Anti-Corrosion Methods and Materials

Effect of carbon dioxide on corrosion of tubular steel in high hydrogen sulfide and carbon dioxide
environments
Hongda Deng, Chunfu Li, Xianlong Cao,
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 Effect of carbon dioxide on corrosion of tubular
steel in high hydrogen sulfide
and carbon dioxide environments
Hongda Deng
School of Metallurgical and Materials Engineering, Chongqing University of Science and Technology, Chongqing, China
Chunfu Li
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengde, China, and
Xianlong Cao
School of Metallurgical and Materials Engineering, Chongqing University of Science and Technology, Chongqing, China

Abstract
Purpose The present work primarily aims to study the corrosion characterization of tubular steel API-P110 in high H2S containing solution with or
without CO2.
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Design/methodology/approach Corrosion behaviors of steel in buffered solutions containing 50 percent H2S and various levels of CO2
concentration were investigated via weight-loss method, SEM and EDS. The effects of CO2 on corrosion occurred on the metal were analyzed by
electrochemical techniques.
Findings Corrosion rates of steel decreased as the CO2 content in H2S/CO2 solution increased. It was observed for the tubular steel to experience an
increase in corrosion rate at concentrations 17 percent CO2 or 34 percent CO2 in 50 percent H2S while when further increasing concentration of CO2 to
50 percent the corrosion rate decreases. Increased CO2 content in H2S/CO2 led to fewer anions desorbing and fewer reactants adsorbing, e.g. H ,
H2CO3. As a result, cathodic reaction rate decreased and the amount of hydrogen absorbed decreased.
Originality/value The experimental results showed that corrosion alleviated when increasing CO2 content in high H2S and CO2 containing
environment.

Keywords Corrosion, Electrochemical, Materials, Mechanisms, Microscope, Oil and gas, Steel

Paper type Research paper

1. Introduction
In natural gas fields, hydrogen sulfide (H2S) and carbon dioxide
(CO2) commonly coexist. From explored gas fields, the
concentrations of H2S and CO2 can range a few ppm to
92 percent (Zhu et al., 2004). To date, many exploited gas fields
in China have natural gases containing high concentrations of
H2S and CO2, of which, many exceed 5 percent in content.
In such corrosive environments, tubular steel suffers severe
corrosion. However, no existing corrosion theory explained the
observed corrosion behaviors. Currently, available theories
(Anderko and Young, 1999; Anderko, 2000; Waard and
Milliams, 1975; Nesic et al., 1996; Bolmer, 1965; Ewing,
1955; Schmitt, 1983) could only explain corrosion behaviors for
corrosive environments which contained only high H2S or CO2
content gases, or the corrosive behaviors under high H2S
environment with low CO2 content (Anderko and Young, 1999;
Kermani and Morshed, 2003; Ramanarayanan and Smith, 1996;
Smith and Miller, 1975; Sardisco and Pitts, 1965).
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Studies show that the addition of minor amounts of CO2 gas
into high H2S containing solution changed the corrosive
behavior of steel (Ramanarayanan and Smith, 1996; Smith and
Miller, 1975; Sardisco and Pitts, 1965). A small concentration
of CO2 when added to the H2S containing solution could
accelerate the corrosive effect of the solution on the steel.
However, the corrosion rate would decrease if the CO2 content
rose above a certain degree (Ramanarayanan and Smith, 1996).
It was hypothesized that the corrosive property of H2S
containing solution could be affected by CO2 in following
ways; by changing adsorptive sites of H2S on sulfide scale
(Ramanarayanan and Smith, 1996), by accelerating the
cathodic reaction through an increase in the concentration of
hydrogen ions in the solution (Smith and Miller, 1975), or by
producing protective or nonprotective scale on the steel surface
(Sardisco and Pitts, 1965). As little research had been reported
on these phenomena, there were no theories on the effects of
CO2 on corrosion in high H2 S and CO2 containing
environments. In consequence, there are various hypotheses
about the role of CO2 during corrosion in H2S solutions.
For instance, CO2 might change the corrosion rate
(Ramanarayanan and Smith, 1996), or CO2 might not affect

The authors would like to acknowledge the financial (2010BB4292)

Anti-Corrosion Methods and Materials
58/4 (2011) 196 204 support by Chongqing Science and Technology Commission. They would
q Emerald Group Publishing Limited [ISSN 0003-5599] like to express thanks also to Chun-fu Li and Xian-long Cao for revisions
[DOI 10.1108/00035591111148911] they recommended, and for experimental help from Peng-fei Wang.

196
 Effect of CO2 on corrosion of tubular steel
Hongda Deng, Chunfu Li and Xianlong Cao
the corrosion condition (Huang and Shaw, 1992). Thus, it is
useful to study the effects and behaviors of CO2 especially in
high H2S and CO2 containing solutions in order to understand
the complex corrosion phenomena which can occur in natural
gas fields with high concentrations of H2S and CO2.
The aim of the study was to investigate corrosion behaviors of
tubular steel API-P110 in acidic solution saturated with high H2S
and/or CO2 mixture gases. By using the weight-loss method,
scanning electron microscope (SEM) and EDS, the study further
investigated the effects of CO2 on corrosion in the above
environments. The study also explored the cathodic and anodic
reactions during corrosion and the changes of adsorption and
desorption at the metal-solution interface using potentiodynamic
scans and single potential step chronoamperometry. Finally, the
occurrence of cathodic and anodic reactions in the high H2S and
CO2 content environments are considered to explain the
polarization experimental results.
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2. Methodology
2.1 Material and environment
The material under test was tubular steel API-P110 (Pangang
Group Chendu Steel & Vanadium Co., Ltd, China), with the
chemical composition and mechanical properties as shown in
Table I. The experimental solutions were prepared by dissolving
5 percent NaCl in distilled water and then saturated with mixed
gas containing 50 percent H2S and different contents of CO2.
In the solutions, acetic acid (HAc) and sodium acetate (NaAc)
were used for adjusting the pH (pH 2.7 ^ 0.1). All reagents
used were analytical-reagent grade in the electrolyte solutions.
After deaerated using pure nitrogen (N2) gas for 1 h, the
buffered 5 percent NaCl solution was introduced into an
airtight experimental test rig and the mixed gas was bubbled at a
flow rate of 0.08 l/min per litre of solution. The mixed gas
included gas contents consisting of: 50 vol.% H2S, 50 vol.%
H2S and 17 vol.% CO2, 50 vol.% H2S and 34 vol.% CO2,
50 vol.% H2S and 50 vol.% CO2, with the balance being N2.
The purities of H2S, CO2, and N2 in the mixed gases were 99.5,
99.9 and 99.9 percent, respectively.
Weight-loss tests and electrochemical measurements were
carried out in four buffered acid corrosive solutions as noted
below:
1 in 5 percent NaCl buffered solution, saturated with a
mixture gas of 50 vol.% H2S (hereafter referred to as in 50
percent H2S);
2 in 5 percent NaCl buffered solution saturated with mixture
gas of 50 vol.% H2S and 17 vol.% CO2 (hereafter referred to
as in 50 percent H2S/17 percent CO2);
3 in 5 percent NaCl buffered solution saturated with mixture
gas of 50 vol.% H2S and 34 vol.% CO2 (hereafter referred to
as in 50 percent H2S/34 percent CO2); and
4 in 5 percent NaCl buffered solution saturated with mixture
gas of 50 vol.% H2S and 50 vol.% CO2 (hereafter referred to
as in 50 percent H2S/50 percent CO2).
Table I Chemical compositions (wt%) and mechanical properties of P110 tubular steel
C Si Mn V Ti Cr
0.25 0.20 1.40 0.012 0.03 0.15 0.012
Anti-Corrosion Methods and Materials
Volume 58 Number 4 2011 196 204
2.2 Weight-loss tests
Tubular steel P110 was cut into 20 20 2 mm specimens.
Three specimens were abraded progressively with 400, 600 and
800-grit silicon carbide papers, and subsequently degreased
with acetone and dewatered with ethanol. After being dried,
they were weighed using an electronic balance (FA1004,
ShangHai FangRui Instrument Co., Ltd) with a precision of
0.1 mg. Subsequently, the dimensions of the specimens were
measured. They then were cleaned for 5 min with alcohol,
ethanol, and distilled water, respectively. Finally, the specimens
were immersed immediately in the test solution. After
immersion in the solution for 192 h, test specimens were
taken out, descaled in a solution of 10 percent sulfuric acid and
5 g/l thiourea. The specimens then were reweighed after being
dewatered in ethanol and dried under a flux of pure N2. General
corrosion rates were calculated based upon the average weight
loss of the specimens.
The morphology and composition of the scales of corroded
specimens were analyzed using a SEM (Hitachi, S450) fitted
with energy dispersive X-ray (EDS). The images were taken
at an operating accelerating voltage of 25 kV.
2.3 Electrochemical measurements
A three electrode test setup was used, which comprised
the working electrode (tubular steel API-P110), reference
electrode (a saturated calomel electrode), and counter electrode
(platinum). Tubular steel specimens, with dimensions of
10 10 2 mm, were pretreated similarly to the pretreatment
of weight loss specimens. After pretreatment, the specimens
were embedded in a thermosetting plastic, leaving a 0.25 cm2
exposed area. The exposed surface was polished with 3 mm
alumina powder, then cleaned with distilled water followed by
ethanol for 1 min in an ultrasonic bath, respectively. Prior to
electrochemical experiments, the working electrode was
immersed in a solution of 50 percent H2SO4 at 248C until
bubbles formed; this was to eliminate any oxide that had formed
on the surface of working electrode during grinding. After a
brief wash in distilled water, the working electrode was
immediately immersed into the corrosive solution.
When the equilibration potential (E0) had stabilized within
^ 1 mV within 10 min after the electrodes had been immersed
into the corrosive solution, electrochemical experiments were
performed using a PGSTAT12 (Autolab) at 248C.
Electrochemical polarization curves were recorded at a
scanning rate of 10 mV/min, and the analysis of the
polarization curves was performed using the software supplied
by Autolab. Transient polarized current density-dependent
time curves at the cathodic polarized overpotential ((Dwc) of
50 mV from E0 were measured for a duration of 10 s.
3. Results
3.1 Corrosion rates from weight-loss tests
The experiments showed supporting evidence for a change in
corrosion rate with the addition of CO2 into H2S solution for
P110 steel, as shown in Figure 1. It was observed that a
considerable decrease in corrosion rate (VL) occurred when the
Ni Cu Mo sb /MPa ss /MPa d/% HRC
, 0.01 0.01 975 890 15.74 31
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 Effect of CO2 on corrosion of tubular steel Anti-Corrosion Methods and Materials
Hongda Deng, Chunfu Li and Xianlong Cao Volume 58 Number 4 2011 196 204

Figure 1 Weight-loss corrosion rate changed with CO2 content in Figure 3 Scale was made up with acicular grains
50 percent H2S containing aqueous solution

1.8

1.7

1.6
VL /mm.a1

1.5

1.4

1.3

1.2

1.1
0 10 20 30 40 50
% CO2
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Note: Magnified image of figure 2

content of CO2 was increased from 17 to 50 percent in the H2S
mixture (hereafter referred to as in H2S/CO2). On the other Figure 4 Morphology of descaled steel exposed in 50 percent H2S
hand, VL in 50 percent H2S/17 percent CO2 and in 50 percent containing aqueous solution
H2S/34 percent CO2 exhibited obvious higher corrosion rates
than those observed in 50 percent H2S, and considerably lower
corrosion rates in 50 percent H2S/50 percent CO2. These
results reveal that adding CO2 could accelerate or decelerate
corrosion in solutions containing chlorides and 50 percent
H2S. Furthermore, increasing the CO2 content to around
50 percent in H2S/CO2 reduced the corrosion rate of the steel. It
is believed that the observed phenomena could be related to the
presence of scale that covered the exposed surface (Ren et al.,
2005). In 50 percent H2S, a thick coarse corrosion scale covered
the surface of the specimen (Figure 2), which was made up of
acicular grains (Figure 3). Holes in the film due to pitting
(Figure 4), and cracks that appeared to be related to stresses
within the scale, were evident in the scale. A similarly thick
coarse scale was produced on the surface of the steel corroded in
50 percent H2S/17 percent CO2 (Figure 5). However, the
dimensions of holes in the scale formed in the above corrosive
solution were greater than was the case in the 50 percent

Figure 2 Morphology of scale of P110 tubular steel exposed in Figure 5 Morphology of scale of P110 tubular steel exposed in
50 percent H2S containing aqueous solution 50 percent H2S containing aqueous solution with 17 percent CO2

198
 Effect of CO2 on corrosion of tubular steel Anti-Corrosion Methods and Materials
Hongda Deng, Chunfu Li and Xianlong Cao Volume 58 Number 4 2011 196 204

H2S environment. Thus, corrosive reactants in 50 percent Table II EDS analytical results of corrosion scales of steel P110 tested
H2S/17 percent CO2 environment passed more easily through in 50 percent H2S containing aqueous solution with and without CO2
the scale and reached the metal-solution interface, and hence
the corrosion rate tended to increase. A continuous scale CO2 (%) C O S Na Cl Mn Fe
without any cracks (Figure 6) covered the surface of the 0 W% 8.26 38.47 15.25 0.58 0.45 0.29 36.69
specimen in 50 percent H2S/50 percent CO2, which was made 50 W% 14.15 46.37 11.58 0.28 0.73 26.91
up by compact colloidal grains (Figure 7). The dimension of
holes in the scale produced in this environment were smaller
than were those in the 50 percent H2S environment, so corrosive containing 50 percent H2S, the corrosion scale consisted mainly
media would have more difficulty in passing through the scale. of sulfides, such as pyrrhotite (FeS1 x) (Ren et al., 2005).
As a result, the corrosion rate of the steel in 50 percent H2S/50 However, the weight percentages of C and O in 50 percent H2S/
percent CO2 was alleviated (Figure 1). 50 percent CO2 were higher than was the case in 50 percent
H2S. Meanwhile, the weight percentage of S in 50 percent H2S/
3.2 Corrosion scale analysis 50 percent CO2 was comparatively lower than that in 50 percent
The chemical compositions of the scales formed in H2S H2S. This suggests that carbonate as well as sulfide exist in the
environments with and without CO2 are shown in Table II.
corrosion scale formed in 50 percent H2S/50 percent CO2. When
According to Table II, major atoms of S, O, C and Fe appeared in
adding 50 percent CO2 in 50 percent H2S, the weight percentage
the scale, and minor atoms of Cl and/or Na were evident due
of S decreased, which indicates that sulfide in scale decreases and
to the traces of the electrolyte salts remaining in scale. Mn
carbonate increases due to a decrease in the number of adsorptive
atoms also were evident in the scale. In the solution only
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sites for H2S on the scale (Ramanarayanan and Smith, 1996).

Figure 6 Morphology of scale of P110 tubular steel exposed in
50 percent H2S containing aqueous solution with 50 percent CO2
Thus, electrons or charge transfers are more difficult through
scale in 50 percent H2S/50 percent CO2, and as a result, the
corrosive rate is less in 50 percent H2S/50 percent CO2 than is the
case in 50 percent H2S, due to the content changes of electrically
conductive sulfide (Lee, 2004) and insulative carbonate.

3.3 Electrochemical corrosion behavior

Potentiodynamic sweeps for P110 tubular steel in the solutions
dissolved with different mixture gases are shown in Figure 8. No
passivity was shown on anode polarization curves measured in
different corrosive solutions. The same result was observed in
buffered acetic acid solutions containing chlorides with H2S
(Veloz and Gonzalez, 2002). This suggests that active dissolution
occurred on the surface of the steel in H2S containing solution
with or without CO2. At more negative or more positive polarized
overpotentials (Dw), CO2 affects distinct anodic and cathodic
current densities. When the same cathodic overpotential (Dwc)
was applied to the electrodes, the cathode current densities (ic)
decreased with the increasing content of CO2 in H2S/CO2. This
finding revealed that increasing CO2 depressed the cathodic
reaction in H2S/CO2. In contrast to ic in 50 percent H2S, ic
increased in 50 percent H2S/ 17 percent CO2 and in 50 percent
Figure 7 Scale was made up with compact grains
Figure 8 Polarization curves of P110 tubular steel testing in H2S
containing aqueous solution with different concentrations of CO2

100 b
c
d
50 a
0
j /mVSCE

50

100
H2S 50%, CO2 0% (a) b
150
H2S 50%, CO2 17% (b) c
200 H2S 50%, CO2 34% (c) a
250 H2S 50%, CO2 50% (d) d

300
0.01 0.1 1
Note: Magnified image of figure 6 i/mA.cm2

199
 Effect of CO2 on corrosion of tubular steel
Hongda Deng, Chunfu Li and Xianlong Cao
H2S/34 percent CO2, which indicates that adding 17 percent
CO2 and 34 percent CO2 accelerated the cathode reaction.
However, the ic in 50 percent H2S/50 percent CO2 was lower
than was the case in 50 percent H2S, which suggests that adding
50 percent CO2 slowed down the cathode reaction. The anode
current density (ia) increased significantly with increasing
content of CO2 in H2S/CO2 mixtures. This suggests that
increasing the CO2 content accelerated the anode reaction in the
H2S/CO2 environments. Meanwhile, ia in H2S/CO2 was less than
that in H2S, suggesting that adding CO2 comparatively slowed
down the anode reaction in 50 percent H2S.
According to the results shown in Table III, bc was larger than
ba, which indicates that the corrosion reaction rate was
controlled by the cathodic reaction (Bard and Faulkner,
2005). If the electron number needed for the cathodic reduction
reaction was one, and the charge transfer step acts as the step of
controlling the cathodic reaction rate at 248C, the cathode Tafel
slope (bc) is about 118 mV (Bard and Faulkner, 2005). From
Table III, bc in H2S and in H2S/CO2 are over 118 mV,
suggesting that the diffusion condition also acted as a cathodic
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reaction rate determining step (RDS), as well as the charge
transfer step. When the charge transfer step acts as the
controlling anodic reaction rate step, and the electron number
required for the anodic reaction is two, the anode Tafel slope
(ba) is about 60 mV (Bard and Faulkner, 2005). In Table III, ba
in H2S or in H2S/CO2 is about 60 mV, which suggests that only
the charge transfer step acted as anodic reaction RDS.
The Ecorr value of the steel moved towards the more negative
direction with the increasing CO2 content in H2S/CO2. Also,
note that the Ecorr value of the steel in H2S was more negative
than was the case in H2S/CO2 (Table III). Ecorr is related closely
to the concentration of Fe2 at the interface between metal and
solution, because the corrosion reaction rate was controlled by
the cathodic reaction, and the concentration change of Fe2 in
the metal-solution interface correlates with the change of the
cathodic reaction rate in H2S/CO2. With increasing CO2
content in the H2S/CO2, the coverage of CO2,ad increased and
the coverage of reactants, e.g. H2Sad and H2CO3,ad, decreased
(as is considered in the Discussion). So ic will decrease with
increasing CO2 content in H2S/CO2, and results in the Ecorr of
steel moving towards more negative potentials with the
increasing CO2 in H2S/CO2.
As shown in Table II, the corrosion rate (icorr) slowed with the
increasing CO2 levels in H2S/CO2. Considering icorr in 50
percent H2S, icorr was larger in 50 percent H2S/17 percent CO2
and in 50 percent H2S/34 percent CO2 than was the case in 50
percent H2S, but was lower in 50 percent H2S/50 percent CO2.
Similar changes of V2 with CO2 content in the same corrosive
environments also were observed. With increasing CO2 in
H2S/CO2, corrosion rate (icorr) decreased, which could have
resulted from a decline in the cathodic reaction rate. When
Table III Electrochemical parameters based on polarized curves of
P110 tubular steel tested in 50 percent H2S containing aqueous solution
with different content of CO2
CO2 (%) bc /mV. dec2 1 ba /mV. dec2 1 Ecorr./mV icorr /mA.cm2 2
0 2 226.67263 67.47179 2 631 0.27286
17 2 287.81136 73.22732 2 593 0.32849
34 2 283.03709 91.26145 2 601 0.29753
50 2 346.21329 82.83234 2 618 0.23709
200
Anti-Corrosion Methods and Materials
Volume 58 Number 4 2011 196 204
adding 17 percent CO2 or in 34 percent CO2 in 50 percent H2S,
the cathodic reaction rate increased, and therefore corrosion
accelerated. However, if adding 50 percent CO2, the cathodic
reaction rate decreased, resulting in a lower corrosion rate.
3.4 Adsorption/desorption at the metal/solution
interface
From above analysis, the cathode reaction rate and anode
reaction rate change with change in the content of CO2 in H2S/
CO2. This relates to the change in the amount of adsorptive
reactants at the interface between the metal and the solution.
Because the cathodic reactions control the corrosion rate in
H2S/CO2, adsorbate adsorption/desorption are involved in the
transient processes of the cathode reaction. The change in the
adsorbate adsorption and desorption reactions at the metal-
solution interface were investigated by using single potential
step chronoamperometry.
The potential step test results on P110 steel at the lower
cathodic overpotential of 50 mV, with a duration of 10 s in H2S
containing solutions with or without CO2, are showed in Figure 9.
Typical transient curves for initial fast current density (i0)
damping and the following steady current density (i1) are
illustrated. Current density decreased with elevation of the CO2
content in the H2S/CO2. Current densities in 50 percent H2S/17
percent CO2 and in 50 percent H2S/34 percent CO2 were greater
comparatively than were those in 50 percent H2S, though less in
50 percent H2S/50 percent CO2. The i0 and i1 values decreased
similarly with increase in the CO2 content of the H2S/CO2.
In transient measurements, i0 indicates the degree of change in
reactant numbers taking part in reduction reactions in the metal-
solution interface before and after the potential step test
(Bard and Faulkner, 2005). Thus, fewer and fewer reactants
took part in the reduction reactions when the CO2 content in
H2S/CO2 increased, according to the change of i0.
Based on the research results (Wandlowski et al., 1996;
Pronkin and Wandlowski, 2003; Hara et al., 2007), several
processes were taking place simultaneously at the metal/
solution interface during transient measurement, such as the
hydrogen atom adsorption process, anions (e.g. Ac2 , HS2 ,
HCO2 22
, CO22 2
3 ,S 3 and Cl ) desorption process, and hydrogen
atom absorption process was independent of time. According to
the same analysis methods (Wandlowski et al., 1996; Pronkin
Figure 9 Results of current density verse time at Dwc 50 mV in
different gases
0.3
0.4
0.5
0.6
0.7
i/mA.cm2
CO2 0%
0.8
CO2 17%
0.9 CO2 34%
1.0 CO2 50%
1.1
1.2
1.3
0 2 4 6 8 10
Time/s
 Effect of CO2 on corrosion of tubular steel
Hongda Deng, Chunfu Li and Xianlong Cao
and Wandlowski, 2003; Hara et al., 2007), the densities of the
hydrogen adsorption process (iHad), and for in the anions
desorption process (iX), and for the hydrogen absorption
process (independent of time) (iHab) cumulatively contribute to
a total current density (it), as expressed with equation (1) for
lower Dwc (e.g. Dwc , 0.09 V) (Wandlowski et al., 1996):
i t qX k1 exp2k1 t qH ad k2 exp2k2 t i H ab 1 (Parkins, 1999; Gray et al., 1999).
where qX is the charge of anions in solution for the desorption
process, k1 is a rate constant for the desorption process, qHad is
the charge of hydrogen adsorption participating in reduction
reaction, k2 is a rate constant for hydrogen adsorption, and iHab
represents the currency density in hydrogen atom absorption
process. Curve fits for current density vs time (Figure 9)
measured in different solutions with equation (1) by use of
Levenberg-Marquardt non-linear least squares (Marquardt,
1963), and fitting results and the contributions of ix and iHad to
it, are shown in Table IV and Figure 10. It is evident that the
experiment results fitted well with equation (1), according to
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Figure 10 and r2 (Table IV).
In Figure 10, ix is bigger than iHad in different environments,
which indicated that the anions desorption process was the
controlling step in the interface reactions in H2S and in H2S/
CO2. The qx value deceased with the increasing CO2 content in
H2S/CO2, which indicates that the more CO2 content in H2S/
CO2, the fewer anions will be desorbed. The qx value in 50
percent H2S/17 percent CO2 was significantly higher than that
in 50 percent H2S, while substantially less in 50 percent H2S/50
percent CO2. In other words, adding 17 percent CO2
accelerated anions desorption tremendously in 50 percent
H2S, but adding 50 percent CO2 slowed down the rate of anion
desorption. On the other hand, k1 increased with the increasing
CO2 content. Among the investigated solutions, k1 changed a
little when the content of CO2 was increased from 0 to
34 percent, and the maximum k1 value appeared in 50 percent
H2S/50 percent CO2. However, k1 contributed a little to iX. The
maximum qHad was observed in 50 percent H2S/50 percent
CO2, and the minimum value in 50 percent H2S. The
maximum k2 appeared in 50 percent H2S/34 percent CO2,
and minimum value in 50 percent H2S/17 percent CO2. These
results indicate that the rate of hydrogen adsorption at lower Dwc
was affected markedly by the components in the solution. This
may be related to the lower electric field strength that fails to
compel all of the anions in outer Helmholtz plane (OHP) into
the diffusion layer (DL) (Figure 11), and interferes with
hydrogen adsorption. Because iHab was higher than iHad, the
absorptive hydrogen atom is the main form of hydrogen at the
electrode. With the increasing content of CO2 in H2S/CO2, iHab
declines. This also indicated that less hydrogen was being
produced. Compared with the situation in 50 percent H2S,
adding 17 percent CO2 accelerated hydrogen absorption,
but adding 50 percent CO2 depressed hydrogen absorption.
Table IV Fitting results of currency density verse time in different acid gas environments at different Dwc with equation (1)
CO2 (%) qx2 /mC.cm2 2 k1 /ms2 1 qHad/mC.cm2 2
0 20.86508 0.2554
17 21.54351 0.27663
34 20.79817 0.27768
50 20.78389 0.39411
Anti-Corrosion Methods and Materials
Volume 58 Number 4 2011 196 204
4. Discussion
When gas containing high contents of H2S and CO2 is dissolved
in brine solution, H , HS2 , S22 , HCO2 22
3 , CO3 , hydrated H2S
and H2CO3 may exist simultaneously in solution (Parkins,
1999; Gray et al., 1999). As for the solution of pH , 3 is
concerned, H , hydrated H2S and CO2 are the main forms
4.1 CO2 effect mechanism
The double-layer model proposed by Bockris et al. (1965)
could be used to describe the change in adsorbate coverage at
the interface between the metal and the solution before and
after a potential step transient. Before the potential step is
triggered, dipole water and specific adsorbates such as Cl2 ,
HS2 , cover the inner Helmholtz plane (IHP) of Bockris
model. The other anions, cations, e.g. H , and dipole
hydrated CO2, dipole Hydrogen sulfide, dipole H2CO3 and
water, form the OHP, as is shown by Figure 11(A) (Deng
et al., 2010). After the potential step is triggered towards a
more negative value, the dominating adsorptive species is
dipole water, which covers the IHP. The main adsorbates of
the dipoles are hydrated CO2, dipole H2S, and H , which
populate the OHP. Most anions are expelled into DL due to
the repulsive force that is present between the anions and the
electrons on the electrode, as shown in Figure 11(B).
The coverage of CO2dipoles in the OHP increased with the
increasing content of CO2 in the H2S/CO2. Accordingly, this
will affect the coverage of the other adsorbates in OHP and, as a
result, the amount of reactants, e.g. H and H2CO3 dipole
(as shown in following discussion) in the OHP will decrease.
At the same time, the numbers of anions in OHP, i.e. HS2 ,
HCO2 2
3 and Ac , and the extent of the hydrogen absorption
caused by the increasing coverage of CO2 dipoles (and therefore
the i0 and ic values at the same cathodic overvoltage) decreases.
It appears that corrosion rate declines when the electrochemical
corrosion cell is controlled by the cathodic reaction.
Compared with in 50 percent H2S, adding 17 percent CO2
accelerates anions diffusion into the DL, so more reactants are
adsorbed in the OHP. On the other hand, adding 17 percent
CO2 provides additional reactants, i.e. H2CO3 (as shown in the
following discussion). Hence, 17 percent CO2 addition
increased the cathodic current density, as well as the corrosion
rate. However, by adding 50 percent CO2 anion diffusion into
the DL was slowed, so fewer reactants was adsorbed in OHP,
and therefore 50 percent CO2 content depresses the cathodic
reaction, which results in a decreased corrosion rate.
4.2 Cathodic and anodic reactions
Cathode reactions in the solution only containing H2S are
shown as follows (Kawashima et al., 1976):
H 2 S ad e ! H 2 S 2 2
ad
H 2 S2
ad H
ad ! H 2 S ad 2 H ad 3
k2 /ms2 1 iHab /mA.cm2 2 r2
2 0.09952 3.26456 2 0.45021 0.99618
2 0.15583 2.92540 2 0.45313 0.99841
2 0.12045 8.41078 2 0.45095 0.99662
2 0.16063 4.72119 2 0.39091 0.99655
201
 Effect of CO2 on corrosion of tubular steel Anti-Corrosion Methods and Materials
Hongda Deng, Chunfu Li and Xianlong Cao Volume 58 Number 4 2011 196 204

Figure 10 Contribution of iHad and iX to itotal in the environment containing of (a) 50 percent H2S/0 percent CO2, (b) 50 percent H2S/17 percent CO2,
(c) 50 percent H2S/34 percent CO2 and (d) 50 percent H2S/50 percent CO2 at Dwc 50 mV

0.1 iHadt iHadt

0.0 0.0
ix t
0.1
ix t
0.2 0.2
0.3
0.4 0.4

i /mA.cm2
i /mA.cm2

0.5
0.6 0.6

0.7
0.8
0.8 itotalt itotalt
0.9 ( fitting data ( fitting data
experiment data) 1.0 experiment data)
1.0
1.1
1.2
1.2
0 2 4 6 8 10 0 2 4 6 8 10
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Time/s Time/s
(a) (b)

iHadt 0.2
iHadt
0.0
0.0
ix t
ix t
0.2
0.2

0.4 0.4
i /mA.cm2

i /mA.cm2

0.6 0.6

0.8
0.8
itotal-t itotal-t
1.0
( fitting data ( fitting data
1.0 experiment data) experiment data)
1.2
1.2
1.4
0 2 4 6 8 10 0 2 4 6 8 10
Time/s Time/s
(c) (d)

Figure 11 Initial double-layer model (a) and final one (b) in the diffusion-controlled process is present for the cathode
solution dissolved with high contents of H2S and CO2 before and after reduction reactions (Huang and Shaw, 1992).
potential stepping In buffered solution, CO2 contributes little to the change of
pH. Therefore, CO2 does not affect H2S corrosion by the way of
CO2.H2O increasing the concentration of hydrogen ions in the buffered
H2CO3
H2.CO3 HCO3
solution (Huang and Shaw, 1992). According to the
HS CO2.H2O Ac experimental results in the present paper, the CO2 content in

HCO3
H2S/CO2 affects distinctly the ic as measured in the buffered
Cr H+ H+ Cr solution. Meanwhile, bc in H2S/CO2 is greater than 118 mV.
H2S HS These values indicate that the reduction reaction of the H2CO3
HS H2S
Ac compound occurred at the surface of the steel, and the H
reduction reaction also occurs, as is shown by equation (5):
IHP OHP DL IHP OHP DL
(a) (b)
H 2 CO3;ad e ! H ad HCO2
3;ad 5

H 2 S ad 2 H ad M ! H 2 S ad M 2 H ad 4 Cathodic Tafel slopes in H2S/CO2 were greater than was the

case in solution containing only H2S, which suggests the
That is to say, H2S acts as a bridge to transfer one electron for hydrating reaction of CO2 (equation (6)) is the RDS of
the H reduction reaction. In 50 percent H2S, the cathodic equation (5) (Schmitt and Rothman, 1977), as well as for the
Tafel slope is over 118 mV, which indicates that the same H2S effect of H2S diffusion processes in equation (2).

202
 Effect of CO2 on corrosion of tubular steel
Hongda Deng, Chunfu Li and Xianlong Cao
RDS
CO2;ad H 2 O ! H 2 CO3;ad 6
Hence, in environments containing high contents of H2S and
CO2, the cathodic reduction reactions include equations (2)
and (5), and H2S diffusion process and equation (6) co-control
the cathodic reaction rate.
At present, the reaction of Fe (oxidized iron) ions is widely
accepted. It is agreed that the oxidation reaction was effected
by HS2 in the solution dissolved H2S, as following (Iofa et al.,
1964):
Fe H 2 S H 2 O ! FeHS 2
ad H 3 O 7 CO2 content in H2S/CO2, the coverage of CO2,ad increases,
RDS
FeHS 2
ad ! FeHS ad 2e 8
FeHS
ad H 3 O ! Fe
2
H 2S H 2O 9
In reaction (Iofa et al., 1964), H2S worked as a catalyst for the
anodic reaction. However, the oxidation reaction might be
effected by HS2 dissolved in H2S solution (Parkins, 1999) or
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HCO2
3 dissolved in CO2 solution (Davies and Burstein,
1980). Comparing with H2S, adding CO2 slowed down ia and
caused minimal changes of the Tafel slope, so the reactions of
the oxidized iron ions were produced not only from the causes
described by equations (7)-(9), but also according to the that
given by equation (10).
Fe HCO2
3 ! FeCO3 H 2e 10
Therefore, equations (8) and (10) can coexist on the electrode
in solutions containing dissolved high concentrations of H2S
and CO2.
To prove above model, the theoretical predictions are
compared with the experimental results.
According to both equations (2) and (5), equation (11)
(Bard and Faulkner, 2005) is obtained:
i 0;1 exp2ac;1 FDwc =RT
ic
1 i 0;1 =i lim ;1 exp2ac;1 FDwc =RT
11
i 0;2 exp2ac;2 FDwc =RT
0;2
1 i =i lim ;2 exp2ac;2 FDwc =RT
where i 0;1 FH 2 S ad
K , and i 0;2 FH 2 CO2;ad
K .
H 2 S ad
and H 2 CO2;ad
are the concentrations of adsorptive
H2S and H2CO3, and i lim ;1 and i lim ;2 are the limited diffusion
densities of H2S and H2CO3. ac,1 andac,2 are the symmetry
factors of equations (2) and (5). F is the Faraday constant,
K is reaction rate constant on electrode at standard hydrogen
potential and at standard condition. (For example, the
concentrations of oxide and reduction reactions are 1 mol/l.)
With the increasing CO2 content in H2S/CO2, the coverage
of CO2,ad increases, and the coverage of H2Sad and H2CO3,ad
decreases according to the Langmuir isotherm. Based on
equation (11), ic decreases with increasing CO2 content.
However, due to the additional contribution of H2CO3
reduction, adding CO2 would actually increase ic in H2S-
based solution. Because the coverage of CO2,ad plays the
predominant role in the interface between the metal and the
solution in H2S based environments with higher CO2
contents, the coverage of H2Sad and H2CO3,ad decreases
sharply, so ic would be less than is the case in H2S solution.
These predictions agreed with the cathodic experimental
results.
203
Anti-Corrosion Methods and Materials
Volume 58 Number 4 2011 196 204
From the equations (8) and (10), equation (12) (Bard and
Faulkner, 2005) is obtained:

2   
HS ad 2aa;1 FDwa
i a 2FK exp
H
RT
h i 12
HCO3;ad
2
 
2aa;2 FDwa
2FK exp
H
RT
where H
, HS 2 2
ad
and HCO3;ad
are the concentrations of H
2 2
and adsorptive HSad and HCO3;ad , and aa,1 and aa,2 are the
symmetry factors of equations (8) and (10). With increasing
so more HCO2 3;ad is produced, and results in an increase in ia
according to equation (12). However, because the coverage
effects of CO2,ad, ia in H2S/CO2 is lower than in H2S. These
predictions agree with the anodic experimental results.
5. Conclusions
The effect of CO2 on corrosion of tubular steel P110 was
investigated by exposing it in solutions containing high contents
of H2S and CO2. Weight loss rates and the corrosion densities
decreased with an increase in the CO2 content of H2S/CO2.
Scale consisting of sulfide and carbonate was observed in H2S/
CO2 containing environments. The cathodic reaction rate
decreased with increase in the CO2 content, due to the
increasing coverage of CO2 absorbate. The anodic reaction
rate increased with the increasing CO2 content, due to the
increase in HCO2 3;ad . With the increasing CO2 content in the
H2S/CO2 solution, fewer anions were desorbed and fewer
hydrogen ions were absorbed, therefore, fewer reactants could
take part in the reduction reaction. In solution containing high
contents of H2S and CO2, the cathodic reduction reactions
included H2S and H2CO3 reduction reactions, and the anodic
oxidation reaction also was affected simultaneously by HS2 and
HCO2 3 ions. The experimental results indicated that CO2 could
accelerate and also could inhibit the corrosion attack in high
H2S containing environments.
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Corresponding author
Hongda Deng can be contacted at: dhd7730@163.com
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