
have been conducted in laboratory scale systems, such as the rotating cylinder
electrode cell or the laboratory scale ow loop, under a water or a wateroil phase
[39]. Very little is understood about inhibitor performance in large diameter
multiphase ow system.
In a previous work, the authors examined the inhibition behaviors of the imi-
dazoline based inhibitors under multiphase ow in large pipelines by using EIS [10].
It has been found that the inhibitor lms in slug ow are more porous than in full
pipe ow. It is suggested that the turbulence and bubble in slug ow degrade the
inhibitor performance and increase the corrosion rate.
In this work, the inhibition performance of imidazoline based inhibitor in dif-
ferent slug ows were examined using EIS technique. The eect of Froude number of
slug ow on the inhibition performance was discussed.

2. Experimental

Experiments were carried out in a 101.6 mm i.d., 15 m long acrylic pipeline. The
schematic layout of the system is shown in Fig. 1. The detail description of this
system has been reported [1]. The liquid is forced under gate E into the 101.6 mm i.d.
Plexiglas pipe where it forms a fast moving liquid lm. The carbon dioxide gas is also
introduced into the system at port F. The gas/liquid mixture passes through the
Plexiglas pipeline. All the measurements are taken in the test section G located 8 m
downstream from the gate. This system can generate two ow conditions. They are
full pipe ow and stationary slug ow. Full pipe ow is a ow pattern with a single
liquid phase owing along the ow loop without feeding gas. The ow rate of liquid
phase is controlled by a bypass line B and is measured by a calibrated orice meter
D. For the slug ow experiments, a hydraulic jump [1] is generated and moved into
the test section by controlling the gas ow at the inlet F under a certain liquid ow
rate. In this work, Froude numbers 6, 9 and 12 are used.
Studies are carried out using the ASTM substitute saltwater and carbon dioxide
gas. The system temperature and pressure are maintained constant at 40C and 0.136
MPa for all experiments. The pH value of the saltwater solution is about 5.6 and the
 T. Hong et al. / Corrosion Science 44 (2002) 101112 103

Fig. 1. Experimental system.

conductivity of saltwater is around 0.046 X 1 cm 1 . The inhibitor used in this work is

an imidazoline based inhibitor formulated with the commercial grade imidazoline
and dimertrimer acid. The composition of the inhibitor is shown in Table 1. The
inhibitor concentration is 100 ppm. The inhibitor is injected into the ow loop
system and fully mixed with the test solution before the EIS probe is installed into
the system.
The EIS probe is inserted into the test section G as shown in Fig. 2, and is ush
mounted with the pipe wall. A three-electrode arrangement is used in this work. The
working electrode is made of C-1018 carbon steel. The counter and reference elec-
trodes are made of 316L stainless steel. The chemical compositions of C-1018 carbon
steel and 316L stainless steel are presented in Tables 2 and 3, respectively. 316L
stainless steel has been evidenced as a suitable reference electrode in carbon dioxide
saturated ASTM saltwater at the constant temperature of 40C [10]. The surface area

Table 1
Inhibitor formulation used in this study
Chemical component Concentration by weight (%)
IC-16 imidazoline (P CHEM) 25.0
Acetic acid 7.5
Water 5.0
Isopropyl alcohol (IPA) 62.5
104 T. Hong et al. / Corrosion Science 44 (2002) 101112

Fig. 2. Test section.

Table 2
Chemical composition of type C-1018 carbon steel (wt.%)
C Si P S Mn Al Fe
0.21 0.38 0.09 0.05 0.05 0.01 Balance

Table 3
Chemical composition of type 316L stainless steel (wt.%)
C Si Ni S Mn Mo Cr Fe
0.02 0.80 14.00 0.02 1.10 2.00 17.00 Balance

of each electrode is 0.785 cm2 (diameter is 10 mm). The distance between the centers
of each electrode is about 13 mm as shown in Fig. 3.
Once the de-oxygenation process is complete, the EIS probe, which is polished by
600-grid sandpaper then rinsed with acetone and distilled water for several times, is
inserted into the test section and the EIS measurement was started. The AC im-
pedance spectra in this work are generated by Gamry CMS300 corrosion monitoring
system and analyzed using the accompanying software. The EIS measurements are
carried out at the open circuit potential with amplitude of 10 mV AC potential in the
frequency range of 20 mHz to 5 kHz.

3. Results and discussion

Fig. 4 shows the Nyquist plots for C-1018 carbon steel exposed to carbon dioxide
saturated ASTM saltwater with 100 ppm inhibitor under slug ow of Fr 6. The
 T. Hong et al. / Corrosion Science 44 (2002) 101112 105

Fig. 3. EIS probe used in the ow loop system.

Fig. 4. The Nyquist plots for C-1018 carbon steel exposed to CO2 saturated ASTM saltwater with 100
ppm inhibitor under slug ow of Fr 6 with various times.

Nyquist plot measured at each exposure time presents one depressed semicircle with
a long tail at low frequency region. The tails are inclined at an angle of 45 to the
real-axis at the very low frequencies. This indicates that, for each exposure time, the
diusion process of ions takes place on the electrode. From Fig. 4, it can be also
106 T. Hong et al. / Corrosion Science 44 (2002) 101112

observed that the diameter of semicircle increases with increasing time. This means
that the corrosion rate becomes lower at longer exposure time.
There are two methods to describe the EIS spectra for the inhomogeneous lms
on the metal surface or rough and porous electrodes. One is the nite transmission
line model [11]. The other is the lmed equivalent circuit model, which is usually
proposed to study the degradation of coated metals [12,13]. It has been suggested
that the EIS spectra for the metal covered by organic inhibitor lms are very similar
to the failed coating metals [14]. Therefore, in this work the lmed equivalent circuit
model is used to describe the inhibitors-covered metal/solution interface under ow
conditions.
The standard circuit model for coating metals/solution interface used extensively
in the literature is shown in Fig. 5a [12,13]. Here Rs is the solution resistance, Rf and
Cf are the coating lm resistance and capacitance, respectively. Rt is the charge
transfer resistance, Cdl is the double layer capacitance that characterizes the charge
separation between metal and electrolyte interface and Zw is the Warburg impedance.
Zw can be presented as [15]
1=2
Zw rx 1 j 2
where r is the Warburg coecient, X cm2 s 1=2
; x 2pf rad s 1 .

Fig. 5. (a) Equivalent circuit model for interpreting the coating metal. Rs , solution resistance; Rf , coating
lm resistance; Cf , coating lm capacitance; Rt , charge transfer resistance; Cdl , double layer capacitance;
Zw , Warburg impedance. (b) Simplied equivalent circuit model for the metal covered by porous inhibitor
lms (C Cf Cdl ).
 T. Hong et al. / Corrosion Science 44 (2002) 101112 107

The model as shown in Fig. 5a includes two parallel resistance and capacitance
combinations and Warburg impedance, which are considered to contain coating
lm, metal substrate and diusion information [12,13]. Two semicircles and a dif-
fusion tail would be expected on the Nyquist plot. However, it is dicult to nd two
semicircles for C-1018 carbon steel exposed to the inhibitor containing solution in
Fig. 4. This could result from that imidazoline adsorbed on the metal surface forms a
monolayer [4,14] and the high rate of wall shear stress of the turbulent ow makes
the inhibitor lm porous. It can be considered that the inhibitor lm resistance (Rf ) is
much smaller than the charge transfer resistance (Rt ). The semicircle representing the
inhibitor lm merges with the charge transfer loop [15]. Hence, the EIS spectra as
shown in Fig. 4 are described by a simple equivalent circuit as shown in Fig. 5b [10].
At low frequency, the capacitive component C (C Cf Cdl ) no longer aects the
total impedance value and the total impedance, Zt , can be presented as [15]
Zt Rs Rt Zw 3
According to Eq. (2), the Warburg impedance, Zw , is dependent on its coecient,
r. In another word, r represents the diusion resistance within the inhibitor lm. The
larger the value of r, the more dicult the ions diuse through the pores through the
inhibitor lms, showing that the inhibitor lms are less porous or have pores with
smaller equivalent diameter [10].
The Warburg impedance coecient r can be obtained from Eq. (4) by using the
Nyquist impedance plots of Fig. 4 at low frequencies where the diusion tails are
inclined at the angles of 45 to the resistive axis as shown in Fig. 6 [13].
r bx1=2 4
where b is the resistive component of impedance at which the diusion tail begins to
be inclined at an angle of 45 to the resistive axis, and x 2pf (f is a frequency at
which the diusion tail begins to be inclined at an angle of 45 to the resistive axis).

Fig. 6. Calculation of Rt and r.

108 T. Hong et al. / Corrosion Science 44 (2002) 101112

Fig. 7 shows the results of r measured in saltwater with 100 ppm inhibitor under
slug ow of Fr 6. It is found that the value of r increases with exposure time.
Increase in r implies decrease in amount of the ions for diusion through the in-
hibitor lm. This might indicate that the inhibitor lm is less porous or becomes
thicker at longer exposure time. On the other hand, the charge transfer resistance, Rt ,
increases with increase in time as shown in Fig. 8. This means that the corrosion rate
decreases when the exposure time is increased. These demonstrate that the corrosion
inhibitor has a good performance of corrosion protection by forming more compact
inhibitor lms on the metal surface at longer exposure time.
Figs. 9 and 10 show the Nyquist impedance plots measured in slug ow at Fr
number 9 and 12. It is observed that, for both of the slug ow conditions, the dia-
meters of semicircles increase with the time and the diusion processes are pre-
sented for all exposure times. In order to compare the inhibitor performance under
dierent slug ow conditions, the results of Rt and r which are obtained from Ny-
quist impedance plots (Figs. 4, 9 and 10) are summarized in Figs. 11 and 12, re-
spectively. For each of slug ow condition, Rt and r increases with increasing
exposure time. This has been suggested to originate in the thicker or less porous
inhibitor lm formed on the metal surface at longer exposure time. It can be also
found that, at a given exposure time, both Rt and r decrease with increasing the
Froude number of slug ow. These facts indicate that the performance of the in-
hibitor is aected by the ow conditions. Because there is a highly frothy turbulent
region in slug ow, the gas in this region is in the form of pulse of bubbles. These
bubbles are trapped by the mixing vortex and shot to the bottom of the pipe where

Fig. 7. The relationship between the Warburg impedance coecient and exposure time in ASTM salt-
water with 100 ppm inhibitor under slug ow of Fr 6.
 T. Hong et al. / Corrosion Science 44 (2002) 101112 109

Fig. 8. The relationship between the charge transfer resistance and exposure time in ASTM saltwater with
100 ppm inhibitor under slug ow of Fr 6.

Fig. 9. The Nyquist plots measure in ASTM saltwater with 100 ppm inhibitor in slug ow of Fr 9.

they can impact and collapse on the pipe walls [1]. Some inhibitor lms, which have
been adsorbed on the metal surface, are damaged by the turbulence and bubble
110 T. Hong et al. / Corrosion Science 44 (2002) 101112

Fig. 10. The Nyquist plots measured in ASTM saltwater with 100 ppm inhibitor under slug ow of
Fr 12.

Fig. 11. Changes in charge transfer resistance with exposure time under dierent slug ow conditions.
 T. Hong et al. / Corrosion Science 44 (2002) 101112 111

Fig. 12. Changes in Warburg impedance coecient with exposure time under dierent slug ow con-
ditions.

impact and washed away from the metal surface. The turbulence and bubble are
dependent on the Froude number of slug ow. The higher Froude number of slug
ow results in the higher turbulence and the higher frequency of bubble pulse on the
metal surface. Therefore, the inhibitor lm in higher Froude number of slug ow
becomes thinner and more porous, leading to lower corrosion resistance and War-
burg impedance coecient.

4. Conclusions

EIS technique is used to study the inhibition performance of corrosion inhibitors

under slug ow conditions in large pipelines. The following conclusions are obtained.

1. For each of slug ow condition, Rt and r increase with increasing exposure time.
This might indicate that the corrosion inhibitor has a good performance of corro-
sion protection by forming more compact inhibitor lms on the metal surface at
longer exposure time.
2. The eect of Froude number of slug ow on the inhibitor performance is signi-
cant. The higher the Froude number of slug ow, the thinner or more porous the
inhibitor lm formed on the surface of steel, showing that the corrosion resistance
becomes lower.
112 T. Hong et al. / Corrosion Science 44 (2002) 101112

References

[1] J.-Y. Sun, W.P. Jepson, SPE Paper 24787, 1992, p. 215.
[2] W.P. Jepson, Third International Conference on Multiphase Flow, The Hague, Netherlands, 1987,
p. 187.
[3] Y.J. Tan, S. Bailey, B. Kinsella, Corros. Sci. 38 (10) (1996) 1681.
[4] Y.J. Tan, S. Bailey, B. Kinsella, Corros. Sci. 38 (9) (1996) 1545.
[5] D. Klenerman, J. Hodge, M. Joseph, Corros. Sci. 36 (2) (1994) 301.
[6] A. Edwards, C. Osborne, S. Webster, et al., Corros. Sci. 36 (2) (1994) 315.
[7] C. Neice, G.T. Solvi, S. Skjerve, Br. Corros. J. 32 (4) (1997) 269.
[8] Y.J. Tan, B. Kinsella, S. Bailey, Br. Corros. J. 32 (3) (1997) 212.
[9] S. Bailey, Y.J. Tan, B. Kinsella, Br. Corros. J. 32 (1) (1997) 49.
[10] Y. Chen, T. Hong, M. Gopal, W.P. Jepson, Corros. Sci. 42 (2000) 979.
[11] J.R. Park, D.D. Macdonald, Corros. Sci. 23 (4) (1983) 295.
[12] G.W. Walter, Corros. Sci. 32 (10) (1991) 1041.
[13] G.W. Walter, Corros. Sci. 30 (6/7) (1990) 617.
[14] F. Mansfeld, Electrochem. Acta 35 (10) (1990) 1533.
[15] G.W. Walter, Corros. Sci. 26 (9) (1986) 681.