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Corrosion Science 48 (2006) 23632379

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Carbon-steel corrosion in multiphase


slug ow and CO2
J. Villarreal, D. Laverde *, C. Fuentes
Universidad Industrial de Santander, School of Chemical Engineering,
P.O. Box 678 Bucaramanga, Colombia
Received 1 June 2004; accepted 10 September 2005
Available online 9 November 2005

Abstract
Hydrocarbon multiphase ow may exhibit various geometric congurations or ow patterns. One
of these ow patterns is known as multiphase slug ow. If CO2 is present in hydrocarbons, the steel
pipelines can be corroded as this process is probably enhanced by slug ow turbulence. A hydrodynamic circuit was built to study the CO2 corrosion rates under dierent slug ow conditions. The
experimental results show how the corrosion rate of a carbon-steel electrode varies according to
the ow turbulence. The higher slug frequency used in this study was 80 slugs/min. Experimental
results for pressure drop and slug length are in agreement with the Dukler and Hubbard [A model
for gasliquid slug ow in horizontal and near horizontal tubes, Ind. Eng. Chem. Fundam. 14 (1975)
337347] multiphase ow model. Furthermore, the experimental slug frequencies are well correlated
by the Shell and Gregory [Correlation of the liquid volume fraction in the slug for horizontal gas
liquid slug ow. Int. J. Multiphase Flow 4 (1978) 3339] equations in horizontal pipes.
2005 Elsevier Ltd. All rights reserved.
Keywords: Flow loop; Multiphase slug ow; Horizontal ow; CO2 corrosion; Mass transport; Hydrodynamics

1. Introduction
CO2 corrosion in hydrocarbon production and transportation pipelines is dicult
to understand, predict, and control. The hydrocarbons coming from the reservoirs in
*

Corresponding author. Fax: +57 7 6350540.


E-mail addresses: jvillarreal@corrosion.uis.edu.co (J. Villarreal), dlaverde@uis.edu.co (D. Laverde),
cfuentes@corrosion.uis.edu.co (C. Fuentes).
0010-938X/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2005.09.003

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pipelines form a multiphase complex mixture (gas, liquids and solids) with dierent ow
patterns that, due to highly turbulent hydrodynamics, can cause erosion and corrosion.
Slug ow is one of these high turbulent ow patterns. This ow is characterized by a turbulent front, a liquid lm and a gas phase package that travels above the lm. The slug
front is considered to be highly turbulent due to the mixture of liquid, gas and solid phases
that, in turn, can produce erosion/corrosion on the pipeline surface.
Many studies on the corrosion caused by CO2 in aqueous phases can be found in the
open literature [112]. Various factors have been considered such as CO2 partial pressure,
temperature, uid composition, and materials metallurgy. Nevertheless, very little is
known about the eect of multiphase ow on CO2 corrosion. Most of the above mentioned studies have been carried out in laboratories using cells, disks, rotary cylinders
and autoclaves. Corrosion studies under multiphase ow require hydrodynamic circuits
to be built in pipes of considerable length to obtain dierent ow patterns and therefore
they are very scarce.
Jepson et al. [10] examined the CO2 corrosion in carbon-steel pipes under multiphase
slug ow conditions. These studies were initially conducted in large-diameter pipes such
as the Alaskan pipeline. Long slugs with low frequencies (around 20 slugs/min) are formed
due to high uid velocities.
Models and empirical correlations have been developed to explore and predict slugs
hydrodynamics [13,14], but they generally require further validation since they are only
applicable in very specic cases.
This paper presents the CO2 corrosion rate results obtained with a steel-carbon electrode exposed to an aqueous phase with CO2. The eect of the slug frequency up to a value
of 80 slugs/min is analyzed. The dierences between the corrosion rate obtained in experiments with a single aqueous phase and an aqueous multiphase slug ow are explained.
Furthermore, the change in corrosion rate when rened oil or solids are added to an aqueous phase was also considered.
As a nal result, the equation given by Jepson et al. [12] to calculate the corrosion rate
as a function of slug frequency, pressure gradient and temperature was slightly modied to
extend the frequency range of application.
2. Experimentation methodology
Fig. 1 shows the hydrodynamic circuit or multiphase ow loop designed and built to
study the slug ow pattern experimentally. It was built with SS 316 steel pipes and a transparent 5 cm diameter PVC pipe. The main parts of the circuit such as tanks, pumps and
instruments were manufactured with materials that exhibit better resistance to corrosion,
such as SAE 316 SS and Hastelloy. Registration and control of variables were conducted
by means of a programmable logical controller SLC-500. The 25-m long horizontal, transparent test section was designed with special consideration for the stable formation of
slugs. The corrosion measurement cell was designed to have fully developed hydrodynamic
and mass transfer [15] layers on the electrodes. The steel electrodes measured 8 cm length
and were placed at the bottom of the pipe.
The experimental CO2 partial pressure was xed at 0.1358 MPa (5 psig) and the temperature at 40 C. The equipment, the electrochemical cell and the electrodes were prepared
before each experiment. Other activities before starting the experimental test included:
cleaning of the hydrodynamic circuit with distilled water, supply of CO2 to the separation

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Fig. 1. Flow loop scheme.

J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

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J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

tank for 12 h, preparation of electrodes following the ASTM G-1 protocol, adjustment of
pressure with gaseous CO2 and temperature adjustment. The chemical composition of the
carbon-steel electrodes was veried to conform to the carbon-steel AISI-SAE 1020 with
ferrite and perlite metallurgical structure.
The test procedure consisted of the following steps: rst, adjustment of variables such
as uid velocity, temperature, and pressure; second, connection of the electrochemical cell
to the Potentiostat/Galvanostat EG&G Princenton M-273-A; third and last, recording of
the resistance polarization data (LPR), corrosion currents, limiting cathodic currents, and
solution resistance, by means of direct current electrochemical techniques such as linear
polarization LPR, Tael and, impedance spectroscopy EIS. The following experimental
variables were monitored: CO2 concentration, O2 dissolved in the aqueous phase by colorimetric techniques, pH, dissolved iron, and chlorides. CO2 aqueous concentration was
kept between 500 and 600 ppm, O2 between 5 and 20 ppb, Fe++ between 3 and 6 ppm,
and pH between 4.2 and 4.3. Data related to pressure, temperature, density, and uid viscosity, pressure gradient in the 10-m test section, phase ow velocity, slug frequency, and
slugs characteristic length were recorded by circuit instrumentation. Slug frequencies were
obtained by measuring and recording electric pulses generated by the slug passage through
platinum electrodes located at the pipe top. The slugs characteristic length was visually
measured at the transparent section of the horizontal pipe.
The rst experiments were conducted with a single CO2-saturated aqueous phase owing through the whole pipe of the multiphase loop. The electrode corrosion rate was measured at dierent uid velocities. Tael plots showed the limiting cathodic currents. The
diusion current of the species H+ and H2CO3 were calculated and a corrosion cathodic
mechanism for CO2 reactions was proposed based on experimental results.
The experiment continued with corrosion analysis under multiphase slug ow conditions, analyzing the change of corrosion rate with slug frequency changes. Correlations
from previous studies [13,14,16] were analyzed to nd the values of some parameters that
characterize the slugs, such as the length of their parts, pressure drop, and ow rate of
their phases, liquid holdups, and slug frequencies. These correlations were also compared
10

Liquid velocity (m/s)

dispersed bubbles
test area
slug
1
slug

annular
0.1
smooth stratified

0.01
0.01

0.1

wavy
stratified

10

100

Gas velocity (m/s)


Fig. 2. Flow map based on the Shoham [17] model and the experimental uid properties.

J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

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with experimental results. Initially, a map of the ow regions was drawn based on the Shoham [17] model, which requires data about the physical and mechanical properties of the
phases. The map, shown in Fig. 2, veries that experimental conditions correspond to multiphase slug ow and the visual observation of slugs in the transparent section. Corrosion
rate was measured for liquid phase velocities of 1.18, 1.75 and 2.25 m/s, and gas phase
velocities ranging between 0.384 and 2.69 m/s. Jepson et al. [10] used the dimensionless
Froude number as the slug turbulence main characteristic. In this study, the Froude number was calculated at experimental conditions and compared with the results published by
the above mentioned author.
Finally, preliminary experiments were conducted with the addition of rened white oil
to the aqueous phase to observe the change in corrosion rates due to the presence of oil.
We also added quartz silica sand measuring 150 lm diameter and 1% concentration in
water to analyze the change in corrosion rates due to erosive eects.
3. Results and discussion
The corrosion rate results as a function of liquid velocity for a single aqueous phase
ow are shown in Fig. 3. The corrosion rate shows an initial increase with uid velocity,
up to a value of 2.0 mm/year at a liquid velocity of 0.55 m/s. For liquid velocities greater
than 0.55 m/s, a small reduction and corrosion rate stabilization were observed. This latter
eect is probably due to the fact that corrosive species transferred by movement are not as
important as the electrochemical reactions at experimental ow conditions, and therefore
corrosion rate is not aected by the uid ow rate. At the highest liquid velocities, the corrosion begins to increase again. This increased high turbulence is likely removing the protective layers formed by corrosion products, thus producing greater corrosion rates. A
similar eect has been observed by other researchers [3,5] in experiments conducted on
pipe ows and on rotational cylinders.
On the other hand, potentiodynamic Tael plots were obtained for this single aqueous
phase experiment. A limiting cathodic current behavior corresponding to reduction reactions of the species present in the experimental corrosive aqueous phase was observed in

Corrosion rate (mm/year)

0
0

0.5

1.5

2.5

Liquid velocity (m/s)


Fig. 3. Carbon-steel 1020 electrode corrosion rate for single aqueous phase ow, distilled water, 1% of NaCl,
saturated with CO2, 40 C, 0.1358 MPa.

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J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

this plot. The limiting cathodic current values, obtained from the experimental Tael
slopes, were plotted vs. uid velocity as shown in Fig. 4. Note that the curve leaves the
Y axis with a value of 0.18 mA/cm2 and increases with the uid velocity. Fig. 4 also shows
H+ and H2CO3diusion current curves calculated by equations found in the literature.
Note that the experimental limiting cathodic currents are not equal to the diusion currents as found in strong acid solutions.
The curve of the limiting cathodic current illustrated in Fig. 4 shows a diusion limiting
current that increases with uid velocity, and another ow independent limiting current
with a value of 0.18 mA/cm2. Furthermore, it is possible to state that the ow dependent
limiting cathodic current would likely be composed by contributions of diusion currents
that, in turn, are caused by the H+ and H2CO3 proton reductions transferred from the
solution towards the metal surface.
Fig. 5 compares the behavior of the experimental corrosion current and the limiting
cathodic current as uid velocity is changed. Note that the corrosion current is lower than
the cathodic limiting current; this observation was also reported by Mendoza-Florez and
Turgoose [8] in rotational cylinder tests at 20 C. Eriksrud and Sontvedt [6] and MendozaFlorez and Turgoose [8] also concluded that the corrosion rate is not aected by uid
velocities greater than 0.5 m/s. At high uid velocity the mechanism changes to a controlled reaction rate on the metal surface.
The behavior of the cathodic limiting current can indicate two issues: rst, a corrosion
process dominated mainly by diusion of corrosive species such as H+ and H2CO3 occurring at low uid velocities; and second, when the limiting cathodic current is not equal to
the H+ cathodic diusion current, the limiting cathodic current is probably formed by the
sum of several cathodic currents. This phenomenon has been previously explained by some
researchers, Schmitt and Rothman [5], Turgoose and Cottis [2], Eriksrud and Sontvedt [6]
by Eq. (1), in which the total limiting cathodic current, ICL, is the sum of an independent
ow current, II, plus a dependent ow current, ID
I CL I I I D

1
+

1.4

D.C. H

1.2

D.C. H2CO3
C.L.C.

I (mA/cm2)

1
0.8
0.6
0.4
0.2
0
0

0.5

1.5

2.5

Liquid velocity (m/s)


Fig. 4. Limiting cathodic current (LCC) obtained from experimental data, for single aqueous phase, distilled
water, 1% of NaCl, saturated with CO2, 40 C, 0.1358 MPa, and diusion currents of the ions H+ (DC H+) and
carbonic acid H2CO3 (DC H2CO3) from equations taken from the literature.

J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

I (mA/cm2)

1.3
1.2
1.1
1

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C.C.
C.L.C.
D.C. H

0.9
0.8
0.7
0.6
0.5
0.4

0.3
0.2
0.1
0
0

0.25

0.5

0.75

1.25

1.5

1.75

2.25

2.5

Liquid velocity (m/s)


Fig. 5. Experimental limiting cathodic current (LCC), Experimental corrosion current (CC), and theoretical
diusion current of the H+ (DC H+), for single aqueous phase ow, distilled water, 1% of NaCl, saturated with
CO2, 40 C, 0.1358 MPa.

The independent limiting cathodic ow current II is related to the carbonic acid (H2CO3)
direct reduction that can be adsorbed in the surface of the metal, as it is shown by previous
impedance spectroscopy experiments. This experiment demonstrated the existence of
inductive loops that are typical of acids adsorbed on metal surfaces. H2CO3 direct reduction is also an explanation for higher carbon-steel corrosion when exposed to an aqueous
solution with CO2 than steel corrosion in an aqueous solution with a strong acid (HCl) in
equivalent concentration.
Therefore, based on the evidence resulting in this research, reactions that cause the
independent cathodic current, II, are explained as follows:
CO2 ads H2 O H2 CO3 ads
H2 CO3 ads e ! Hads

HCO
3

2
3

Reaction (2) corresponds to the adsorbed CO2 hydration to form the adsorbed carbonic
acid, H2CO3 ads, while reaction (3) corresponds to H2CO3 ads direct electrochemistry reduction. The proposed reaction mechanisms for the independent uid ow cathodic currents
are explained by Eqs. (2) and (3). A similar mechanism was proposed by Eriksrud and
Sontvedt [6] with experiments conducted in a 2.5 cm diameter hydrodynamic circuit of
a, with a 4% NaCl solution at a temperature of 20 C.
On the other hand, we suggest that the electrochemical reactions that can cause the
dependent ow current, ID, that is, the second right term in Eq. (1), corresponds to the
reactions given below, according to the experimental results

H
sol ! Hads

H2 CO3 sol ! H2 CO3 ads ! H
ads HCO3 ads

4
5

H
ads e ! Hads
Hads Hads ! H2 ads

6
7

H2 ads ! H2 sol

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J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

Eqs. (4)(8) are the proposed uid ow dependent reactions and are similar to reactions
given by Schmitt and Rothman [5], and Turgoose and Cottis [2] who worked with disks
and rotational cylinders and with Na2SO4 solutions. Even though the experimental conditions used in this study, i.e., distilled water, 1% NaCl, saturated with CO2, 40 C,
0.1358 MPa, 5 cm pipe inside diameter, are dierent from those used in other studies,
the proposed mechanism for CO2 corrosion on steel pipes is similar.
3.1. Corrosion by CO2 in multiphase slug ow
The corrosion rate obtained for each liquid surface velocity of 1.18, 1.75 and 2.25 m/s,
and gas surface velocities of 0.384, 0.769, 1.154, 1.92 and 2.69 m/s are shown in Fig. 6.
Fig. 6 also shows the value of the corrosion rate under static conditions obtained in tests
outside the multiphase loop.
Fig. 6 shows that the highest corrosion rate, 3.63 mm/year, is obtained when the liquid
surface velocity is 1.18 m/s. If the liquid surface velocity increases, corrosion rate values
decrease. See how dierent corrosion rates are at liquid surface velocities of 1.18 and
1.75 m/s. A possible explanation for this behavior is the relationship of the surface velocity
that each phase maintains in relation to each other. Slugs with dierent turbulent characteristics are formed according to the surface velocity and the relationship between them.
For example, for a surface gas velocity of 1.154 m/s, and the lowest surface liquid velocity
of 1.18 m/s, the values corresponding to slug total length and heads are higher than those
obtained at higher liquid velocities. The tests with long slugs demonstrate that their turbulent fronts hit the bottom part of the pipes with more force and cause greater damage than
shortest slugs that do not reach the bottom part of the pipes. This behavior is reected in
the corrosion rates shown in Fig. 6.
The corrosion rate as related to the phases surface velocities can also be analyzed based
on the slug frequency. Fig. 7 shows that for a velocity of 1.18 m/s, the corrosion rate
increases for a frequency range between 0.88 and 1.21 slugs/s. However, the corrosion rate
does not vary considerably above these frequencies, and even decreases very slightly with
slug frequency. For higher liquid surface velocities of 1.75 and 2.25 m/s, the corrosion rate

Corrosion rate (mm/year)

5
4.5

Vsl 1.18 m/s

Vsl 1.75 m/s

3.5

Vsl 2.25 m/s

3
2.5
2
1.5
1
0.5
0
0

0.5

1.5

2.5

Vsg (m/s)

Fig. 6. Carbon-steel 1020 electrode corrosion rate variation with the liquid surface velocity (Vsl) and gas surface
velocity (Vsg), in an aqueous solution, 1% NaCl, N2, CO2, 40 C and 0.13 MPa.

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Corrosion rate (mm/year)

5
4.5

Vsl 1.18 m/s

Vsl 1.75 m/s

3.5

Vsl 2.25 m/s

3
2.5
2
1.5
1
0.5
0
0

Slug frequency (slug/s)


Fig. 7. Eect of Slug frequency changes on carbon-steel 1020 electrode corrosion rate, in an aqueous solution, 1%
NaCl, N2, CO2, 40 C and 0.13 MPa.

is lower than that observed for a velocity of 1.18 m/s and it is almost constant at the highest slug frequencies. An explanation for this eect probably relies on the possible reduction
of slugs turbulence at high frequencies, in cases above 1.21 slugs/s.
The slugs frequency was obtained under dierent experimental conditions by means of
the device designed and installed in the multiphase loop. Frequency is a characteristic
parameter of each slug, and its value depends mainly on the velocity of the phases forming
the multiphase ow. The slug frequencies measured experimentally were compared with
those calculated using some correlations [14,1825] found in the literature. Fig. 8 shows
that the closest correlations to the frequency experimental values found in this experiment
were those found by Shell [14] and Gregory Scott [18].

4.00
Shell

Slug frequency (slug/s)

3.50

Gregory Scott

3.00

Tronconi

2.50

Experimental
2.00
1.50
1.00
0.50
0.00
0

0.5

1.5

2.5

Vsg (m/s)
Fig. 8. Experimental slug frequencies and slug frequencies values calculated by the correlations of Shell [14],
Gregory Scott [18] and Tronconi [25] for the aqueous system 1% NaCl, CO2 and N2, 40 C, 0.1358 MPa,
Vsl = 1.18 m/s.

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J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

Slug frequency (slug/s)

6
Vsl 1.18 m/s
5

Vsl 1.75 m/s


Vsl 2.25 m/s

4
3
2
1
0
0

0.5

1.5

2.5

Vsg (m/s)
Fig. 9. Eect of gas surface velocity (Vsg) on slug frequency at dierent liquid surface velocities for the aqueous
system 1% NaCl, CO2 and N2, 40 C, 0.1358 MPa.

Fig. 9 shows that when the surface liquid velocity is increased from 1.18 to 2.25 m/s, the
slug frequency increases. Nevertheless, for each surface liquid velocity, when the surface
gas velocity is increased the slug frequency decreases. This reduction behavior in slug frequencies occurs when the volumetric gas phase increases, making the slugs and their parts
extend inside the pipe. When the gas phase is reduced, the slugs are shortened and a
greater number of them are transported along the pipe. This eect is proven by measuring
the number of times the head of the slug passes a xed point in the pipe.
The Froude number is another option to analyze corrosion rate behavior based on the
changes in slug characteristic factors and the phases velocity. The Froude number form
dened by Jepson et al. [12] takes into consideration a measure of turbulence level and
indicates the relationship between the inertia and the gravitational forces, as given by
the following equation:
V t  V LTB
Fr p
gH LTB

where Vt is the translational velocity of the slug (m/s); VLTB is the velocity of the liquid
lm of the slug (m/s); g is the acceleration due to gravity, 9.8 m/s2; HLTB is the height
of the liquid lm of the slug (m).
Table 1 shows the information related to Froude numbers calculated by Eq. (9), for the
liquid and gas phases velocity used in the slug tests. The Froude numbers calculated in this
research are lower than those published by Jepson et al. [12]. The dierence is explained by
the gas phase quantity involved in the slugs. High surface gas velocities correspond to high

Table 1
Froude numbers corresponding to the experimental Vsl and Vsg, for the aqueous system at slug ow, 1% NaCl,
CO2 and N2, 40 C, 0.1358 MPa
Vsl (m/s)
Vsg (m/s)
F (slug/min)

1.18
0.384
88.8

1.18
0.769
82.8

1.18
1.154
75

1.75
0.384
174

1.75
0.769
166.8

1.75
1.154
147

2.25
0.384
186.6

2.25
0.769
167.8

2.25
1.154
159.6

Froude number

1.25

2.0

2.8

1.25

2.0

2.8

1.25

2.0

2.8

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Froude numbers. Jepson et al. [12] conducted studies in 10 cm diameter pipes with surface
gas velocities above 2 m/s, corresponding to high Froude numbers and low slug frequencies. In this study, we worked with a horizontal 5 m diameter pipe surface, gas velocities
below 2 m/s, and slug frequencies above 50 slug/min.
Fig. 10, based on data given in Table 1, shows how corrosion rate changes with slug
frequency and Froude number. A similar behavior to that illustrated in Fig. 7 is also
shown in Fig. 10. If the slug frequency is above 73 slug/min the corrosion rate decreases.
Figs. 10 and 11 show that greater corrosion rates are evident when Froude numbers
increase. This behavior was also observed in Jepson et al. [12] studies thus demonstrating
that when the turbulence of the slug heads increases, the corrosion rate also increases.
Fig. 12 was obtained based on data from the Dukler and Hubbard [13] multiphase ow
model. This was also validated and adjusted with experimental data. Results indicate that
the corrosion rate increases with the total pressure drop of the slug based on the fact that
at high slug frequencies the corrosion rate is lower.

Corrosion rate (mm/year)

4
3.5
3
2.5
2
1.5
No Froude 1.25

No Froude 2.0
0.5

No Froude 2.8

0
0

50

100

150

200

Slug frequency (slug/min)


Fig. 10. Eect of slug frequency on carbon-steel 1020 electrode corrosion rate at dierent Froude numbers, for an
aqueous solution 1% NaCl, N2, CO2, 40 C and 0.13 MPa.

Corrosion rate (mm/year)

4
3.5
3
2.5
2
1.5
Slug Frec 82 (s/m)

Slug Frec 163 (s/m)


0.5

Slug Frec 172 (s/m)

0
0

0.5

1.5

2.5

Froude number
Fig. 11. Eect of Froude number on carbon-steel 1020 electrode corrosion rate at dierent slug frequencies, for
an aqueous solution 1% NaCl, N2, CO2, 40 C and 0.13 MPa.

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J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

Corrosion rate (mm/year)

4
3.5
3
2.5
2
1.5
1
Slug Frec 82 (s/m)

0.5

Slug Frec 172 (s/m)

0
0

200

400

600

800

1000

1200

Pressure gradient (Pa/m)


Fig. 12. Carbon-steel 1020 electrode corrosion rate versus the pressure gradient at dierent slug frequencies, for
an aqueous solution, 1% NaCl, N2, CO2, 40 C and 0.13 MPa.

3.2. Mathematical correlation of corrosion rate with operational variables


Jepson et al. [12] developed the equation given below to estimate the CO2 corrosion rate
of carbon-steel pipe transporting an aqueous saline solution saturated with CO2 in a multiphase slug ow.
CR 31  FF  DP =L0:33  P 0:8
CO2  T  exp2671=T

10

0.33

In Eq. (10) FF is the frequency factor; the term (DP/L)


represents the ow pressure gradient, in Pascal/meter; (PCO2)0.8 represents the CO2 partial pressure in Mpascal; and T is
the Kelvin temperature.
The Jepson [12] equation was extended to higher slug frequencies, above 35 slugs/min,
by modifying the frequency factor coecient. The frequency factor, given by Eq. (11), was
obtained as follows: the rst step was to normalize the corrosion rate data; then, normalized data were plotted vs. the logarithm of the slug frequency, F (slugs/min); and nally,
we looked for the equation that better tted the experimental data plot; the result of this
procedure is Eq. (11).
4

FF 136  log F 1114  log F  3413  log F 4633  log F  2350


11
According to Jepsons equation, corrosion rates vary linearly with slug frequencies, at low
frequencies. As shown in Fig. 7, for higher frequency data, corrosion rate is inversely proportional with slug frequency.
Fig. 13 shows corrosion rate data calculated based on the correlation given by Eq. (10).
These data were also compared with those obtained experimentally, thus giving a good
approximation with experimental results.
3.3. Inuences of the oil phase in CO2 corrosion of slug ow
The rst step for this part was to check the existence of slug ow visually under experimental conditions that, in turn, were also conrmed with the ow map obtained with the

J. Villarreal et al. / Corrosion Science 48 (2006) 23632379

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Corrosion rate (mm/year)

4
3.5

experimental data
correlation data

3
2.5
2
1.5
1
0.5
0
0

50

100

150

200

Slug frequency (slug/min)


Fig. 13. Carbon-steel 1020 electrode corrosion rate calculated using the modied Jepson correlation and
compared with experimental values at dierent slugs frequencies, Vsl: 1.18, 1.75, 2.25 m/s, Vsg: 0.38, 0.769 and
1.154 m/s, for an aqueous solution, 1% NaCl, N2, CO2, 40 C, 0.13 MPa.

Shoham [17] model. Corrosion rate values were obtained by the linear polarization resistance LPR technique. The objective was to nd some preliminary concepts about the eect
that the water-rened oil dispersion, as part of the slug ow, can cause to the carbon-steel
corrosion rate in this study. A surface liquid velocity of 1.18 m/s was selected for this test
for two reasons: rst, in agreement with previous studies, dispersion is more stable and
durable at this velocity; and second, to facilitate the comparison with results obtained with
multiphase aqueous slug ow that showed the highest corrosion rate.
Fig. 14 shows that no substantial changes are caused by the presence of the oil dispersed
phase in a proportion of 70% CO2 aqueous solution and 30% rened oil. Tensoactive
agents were not used in this case; dispersion was mechanical and not chemical, and the
mineral oil used is an inert hydrocarbon fraction. The presence of oil drops does not seem
to interfere substantially in the diusion processes and in the surface reactions of causing
corrosion agents.

Corrosion rate (mm/year)

8
Aqueous solution

Dispersed oil

6
5
4
3
2
1
0
0

0.5

1.5

2.5

Vsg (m/s)
Fig. 14. Comparison of the corrosion rate of a carbon-steel 1020 electrode with and without the presence of oil,
for an aqueous solution, 1% of NaCl, water oil 70/30 ratio, CO2, N2, 40 C, 0.13 MPa, Vsl: 1.18 m/s.

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If an oil phase is present in a corrosive solution, it is generally expected that this phase
reduces the corrosion rate to some extent. However, this study shows that the 70/30 ratio
of mineral oil and water does not reduce corrosion rates. The possible reason is that the
test electrode was not completely impregnated by the oil due to the high turbulence of
the slug. This allowed the CO2 aqueous phase to arrive to the metallic surface without
any obstacles and, therefore, the corrosion rate exhibited almost the same value as that
obtained with multiphase aqueous slug ow experiments.
Another possible reason for this small inuence of dispersed oil on the corrosion rate is
that rened white oils, such as this mineral oil, have lost some natural compounds compared to the crude oil in the wells. These natural components could be responsible for
the corrosion rate reduction, as some studies conducted in autoclaves show [2628]. But
in some cases, even using crude oils that have these protective compounds, the turbulence
of the uid removes them. This behavior has been observed in some wells in the petroleum
elds.
An important experimental result was also found: the Electrochemical Impedance Spectroscopy technique (EIS) was used to measure the solution resistance (Rs), polarization
(Rp) and charge transfer (Rt). The polarization resistance (Rp) values obtained with the
direct current method (LPR) are very close to those obtained by the EIS technique. Since
results obtained by either technique are very close, either experimental technique can be
used to calculate corrosion rates with the same degree of condence.
Slug frequencies obtained experimentally are very close to the predictions stated by the
Shell [14] and Gregory [18] correlations. This behavior was also obtained for the multiphase aqueous slug ow system. Experimental values for characteristic slugs parameters
such as length and pressure drops are favorably compared to the predictions given by
the Dukler and Hubbard [13] model.
The results obtained in these tests for a liquid surface velocity of 1.18 m/s and gas surface velocities ranging from 0.769 up to 1.92 m/s show that slugs frequencies decrease as
gas surface velocity increases. Nevertheless, the total length of slugs, the pressure drops
and the translational velocity increase.

Corrosion rate (mm/year)

6
Aqueous solution

Sand 1%
4
3
2
1
0
0

0.5

1.5

2.5

Vsg (m/s)
Fig. 15. Comparison of the corrosion rate of a carbon-steel 1020 electrode with and without the presence of sand,
for an aqueous solution, 1% NaCl, silica sand of 150 lm, CO2, N2, 40 C, 0.13 MPa.

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3.4. Inuences of addition of solids on CO2 corrosion in multiphase slug ow


Solids of a known size (150 lm diameter) were added to the CO2 aqueous phase to analyze their eect on corrosion rates under multiphase slug ow. The results obtained for
corrosion rates when a solid phase (1 wt.%) is added to the aqueous phase are shown in
Fig. 15. At a liquid velocity phase of 1.18 m/s, the presence of the solids caused a slight
increment in the corrosion rate. The possible reason for this slight increment is the combined action of the erosioncorrosion processes due to a high turbulence in the head or
front of the slugs that, in turn, can remove the protective lms formed by corrosion products. The solids suspended on the aqueous phase increase corrosion rates even at such low
solid concentration used in this study (1 wt.%).
The results obtained in this section of the study show that the presence of abrasive solids in the system is very interesting. Their impact deserves further research due to their
high inuence on operational and economic aspects of the oil and gas industries.
4. Conclusions
1. Based on the experimental conditions of this study, that is, single aqueous phase ow
using a 5-cm diameter pipe, aqueous saline solution with a concentration of 1% of NaCl
saturated with CO2, the corrosion rate is governed by a diusion mechanism of the corrosive species H+ and H2CO3 at low liquid surface velocities. For surface liquid velocities above 0.5 m/s, the corrosion rate is controlled by a combined mechanism of
diusion and electrochemical reactions kinetics.
2. The corrosion rate increases with slug frequency up to a value of 73 slugs/min. For slug
frequencies higher than 73 slugs/min the corrosion rate decreases with slug frequency.
An explanation for this decrease in corrosion rate at high slug frequency relies probably
on a decrease of turbulence in the front part of the slugs and therefore the slugs heads
do not impact the bottom of the pipe. For a given low liquid surface velocity (1.18 m/s),
the slug liquid lm is thin. For high gas surface velocity (2.69, 1.92 and 1.154 m/s, frequencies below 1.21 slugs/s) high turbulent slug heads are produced that can reach the
bottom of the pipe and remove the protective layers. If slug frequency is increased while
keeping the high slug turbulence, more slugs hit the pipe bottom thus increasing the
removal of protective layers. At low gas velocities (0.76 and 0.38 m/s, frequencies above
1.21 slugs/s) the slug frequency increases but the slugs lose strength and do not reach
the bottom of the pipe. This results in less corrosion products removal and the corrosion rate remains stable or decreases. In low gas surface velocity, the liquid lm enlarges
and the transfer of CO2 mass from the lm surface to the pipe wall and the corrosion
rate decrease.
For high liquid surface velocity (1.75 and 2.25 m/s) we have a thicker liquid lm. It is
observed that the lower energy slugs heads do not completely penetrate this thicker
liquid lm. The mass transfer coecient increases due to higher velocity but decreases
with a thicker liquid lm. This probably explains the low corrosion rates observed at
high liquid surface velocities.
Since the Froude number is related to the slug turbulence, the corrosion rate can also be
related to turbulence due to its relation with the Froude number. The experimental data
show that the corrosion rate is directly proportional to the Froude number.

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3. The addition of a rened oil phase forming a dispersion of 70/30% water/oil ratio, saturated with CO2, did not produce considerable changes in the corrosion rate at the
experimental slug ow conditions. This result indicates that no oil protective barrier
is present in the metal surface, probably due to its removal caused by the high slug
turbulence.
4. The addition of solids to an aqueous phase with CO2 under slug ow operation results
in an increase of the corrosion rate. The action of abrasive solids, even at low concentrations such as the one used in this study, probably promote the protective lm
removal and therefore an increase of corrosion rates.
5. The multiphase ow loop is enhanced with compressor addition that, in turn, allows a
higher frequency range. Further research will include the study of a wider frequency
range for aqueous multiphase ow.
6. More studies are required to characterize the hydrodynamic inuence of oilwater suspensions on corrosion rates. Several variables including oil concentration, oil nature,
pressures and temperatures have to be considered.
7. Due to its economical and operational impact on the oil and gas industry, a comprehensive experimental study is required to be conducted for solidoilwater suspensions.
This also requires improvements of the multiphase ow loops.

Acknowledgements
This study was supported by ECOPETROL and Universidad Industrial de Santander.
The authors wish to express their gratitude to Engineers Clemente Retamoso, Jorge Luis
Grosso and Dr. Cesar Vergel for their advice.
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