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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 Studies show that the addition of minor amounts of CO2 gas
into high H2S containing solution changed the corrosive
In natural gas fields, hydrogen sulfide (H2S) and carbon dioxide behavior of steel (Ramanarayanan and Smith, 1996; Smith and
(CO2) commonly coexist. From explored gas fields, the Miller, 1975; Sardisco and Pitts, 1965). A small concentration
concentrations of H2S and CO2 can range a few ppm to of CO2 when added to the H2S containing solution could
92 percent (Zhu et al., 2004). To date, many exploited gas fields accelerate the corrosive effect of the solution on the steel.
in China have natural gases containing high concentrations of However, the corrosion rate would decrease if the CO2 content
H2S and CO2, of which, many exceed 5 percent in content. rose above a certain degree (Ramanarayanan and Smith, 1996).
In such corrosive environments, tubular steel suffers severe It was hypothesized that the corrosive property of H2S
corrosion. However, no existing corrosion theory explained the containing solution could be affected by CO2 in following
observed corrosion behaviors. Currently, available theories ways; by changing adsorptive sites of H2S on sulfide scale
(Anderko and Young, 1999; Anderko, 2000; Waard and (Ramanarayanan and Smith, 1996), by accelerating the
Milliams, 1975; Nesic et al., 1996; Bolmer, 1965; Ewing, cathodic reaction through an increase in the concentration of
1955; Schmitt, 1983) could only explain corrosion behaviors for hydrogen ions in the solution (Smith and Miller, 1975), or by
corrosive environments which contained only high H2S or CO2 producing protective or nonprotective scale on the steel surface
content gases, or the corrosive behaviors under high H2S (Sardisco and Pitts, 1965). As little research had been reported
environment with low CO2 content (Anderko and Young, 1999; on these phenomena, there were no theories on the effects of
Kermani and Morshed, 2003; Ramanarayanan and Smith, 1996; CO2 on corrosion in high H2 S and CO2 containing
Smith and Miller, 1975; Sardisco and Pitts, 1965). environments. In consequence, there are various hypotheses
about the role of CO2 during corrosion in H2S solutions.
The current issue and full text archive of this journal is available at For instance, CO2 might change the corrosion rate
www.emeraldinsight.com/0003-5599.htm (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 Anti-Corrosion Methods and Materials
Hongda Deng, Chunfu Li and Xianlong Cao Volume 58 Number 4 2011 196 204

the corrosion condition (Huang and Shaw, 1992). Thus, it is 2.2 Weight-loss tests
useful to study the effects and behaviors of CO2 especially in Tubular steel P110 was cut into 20 20 2 mm specimens.
high H2S and CO2 containing solutions in order to understand Three specimens were abraded progressively with 400, 600 and
the complex corrosion phenomena which can occur in natural 800-grit silicon carbide papers, and subsequently degreased
gas fields with high concentrations of H2S and CO2. with acetone and dewatered with ethanol. After being dried,
The aim of the study was to investigate corrosion behaviors of they were weighed using an electronic balance (FA1004,
tubular steel API-P110 in acidic solution saturated with high H2S ShangHai FangRui Instrument Co., Ltd) with a precision of
and/or CO2 mixture gases. By using the weight-loss method, 0.1 mg. Subsequently, the dimensions of the specimens were
scanning electron microscope (SEM) and EDS, the study further measured. They then were cleaned for 5 min with alcohol,
investigated the effects of CO2 on corrosion in the above ethanol, and distilled water, respectively. Finally, the specimens
environments. The study also explored the cathodic and anodic were immersed immediately in the test solution. After
immersion in the solution for 192 h, test specimens were
reactions during corrosion and the changes of adsorption and
taken out, descaled in a solution of 10 percent sulfuric acid and
desorption at the metal-solution interface using potentiodynamic
5 g/l thiourea. The specimens then were reweighed after being
scans and single potential step chronoamperometry. Finally, the
dewatered in ethanol and dried under a flux of pure N2. General
occurrence of cathodic and anodic reactions in the high H2S and corrosion rates were calculated based upon the average weight
CO2 content environments are considered to explain the loss of the specimens.
polarization experimental results. 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
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2. Methodology at an operating accelerating voltage of 25 kV.


2.1 Material and environment 2.3 Electrochemical measurements
The material under test was tubular steel API-P110 (Pangang A three electrode test setup was used, which comprised
Group Chendu Steel & Vanadium Co., Ltd, China), with the the working electrode (tubular steel API-P110), reference
chemical composition and mechanical properties as shown in electrode (a saturated calomel electrode), and counter electrode
Table I. The experimental solutions were prepared by dissolving (platinum). Tubular steel specimens, with dimensions of
5 percent NaCl in distilled water and then saturated with mixed 10 10 2 mm, were pretreated similarly to the pretreatment
gas containing 50 percent H2S and different contents of CO2. of weight loss specimens. After pretreatment, the specimens
In the solutions, acetic acid (HAc) and sodium acetate (NaAc) were embedded in a thermosetting plastic, leaving a 0.25 cm2
were used for adjusting the pH (pH 2.7 ^ 0.1). All reagents exposed area. The exposed surface was polished with 3 mm
used were analytical-reagent grade in the electrolyte solutions. alumina powder, then cleaned with distilled water followed by
After deaerated using pure nitrogen (N2) gas for 1 h, the ethanol for 1 min in an ultrasonic bath, respectively. Prior to
buffered 5 percent NaCl solution was introduced into an electrochemical experiments, the working electrode was
airtight experimental test rig and the mixed gas was bubbled at a immersed in a solution of 50 percent H2SO4 at 248C until
flow rate of 0.08 l/min per litre of solution. The mixed gas bubbles formed; this was to eliminate any oxide that had formed
included gas contents consisting of: 50 vol.% H2S, 50 vol.% on the surface of working electrode during grinding. After a
brief wash in distilled water, the working electrode was
H2S and 17 vol.% CO2, 50 vol.% H2S and 34 vol.% CO2,
immediately immersed into the corrosive solution.
50 vol.% H2S and 50 vol.% CO2, with the balance being N2.
When the equilibration potential (E0) had stabilized within
The purities of H2S, CO2, and N2 in the mixed gases were 99.5,
^ 1 mV within 10 min after the electrodes had been immersed
99.9 and 99.9 percent, respectively. into the corrosive solution, electrochemical experiments were
Weight-loss tests and electrochemical measurements were performed using a PGSTAT12 (Autolab) at 248C.
carried out in four buffered acid corrosive solutions as noted Electrochemical polarization curves were recorded at a
below: scanning rate of 10 mV/min, and the analysis of the
1 in 5 percent NaCl buffered solution, saturated with a polarization curves was performed using the software supplied
mixture gas of 50 vol.% H2S (hereafter referred to as in 50 by Autolab. Transient polarized current density-dependent
percent H2S); time curves at the cathodic polarized overpotential ((Dwc) of
2 in 5 percent NaCl buffered solution saturated with mixture 50 mV from E0 were measured for a duration of 10 s.
gas of 50 vol.% H2S and 17 vol.% CO2 (hereafter referred to
as in 50 percent H2S/17 percent CO2); 3. Results
3 in 5 percent NaCl buffered solution saturated with mixture
gas of 50 vol.% H2S and 34 vol.% CO2 (hereafter referred to 3.1 Corrosion rates from weight-loss tests
as in 50 percent H2S/34 percent CO2); and The experiments showed supporting evidence for a change in
4 in 5 percent NaCl buffered solution saturated with mixture corrosion rate with the addition of CO2 into H2S solution for
gas of 50 vol.% H2S and 50 vol.% CO2 (hereafter referred to P110 steel, as shown in Figure 1. It was observed that a
as in 50 percent H2S/50 percent CO2). considerable decrease in corrosion rate (VL) occurred when the

Table I Chemical compositions (wt%) and mechanical properties of P110 tubular steel
C Si Mn V Ti Cr Ni Cu Mo sb /MPa ss /MPa d/% HRC
0.25 0.20 1.40 0.012 0.03 0.15 0.012 , 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).


Thus, electrons or charge transfers are more difficult through
Figure 6 Morphology of scale of P110 tubular steel exposed in scale in 50 percent H2S/50 percent CO2, and as a result, the
50 percent H2S containing aqueous solution with 50 percent CO2 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 Anti-Corrosion Methods and Materials
Hongda Deng, Chunfu Li and Xianlong Cao Volume 58 Number 4 2011 196 204

H2S/34 percent CO2, which indicates that adding 17 percent adding 17 percent CO2 or in 34 percent CO2 in 50 percent H2S,
CO2 and 34 percent CO2 accelerated the cathode reaction. the cathodic reaction rate increased, and therefore corrosion
However, the ic in 50 percent H2S/50 percent CO2 was lower accelerated. However, if adding 50 percent CO2, the cathodic
than was the case in 50 percent H2S, which suggests that adding reaction rate decreased, resulting in a lower corrosion rate.
50 percent CO2 slowed down the cathode reaction. The anode
current density (ia) increased significantly with increasing 3.4 Adsorption/desorption at the metal/solution
content of CO2 in H2S/CO2 mixtures. This suggests that interface
increasing the CO2 content accelerated the anode reaction in the From above analysis, the cathode reaction rate and anode
H2S/CO2 environments. Meanwhile, ia in H2S/CO2 was less than reaction rate change with change in the content of CO2 in H2S/
that in H2S, suggesting that adding CO2 comparatively slowed CO2. This relates to the change in the amount of adsorptive
down the anode reaction in 50 percent H2S. reactants at the interface between the metal and the solution.
According to the results shown in Table III, bc was larger than Because the cathodic reactions control the corrosion rate in
ba, which indicates that the corrosion reaction rate was H2S/CO2, adsorbate adsorption/desorption are involved in the
controlled by the cathodic reaction (Bard and Faulkner, transient processes of the cathode reaction. The change in the
2005). If the electron number needed for the cathodic reduction adsorbate adsorption and desorption reactions at the metal-
reaction was one, and the charge transfer step acts as the step of solution interface were investigated by using single potential
controlling the cathodic reaction rate at 248C, the cathode Tafel step chronoamperometry.
slope (bc) is about 118 mV (Bard and Faulkner, 2005). From The potential step test results on P110 steel at the lower
Table III, bc in H2S and in H2S/CO2 are over 118 mV, cathodic overpotential of 50 mV, with a duration of 10 s in H2S
suggesting that the diffusion condition also acted as a cathodic containing solutions with or without CO2, are showed in Figure 9.
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reaction rate determining step (RDS), as well as the charge Typical transient curves for initial fast current density (i0)
transfer step. When the charge transfer step acts as the damping and the following steady current density (i1) are
controlling anodic reaction rate step, and the electron number illustrated. Current density decreased with elevation of the CO2
required for the anodic reaction is two, the anode Tafel slope content in the H2S/CO2. Current densities in 50 percent H2S/17
(ba) is about 60 mV (Bard and Faulkner, 2005). In Table III, ba percent CO2 and in 50 percent H2S/34 percent CO2 were greater
in H2S or in H2S/CO2 is about 60 mV, which suggests that only comparatively than were those in 50 percent H2S, though less in
50 percent H2S/50 percent CO2. The i0 and i1 values decreased
the charge transfer step acted as anodic reaction RDS.
similarly with increase in the CO2 content of the H2S/CO2.
The Ecorr value of the steel moved towards the more negative
In transient measurements, i0 indicates the degree of change in
direction with the increasing CO2 content in H2S/CO2. Also,
reactant numbers taking part in reduction reactions in the metal-
note that the Ecorr value of the steel in H2S was more negative
solution interface before and after the potential step test
than was the case in H2S/CO2 (Table III). Ecorr is related closely
(Bard and Faulkner, 2005). Thus, fewer and fewer reactants
to the concentration of Fe2 at the interface between metal and
took part in the reduction reactions when the CO2 content in
solution, because the corrosion reaction rate was controlled by
H2S/CO2 increased, according to the change of i0.
the cathodic reaction, and the concentration change of Fe2 in
Based on the research results (Wandlowski et al., 1996;
the metal-solution interface correlates with the change of the
Pronkin and Wandlowski, 2003; Hara et al., 2007), several
cathodic reaction rate in H2S/CO2. With increasing CO2
processes were taking place simultaneously at the metal/
content in the H2S/CO2, the coverage of CO2,ad increased and
solution interface during transient measurement, such as the
the coverage of reactants, e.g. H2Sad and H2CO3,ad, decreased hydrogen atom adsorption process, anions (e.g. Ac2 , HS2 ,
(as is considered in the Discussion). So ic will decrease with HCO2 22
, CO22 2
3 ,S 3 and Cl ) desorption process, and hydrogen
increasing CO2 content in H2S/CO2, and results in the Ecorr of atom absorption process was independent of time. According to
steel moving towards more negative potentials with the the same analysis methods (Wandlowski et al., 1996; Pronkin
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 Figure 9 Results of current density verse time at Dwc 50 mV in
percent H2S, icorr was larger in 50 percent H2S/17 percent CO2 different gases
and in 50 percent H2S/34 percent CO2 than was the case in 50 0.3
percent H2S, but was lower in 50 percent H2S/50 percent CO2.
Similar changes of V2 with CO2 content in the same corrosive 0.4
environments also were observed. With increasing CO2 in 0.5
H2S/CO2, corrosion rate (icorr) decreased, which could have
0.6
resulted from a decline in the cathodic reaction rate. When
0.7
i/mA.cm2

CO2 0%
Table III Electrochemical parameters based on polarized curves of 0.8
CO2 17%
P110 tubular steel tested in 50 percent H2S containing aqueous solution 0.9 CO2 34%
with different content of CO2 1.0 CO2 50%
CO2 (%) bc /mV. dec2 1 ba /mV. dec2 1 Ecorr./mV icorr /mA.cm2 2 1.1
0 2 226.67263 67.47179 2 631 0.27286 1.2
17 2 287.81136 73.22732 2 593 0.32849
1.3
34 2 283.03709 91.26145 2 601 0.29753
0 2 4 6 8 10
50 2 346.21329 82.83234 2 618 0.23709
Time/s

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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

and Wandlowski, 2003; Hara et al., 2007), the densities of the 4. Discussion
hydrogen adsorption process (iHad), and for in the anions
desorption process (iX), and for the hydrogen absorption When gas containing high contents of H2S and CO2 is dissolved
in brine solution, H , HS2 , S22 , HCO2 22
3 , CO3 , hydrated H2S
process (independent of time) (iHab) cumulatively contribute to
and H2CO3 may exist simultaneously in solution (Parkins,
a total current density (it), as expressed with equation (1) for
1999; Gray et al., 1999). As for the solution of pH , 3 is
lower Dwc (e.g. Dwc , 0.09 V) (Wandlowski et al., 1996):
concerned, H , hydrated H2S and CO2 are the main forms
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 4.1 CO2 effect mechanism
process, k1 is a rate constant for the desorption process, qHad is The double-layer model proposed by Bockris et al. (1965)
the charge of hydrogen adsorption participating in reduction could be used to describe the change in adsorbate coverage at
reaction, k2 is a rate constant for hydrogen adsorption, and iHab the interface between the metal and the solution before and
represents the currency density in hydrogen atom absorption after a potential step transient. Before the potential step is
process. Curve fits for current density vs time (Figure 9) triggered, dipole water and specific adsorbates such as Cl2 ,
HS2 , cover the inner Helmholtz plane (IHP) of Bockris
measured in different solutions with equation (1) by use of
model. The other anions, cations, e.g. H , and dipole
Levenberg-Marquardt non-linear least squares (Marquardt,
hydrated CO2, dipole Hydrogen sulfide, dipole H2CO3 and
1963), and fitting results and the contributions of ix and iHad to
water, form the OHP, as is shown by Figure 11(A) (Deng
it, are shown in Table IV and Figure 10. It is evident that the
et al., 2010). After the potential step is triggered towards a
experiment results fitted well with equation (1), according to
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more negative value, the dominating adsorptive species is


Figure 10 and r2 (Table IV).
dipole water, which covers the IHP. The main adsorbates of
In Figure 10, ix is bigger than iHad in different environments,
the dipoles are hydrated CO2, dipole H2S, and H , which
which indicated that the anions desorption process was the populate the OHP. Most anions are expelled into DL due to
controlling step in the interface reactions in H2S and in H2S/ the repulsive force that is present between the anions and the
CO2. The qx value deceased with the increasing CO2 content in electrons on the electrode, as shown in Figure 11(B).
H2S/CO2, which indicates that the more CO2 content in H2S/ The coverage of CO2dipoles in the OHP increased with the
CO2, the fewer anions will be desorbed. The qx value in 50 increasing content of CO2 in the H2S/CO2. Accordingly, this
percent H2S/17 percent CO2 was significantly higher than that will affect the coverage of the other adsorbates in OHP and, as a
in 50 percent H2S, while substantially less in 50 percent H2S/50 result, the amount of reactants, e.g. H and H2CO3 dipole
percent CO2. In other words, adding 17 percent CO2 (as shown in following discussion) in the OHP will decrease.
accelerated anions desorption tremendously in 50 percent At the same time, the numbers of anions in OHP, i.e. HS2 ,
H2S, but adding 50 percent CO2 slowed down the rate of anion HCO2 2
3 and Ac , and the extent of the hydrogen absorption
desorption. On the other hand, k1 increased with the increasing caused by the increasing coverage of CO2 dipoles (and therefore
CO2 content. Among the investigated solutions, k1 changed a the i0 and ic values at the same cathodic overvoltage) decreases.
little when the content of CO2 was increased from 0 to It appears that corrosion rate declines when the electrochemical
34 percent, and the maximum k1 value appeared in 50 percent corrosion cell is controlled by the cathodic reaction.
H2S/50 percent CO2. However, k1 contributed a little to iX. The Compared with in 50 percent H2S, adding 17 percent CO2
maximum qHad was observed in 50 percent H2S/50 percent accelerates anions diffusion into the DL, so more reactants are
CO2, and the minimum value in 50 percent H2S. The adsorbed in the OHP. On the other hand, adding 17 percent
maximum k2 appeared in 50 percent H2S/34 percent CO2, CO2 provides additional reactants, i.e. H2CO3 (as shown in the
and minimum value in 50 percent H2S/17 percent CO2. These following discussion). Hence, 17 percent CO2 addition
results indicate that the rate of hydrogen adsorption at lower Dwc increased the cathodic current density, as well as the corrosion
was affected markedly by the components in the solution. This rate. However, by adding 50 percent CO2 anion diffusion into
may be related to the lower electric field strength that fails to the DL was slowed, so fewer reactants was adsorbed in OHP,
compel all of the anions in outer Helmholtz plane (OHP) into and therefore 50 percent CO2 content depresses the cathodic
the diffusion layer (DL) (Figure 11), and interferes with reaction, which results in a decreased corrosion rate.
hydrogen adsorption. Because iHab was higher than iHad, the
absorptive hydrogen atom is the main form of hydrogen at the 4.2 Cathodic and anodic reactions
electrode. With the increasing content of CO2 in H2S/CO2, iHab Cathode reactions in the solution only containing H2S are
declines. This also indicated that less hydrogen was being shown as follows (Kawashima et al., 1976):
produced. Compared with the situation in 50 percent H2S, H 2 S ad e ! H 2 S 2 2
ad
adding 17 percent CO2 accelerated hydrogen absorption,
but adding 50 percent CO2 depressed hydrogen absorption. H 2 S2
ad H
ad ! H 2 S ad 2 H ad 3

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 k2 /ms2 1 iHab /mA.cm2 2 r2
0 20.86508 0.2554 2 0.09952 3.26456 2 0.45021 0.99618
17 21.54351 0.27663 2 0.15583 2.92540 2 0.45313 0.99841
34 20.79817 0.27768 2 0.12045 8.41078 2 0.45095 0.99662
50 20.78389 0.39411 2 0.16063 4.72119 2 0.39091 0.99655

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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 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 Anti-Corrosion Methods and Materials
Hongda Deng, Chunfu Li and Xianlong Cao Volume 58 Number 4 2011 196 204

RDS From the equations (8) and (10), equation (12) (Bard and
CO2;ad H 2 O ! H 2 CO3;ad 6
Faulkner, 2005) is obtained:
 2   
Hence, in environments containing high contents of H2S and HS ad 2aa;1 FDwa
CO2, the cathodic reduction reactions include equations (2) i a 2FK exp
H  RT
and (5), and H2S diffusion process and equation (6) co-control h i 12
HCO3;ad
2
 
the cathodic reaction rate. 2aa;2 FDwa
At present, the reaction of Fe (oxidized iron) ions is widely 2FK exp
H  RT
accepted. It is agreed that the oxidation reaction was effected

by HS2 in the solution dissolved H2S, as following (Iofa et al., where H , HS 2 2
ad  and HCO3;ad  are the concentrations of H
2 2
1964): and adsorptive HSad and HCO3;ad , and aa,1 and aa,2 are the

symmetry factors of equations (8) and (10). With increasing
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 so more HCO2 3;ad is produced, and results in an increase in ia
FeHS 2
ad ! FeHS ad 2e 8
according to equation (12). However, because the coverage
effects of CO2,ad, ia in H2S/CO2 is lower than in H2S. These
FeHS
ad H 3 O ! Fe
2
H 2S H 2O 9
predictions agree with the anodic experimental results.
In reaction (Iofa et al., 1964), H2S worked as a catalyst for the
anodic reaction. However, the oxidation reaction might be 5. Conclusions
effected by HS2 dissolved in H2S solution (Parkins, 1999) or
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HCO2 The effect of CO2 on corrosion of tubular steel P110 was


3 dissolved in CO2 solution (Davies and Burstein,
1980). Comparing with H2S, adding CO2 slowed down ia and investigated by exposing it in solutions containing high contents
caused minimal changes of the Tafel slope, so the reactions of of H2S and CO2. Weight loss rates and the corrosion densities
the oxidized iron ions were produced not only from the causes decreased with an increase in the CO2 content of H2S/CO2.
described by equations (7)-(9), but also according to the that Scale consisting of sulfide and carbonate was observed in H2S/
given by equation (10). CO2 containing environments. The cathodic reaction rate
decreased with increase in the CO2 content, due to the

Fe HCO2
3 ! FeCO3 H 2e 10 increasing coverage of CO2 absorbate. The anodic reaction
rate increased with the increasing CO2 content, due to the
Therefore, equations (8) and (10) can coexist on the electrode increase in HCO2 3;ad . With the increasing CO2 content in the
in solutions containing dissolved high concentrations of H2S H2S/CO2 solution, fewer anions were desorbed and fewer
and CO2. hydrogen ions were absorbed, therefore, fewer reactants could
To prove above model, the theoretical predictions are take part in the reduction reaction. In solution containing high
compared with the experimental results. contents of H2S and CO2, the cathodic reduction reactions
According to both equations (2) and (5), equation (11) included H2S and H2CO3 reduction reactions, and the anodic
(Bard and Faulkner, 2005) is obtained: oxidation reaction also was affected simultaneously by HS2 and
HCO2 3 ions. The experimental results indicated that CO2 could
i 0;1 exp2ac;1 FDwc =RT
ic accelerate and also could inhibit the corrosion attack in high
1 i 0;1 =i lim ;1 exp2ac;1 FDwc =RT H2S containing environments.
11
i 0;2 exp2ac;2 FDwc =RT
0;2
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Corresponding author
presented at the 12th EPRG/PRCI Biennial Joint Technical
Meeting in Line Pipe Research, Croningen, May. Hongda Deng can be contacted at: dhd7730@163.com

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