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Corrosion behavior of carbon steel in amine-based CO 2 capture system:

effect of sodium sulfate and sodium sulfite contaminants

Article  in  Materials and Corrosion · December 2016

DOI: 10.1002/maco.201609245

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674 DOI: 10.1002/maco.201609245 Materials and Corrosion 2017, 68, No. 6

Corrosion behavior of carbon steel in amine-based

CO2 capture system: effect of sodium sulfate and
sodium sulfite contaminants
W. Emori, S. L. Jiang*, D. L. Duan, O. O. Ekerenam, Y. G. Zheng,
P. C. Okafor and Y. X. Qiao

The effect of sodium sulfate and sodium sulfite on the corrosion behavior of
carbon steel in CO2 capture process with methyldiethanolamine (MDEA)
solution has been studied under an absorber temperature condition (50 8C).The
corrosion behavior was evaluated using electrochemical methods, weight loss
measurements, and surface analytical techniques. Sodium sulfate increased the
system corrosiveness and the rate of corrosion increased with concentration
while sodium sulfite reduced the corrosion rate and the inhibition performance
improved with concentration. Weight loss measurements showed an increase
in corrosion rate with time for sodium sulfate while the inhibition performance
for sodium sulfite was considerably low for the tested concentration.

1 Introduction temperature, high CO2 loading in solution, solution turbulence,

The increasing level of atmospheric carbon dioxide (CO2), the
leading greenhouse gas (GHG), is one of the most challenging
environmental concerns of our age. The atmospheric concentra-
tion of CO2 has increased from 280 ppm during the preindustrial
period to 385 ppm with about half of this increase having
occurred since the mid-1960s [1]. Emissions from fossil fuel-fired
power plants, natural gas processing, and cement plants
represent significant sources of carbon dioxide emissions.
Therefore, carbon capture and storage (CCS) from large point
sources is one option for reducing anthropogenic CO2
emissions [2].
Acid gas absorption process (particularly, the use of amine-
based solvents) has gained attention as a liable option for the
capture of CO2 from flue gas streams emitted from power
plants [3]. This process enhances the overall quality of gas
products and attempts to prevent operational difficulties that
may occur in downstream processes. However, due to elevated
W. Emori, S. L. Jiang, D. L. Duan, O. O. Ekerenam, Y. G. Zheng
CAS Key Laboratory of Nuclear Materials and Safety Assessment,
Institute of Metal Research, CAS, Shenyang 110016 (P.R. China)
E-mail: sljiang@imr.ac.cn
P. C. Okafor
Department of Pure and Applied Chemistry, University of Calabar,
P.M.B. 1115 Calabar (Nigeria)
Y. X. Qiao
School of Materials Science and Engineering, Jiangsu University of
Science and Technology, Zhenjiang 212003 (P.R. China)
CO2 gas flashing, and presence of contaminants and amine
degradation products in the solution, corrosion of process
components sets in. Corrosion in amine-based CO2 capture
processes is one of the most serious operational concerns
affecting safety and process economics as its endgame is usually
unexpected downtime, production loss, and even fatalities [4–6].
Consequently, findings from recent researches have favored the
use of methyldiethanolamine (MDEA, CH3N(C2H4OH)2) as the
most lenient alkanolamine for CO2 capture processes in terms of
corrosion risk because it is a tertiary amine and it does not form
carbamate (R3NCOO
) with CO2 [2,5,7].
Of the various typical flue gas compositions, CO2, O2, and
H2O have been mostly studied with established information on
their effects in alkanolamine-based carbon steel corrosion [8–11].
However, it is pertinent to identify and establish effects of
compounds formed from other flue gas components (sulfur
oxide [SOx], nitrogen oxides [NOx], etc.) on carbon steel corrosion
in CO2 capture systems. A significant class of these compounds
is called heat-stable salts. These salts are essentially the reaction
products of alkanolamine and the acids stronger than CO2. The
acids can either be formed directly from flue gas components or
from amine degradation products. The heat-stable salts become a
major concern as they are non-regenerable during regeneration
reactions thus they remain and accumulate in the absorbent
solution. Corrosion resulting from acid gases in flue gas can be
present in vital parts of the absorber and desorption column of an
amine treatment plant [12].
The choice of the contaminants was aimed at representing
various species typically formed from flue gas reactions. Thus,
sodium sulfate (Na2SO4) and sodium sulfite (Na2SO3)

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Materials and Corrosion 2017, 68, No. 6
represented a commonly found sulfate and sulfite, respectively.
Sodium-based compounds were selected for this study because,
together with iron-based compounds, they are cations with
significant presence within the CO2 capture process [13].
Some literatures have discussed the effects of some of
these salts in different conditions but it is necessary to extend
the knowledge in this area considering the limited
information reported from studies especially for MDEA systems.
Tanthapanichakoon and Veawab [8] reported that heat-stable salts
increased the corrosiveness of carbon steel in MEA-CO2 to
different degrees depending on the salt type and concentration.
Other researchers reported bicine to significantly contribute to
the corrosion of carbon steel while sulfate and formate showed
no noticeable influence on the corrosion behavior in the active
state [14]. However, corrosion inhibitive properties have also
been attributed to sodium thiosulfate [15].
The objective of the present study was to evaluate corrosion
behavior of two sodium-based salts (Na2SO4, Na2SO3) on carbon
steel in MDEA/H2O/CO2/O2 mixture, which represents the
absorber condition of a typical CO2 capture system. The effects of
concentration of the sodium-based salts on the corrosion
behavior of carbon steel were investigated by electrochemical
tests. In addition, weight loss corrosion experiments and surface
analytical techniques were carried out to evaluate the time-
dependent effect of the contaminants and the properties of the
corrosion product layers, respectively.
2 Experimental
2.1 Material
The working electrode was made of carbon steel with a
chemical composition as presented in Table 1. The specimen
for electrochemical measurements was embedded in epoxy
resin with 1.0 cm2 exposed area after polishing and cleaning.
Prior to use for electrochemical test, the surface was
progressively polished with silicon carbide abrasive paper up
to 800 grit, followed by being ultrasonically cleaned with
ethanol and water, and finally dried. The samples for weight
loss and surface analysis (SEM and XRD) had an area of
(2.0  1.0  0.2) cm2 and were polished with silicon carbide
abrasive paper up to 2000 grit.
The electrolyte solution was made up of MDEA with a
concentration of 50% by weight which was prepared from a 99%
MDEA reagent and distilled water. The prepared solution was
then mixed with the contaminant which varied depending on the
studied system. The contaminants used were sodium sulfate
(Na2SO4) and sodium sulfite (Na2SO3). They were of industrial
grade with concentrations above 98%. The conductivity of the
test solution was measured at room temperature. However,
Table 1. Chemical composition (wt%) of the working electrode
Material C Mn P S Cu Si Fe
Carbon steel 0.23 0.79 0.02 0.03 0.29 0.20 Bal.
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Corrosion of carbon steel in amine-based CO2 capture system 675
above 0.1 M, sodium sulfate was not completely soluble in the
test solution and because sodium sulfate has a maximum
solubility in water at 33 8C which decreases with increase in
temperature [16], it is possible that the sodium sulfate remained
insoluble in the test solution at the test temperature (50 8C). To
achieve a typical absorber condition, the test solution was purged
with gas (12% CO2 þ 6% O2 þ 78% N2) and a CO2 loading of
0.13 mol CO2/mol amine was obtained [2]. The purging was for
at least 4 h before the test to achieve equilibrium for the system.
The system equilibrium was confirmed by steady pH values with
time.
2.2 Electrochemical measurements
All electrochemical measurements were carried out in a 0.5 L
glass cell at 50 8C under atmospheric pressure (absorber
condition). The setup included (1) three-electrode corrosion
cell (counter electrode: platinum wire, reference electrode:
saturated calomel reference electrode (SCE); (2) hot plate
equipped with temperature controller; (3) gas (nitrogen, oxygen,
and carbon dioxide) supply set; (4) potentiostat (Gamry
Reference 1000 potentiostat/galvanostat/ZRA); and (5) pH
meter. All potentials in this work were measured versus SCE.
OCP measurement was conducted for 2 h. The EIS measure-
ment was conducted at OCP with a sinusoidal potential
perturbation of 10 mV in a frequency range from 100 to
10 mHz, and the obtained EIS spectra were fitted using the
Gamry software. The potentiodynamic polarization test was
performed from
1.2 to
0.7 V versus OCP at a sweep rate of
0.1667 mV/s. The EIS measurement and potentiodynamic
polarization test were performed when the OCP became
relatively stable.
2.3 Weight loss measurement
Evaluation of the effect of the contaminants on the corrosion of
carbon steel by weight loss measurement was studied at 0.05 M
contaminant concentration. All other test conditions were the
same as those of electrochemical measurements. The specimen
was pre-weighed and suspended in the test solution and retrieved
after 7 days, carefully washed in a pickling acid solution and
rinsed in distilled water, air dried after dipping in acetone and re-
weighed. The weight loss was determined as the difference in
weight of the carbon steel specimen before and after immersion
in the test solution. The weight loss was converted to corrosion
rate using the following expression [17]:
8:76  104  weight lossðgÞ
Corrosion rateðmm=yÞ ¼
areaðcm2 Þ  densityðg=cm3 Þ  timeðhÞ
ð1Þ
2.4 Surface analysis
Scanning electron microscopy (SEM) was used to observe the
surface morphology of the carbon steel specimen, while energy-
dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD)
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
676 Emori et al.
techniques were used to detect the elements and phase
compositions of the corrosion products.
3 Results and discussion
3.1 Conductivity and pH
Corrosion is usually considered as an electrochemical process, so
it is reasonable to assume that the solutions with higher
conductivity will be associated with higher corrosivity. The
results for conductivity and pH measurements in the test
systems are shown in Fig. 1. Despite having solubility challenges
for >0.1 M sulfate at room temperature, the fact still remains that
room temperature conductivity does not directly correlate with
corrosivity but shows a reasonable relationship [16]. The
conductivity of the solutions with the contaminants generally
increased from 0.005 mS/cm for the blank to 1.110 and
0.780 mS/cm at 0.05 M for sulfate and sulfite, respectively. These
values increased steadily up to 2.940 and 2.700 mS/cm,
respectively, at 0.20 M.
The conductivity of a solution depends on the number of
ions present. For dilute electrolyte solution, the molar conduc-
tivity (Lm) can be considered as a constant. The conductivity (k)
of the solution can be written as
k ¼ ^m  c ð2Þ
where c is the molar concentration of the added electrolyte. That is
why addition of sulfate and sulfite increased the conductivity of the
solution and it increased with concentration as mentioned above.
The dissociation constants for aqueous solutions of HSO
4 scans were considered for only the active region of carbon steel as

8
and HSO
3 are 0.01 and 6.6  10 , respectively, at 25 8C, which
shows a significant difference. It can be estimated that even at
our test temperature of 50 8C, the dissociation constant of HSO
4 added to the solutions.
will be much higher than that of HSO
3 . This means that the
concentration of SO2
2

4 ion will be higher than that of SO3 ion,
thus the number of ions present is more in the solution with
sulfate, which caused a higher conductivity as shown in Fig. 1a.
Furthermore, pH measurements for the systems revealed
that the influence of contaminant addition lowered the pH values
Figure 1. (a) Conductivity and (b) pH of the test solutions
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2017, 68, No. 6
from 9.13 recorded for the solution without contaminant. pH
values stabilized at 9.00, 8.95, 8.92, 8.70 for the 0.05, 0.10, 0.15,
and 0.20 M, respectively, for sulfate while they were 9.11, 9.01,
8.96, and 8.87 at the same concentration range for sulfite.
Both SO2
2

4 and SO3 ions are acid radicals of binary acids. In
a neutral solution, they can hydrolyze as follows:



4 þ H2 O ! HSO4 þ OH
SO2
ð3Þ



3 þ H2 O ! HSO3 þ OH
SO2
ð4Þ
These account for the reason why sulfate and sulfite
solutions showed pH > 7. In the present system, the pH was
9.13 without contaminant, which means that the OH
is high
enough to make Equations (3) and (4) react to the reverse
direction thus lowering the pH, as shown above.
Additionally, based on the huge difference in the dissocia-
tion constants for aqueous solutions of HSO


4 and HSO3 , the pH
values for the solution with sulfate are lower than those of their
corresponding solution with sulfite. So when added as
contaminants into the solution with pH of 9.13, the solution
with sulfate showed lower pH value than that with sulfite, as
shown in Fig. 1b.
3.2 Potentiodynamic polarization
Carbon steel showed closely identical curves with active, passive,
and transpassive behaviors for the solutions with and without
contaminants as described in the literature [8,15], but to resolve
the different contaminant effects, potentiodynamic polarization
presented in Fig. 2. It is apparent from the figure that the
cathodic Tafel slopes changed when the contaminants were
From Fig. 2a, the solutions containing sulfate showed slight
increases in the cathodic current density of carbon steel with the
shift of the cathodic curve toward more positive values from that
of blank solution. These observations could be indicative of an
induced corrosion tendency of sulfate on carbon steel. The
overall observed trend is such that an increase in sulfate
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Materials and Corrosion 2017, 68, No. 6 Corrosion of carbon steel in amine-based CO2 capture system 677

Figure 2. Potentiodynamic polarization curves of carbon steel in MDEA solution containing (a) sulfate and (b) sulfite

concentration led to more shift of the cathodic curve of carbon
steel to the positive direction.
On the other hand, the presence of sulfite showed a
reduction in cathodic current densities shifting the cathodic
curve toward lower values (Fig. 2b). This is an indication that
the contaminant functioned as a corrosion inhibitor or retarded
the rate of carbon steel corrosion. Noticeably, the cathodic
curve for each sulfite addition shows a portion of constant
current across a potential range markedly different from the
curve of the solution without sulfite, suggesting that at least
one of the reactions is limited by the rate of reactant transport
to the surface of the working electrode [18]. From the figure,
the cathodic processes are initially characterized by mass
transfer, which may be due to oxygen reduction reaction
(ORR). SO2
3 is a known reducing agent and an oxygen
scavenger. It supplies electrons to dissolved oxygen (oxidizing
agent) thereby reducing the amount of dissolved oxygen in the
system by the following reaction:
1 carbon steel resistance to corrosion. This, therefore, indicates
3 þ O2 $ SO4
SO2
ð5Þ
2

2 that sulfate induced a uniform corrosion on carbon steel and the
The rate of consumption of the dissolved oxygen increased
with increasing sulfite concentration and reached a maximum at
0.15 M sulfite concentration. Subsequent sulfite addition (0.2 M)
did not reveal any obvious change in the cathodic curve.
Carbon steel did not show Tafel behavior in the active state
and as such, the corrosion current density (Icorr), which is usually
used to interpret the corrosion resistance of an active system by
extrapolating the anodic and cathodic Tafel lines to the open-
circuit corrosion potential (Ecorr) [19], could not be obtained for
the different test systems.
3.3 Electrochemical impedance spectroscopy (EIS)
measurement
Nyquist plots for carbon steel in the different test solutions are
shown in Figs. 3a and 4a. For Fig. 3a, the magnitude of the
impedance decreased with the initial sulfate addition and
continued progressively with increase in sulfate concentration.
The decrease in magnitude reflects a continuous decrease in
corrosion increased with increasing sulfate concentration. For

Figure 3. (a) Nyquist and (b) Bode plots of carbon steel in MDEA solution containing sulfate

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678 Emori et al.
Figure 4. (a) Nyquist and (b) Bode plots of carbon steel in MDEA solution containing sulfite
the solution with sulfite (Fig. 4a), the contaminant addition
induced an increase in the magnitude of the impedance. Sulfite
addition above 0.05 M concentration caused a corresponding
increase in the magnitude of impedance up to a maximum at
0.15 M. A slight decrease in impedance was observed after the
0.15 M concentration peak. This indicates that sulfite addition
influenced a corrosion resistance in carbon steel which increased
continuously with the salt concentration until a maximum at
0.15 M concentration. The observed reduction in corrosion
resistance tendency may be due to the generation of opposing
chemical reactions in the test solution and their effects on the
surface of carbon steel as explained by Equation (5).
Figures 3b and 4b depict the phase angle plots of carbon steel
for the same test solutions and experimental data in the Bode
format. Phase angles with concentration were observed to be
decreasing for the sulfate solution (Fig. 3b) and increasing for the
sulfite solution (Fig. 4b) in the lower frequencies but these did not
show clear resolutions at higher frequencies. This is in line with
observations for their corresponding Nyquist plot. In general, the
observations from EIS plots correlated well with the plots from
potentiodynamic polarization for the same test solutions.
Additionally, polarization resistance (Rp) was used to evaluate
the corrosion resistance and this required fitting the EIS spectra
using an equivalent circuit. The equivalent circuit used is shown in
Fig. 5. While Rs is the resistance of the solution, Rct and Cdl
correspond to the charge transfer resistance and capacitance of the
double layer, respectively, and Rf and Cf correspond to the
Figure 5. The equivalent circuit used to fit the EIS spectra
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2017, 68, No. 6
resistance and capacitance of the film, respectively. Due to the
distribution of relaxation times originating from the surface
heterogeneity, a constant phase element (CPE) was used to
describe the frequency dependence of non-ideal capacitive
behavior instead of the ideal capacitance thus improving the
fitting quality [20,21]. However, Cdl and Cf were used for simplicity.
The electrochemical parameters obtained by fitting the EIS data
are presented in Table 2. The validity of the obtained electrochemical
parameters was judged by the small values of chi-square values
(x2) [22]. The Rp is evaluated from the following expression [23]:
Rp ¼ Rct þ Rf ð6Þ
Rp values of carbon steel in the test solutions are shown in
Fig. 6. The Rp value for the solution with sulfate decreased
considerably from 61.61 kV cm2 for the solution without sulfate to
9.42 kV cm2 for the solution with 0.2 M sulfate. This demonstrates a
continuous depletion of the protectiveness formed on the surface of
the metal with every sulfate addition. Rp values for the solution with
sulfite apparently indicates an inhibition effect on carbon steel
corrosion with the contaminant addition. It increased from
61.61 kV cm2 for the solution without the contaminant to a
maximum of 173.48 kV cm2 corresponding to the 0.15 M sulfite
concentration. The value, however, dropped to 151.83 kV cm2 for
0.2 M sulfite. This phenomenon is consistent with the observations
highlighted by the Nyquist and Bode plots. With an exception in the
simulation result of 0.20 M Na2SO4, solution resistance Rs increased
with concentration of contaminants, which is mainly consistent
with the conductivity measurement mentioned in Fig. 1a.
3.4 Weight loss measurement
Figure 7 shows the average corrosion rate of carbon steel for the
solutions with and without the contaminants at 0.05 M after
7 days immersion. The corrosion rates measured by weight loss
generally have similar trends with the results of electrochemical
tests. The corrosion rate for the solution without contaminants
was 0.092 mm/y whereas the solution with sulfate and sulfite
yielded 0.102 and 0.076 mm/y, respectively.
From the data, it is obvious that the corrosiveness of the
solution with sulfate increased over time compared to
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Materials and Corrosion 2017, 68, No. 6 Corrosion of carbon steel in amine-based CO2 capture system 679

Table 2. Electrochemical parameters obtained from the fitting of EIS data

Salt Concentration/M Rs/V cm2 Rct/kV cm2 Cdl/µF/cm2 n Rf/kV cm2 Cf/µF/cm2 n x2

Blank 87.3 2.21 6.6 0.92 59.4 312.1 0.43 2E-04

Na2SO4 0.05 46.2 1.80 7.2 0.93 53.9 355.5 0.41 4E-03
0.10 31.1 3.32 10.2 0.92 49.6 408.2 0.52 6E-03
0.15 24.0 5.50 16.4 0.86 22.9 416 0.51 1E-03
0.20 40.1 2.63 8.1 0.88 6.8 651.5 0.49 1E-03
Na2SO3 0.05 63.7 3.05 7.6 0.91 103.7 249.4 0.50 4E-04
0.10 50.5 13.05 14.6 0.91 134.2 180.8 0.54 4E-04
0.15 47.7 56.08 1.8 0.91 117.4 275.8 0.49 8E-04
0.20 35.4 53.86 18.8 0.92 98.0 15.9 0.32 8E-04

corresponding values of the blank solution while the corrosion Reduction of dissolved oxygen:
rate for the test solution with sulfite typically decreased.
O2 þ 2H2 O þ 4e
$ 4OH
ð10Þ
3.5 Mechanism of contaminant addition on corrosion Reduction of carbonic acid:
process
2H2 CO3 þ 2e
$ 2HCO

3 þ H2 ð11Þ
It is necessary to identify the major reactive species in the test
systems. The standard electrode potential of sodium ion, Naþ Reduction of bicarbonate ion:
(
2.71 V), is lower than that of ferrous ion, Fe2þ
(
0.44 V) [18,24]. This gives the ferrous ion preference for
2HCO


3 þ 2e $ 2CO3 þ H2
2

ð12Þ
gain of electron on the metal surface. Naþ is, therefore,
considered to be negligible in the corrosion reaction study of
Reduction of protonated amine:
the systems. Therefore, the anodic (oxidation) reaction is
2MDEAHþ þ 2e
$ 2MDEA þ H2 ð13Þ
Fe ! Fe2þ þ 2e
ð7Þ
Consequently, the resulting corrosion products formed are:
while the cathodic (reduction) reactions are [14] Formation of iron (II) hydroxide:

Reduction of hydrogen ion:

Fe2þ þ 2OH
$ FeðOHÞ2 ð14Þ
þ

2H þ 2e $ H2 ð8Þ Formation of iron (III) hydroxide: When FeðOHÞ2 is exposed to
oxygen and water, it is oxidized to iron (III) hydroxide
Reduction of water:
1
2H2 O þ 2e
$ 2OH
þ H2 ð9Þ 2FeðOHÞ2 þ H2 O þ O2 $ 2FeðOHÞ3 ð15Þ
2

Figure 6. Dependence of polarization resistance (Rp) of carbon steel in MDEA solution with different concentrations of (a) sulfate and (b) sulfite

www.matcorr.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

680 Emori et al.
Figure 7. Average corrosion rate for the solutions with and without the
contaminants at 0.05 M concentrations after 7 days immersion
Formation of iron (II) carbonate:
Fe2þ þ CO2

3 $ FeCO3 ð16Þ
Dissolved CO2 is the primary corroding agent in alkanol-
amine system [25], thus the formation of FeCO3 predominates.
The corrosion products adhere to the surface of the metal and act
as protective barriers against diffusion of the corroding agents to
the metal surface and thereby hindering further metal dissolution.
Therefore, the effect of the overall protective barrier will depend on
the adherence of the corrosion products and the effects of
reactions of the added contaminants with the corroding agents.
From Table 2 and Figs. 2a, 3a, and 4a, it is evident that the
addition of sulfate accelerated the corrosion reaction of carbon
Figure 8. SEM images and their corresponding EDS analysis for carbon steel surface after 7 days immersion in MDEA solution with (a) no
contaminant, (b) 0.05 M sulfate, and (c) 0.05 M sulfite
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2017, 68, No. 6
steel. This may be the consequence of increase in conductivity
and lowering of pH caused by the presence of sulfate ions
(Fig. 1).
On the other hand, Table 2 and Figs. 2b, 3b, and 4b reveal
that sulfite addition decelerated the corrosion process of carbon
steel. This is in accordance with Equation (2) where SO2

3 ion was
shown to exhibit reducing properties for dissolved oxygen by
supplying electrons to the dissolved oxygen thereby reducing its
amount in the system.
At 0.2 M sodium sulfite, Bode and Nyquist plots revealed
that although the corrosion rates were still inhibited, there was
a slight drop in the inhibitive behavior which was indicated by
the phase angle reduction and drop in the impedance
magnitude, respectively. Equation (2) shows that the increase
in reaction between SO2
3 and O2 resulted in a corresponding
increase in SO2
4 which can ultimately increase the corrosion of
carbon steel in the system. Therefore, when the addition of
SO2
2

3 went beyond 0.15 M, the presence of SO4 became more
deleterious. This observation suggests that there is no direct
relationship between the inhibition performances of sulfite
with concentration.
The result from weight loss experiment (Fig. 7) shows that
though sulfite could inhibit the corrosion process of carbon steel
in the MDEA system, its inhibition efficiency was quite low
(16.7%). Two possible explanations for the low value of inhibition
efficiency is that firstly, while SO2

3 ion removes only dissolved
oxygen by its oxygen scavenging property, it did not affect other
corroding agents in the system. The actions of the other
corroding agents may have played prominent roles in causing
corrosiveness in the system with time. Secondly, since oxygen
was continually purged during the experiment, the amount of
SO2

3 may have been used up with time. The inhibition efficiency
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Materials and Corrosion 2017, 68, No. 6
Figure 9. XRD analysis for corrosion product on carbon steel surface
after 7 days immersion in MDEA solution with (a) 0.05 M sulfate and (b)
0.05 M sulfite
(IE) from weight loss experiment was calculated from the
expression:
Rb
R s
IE ¼  100 ð17Þ
Rb
where Rb and Rs are corrosion rates of carbon steel in the test
solutions without and with the presence of sulfite, respectively.
3.6 Surface analysis
SEM images of carbon steel were taken and EDS analysis
performed in the absence and presence of 0.05 M of sulfate and
sulfite. The SEM image and its corresponding chemical analysis
from the surface of carbon steel after 7 days immersion in the
solution without contaminant is shown in Fig. 8a. The coupon
showed complete surface coverage of corrosion product layer; this
suggests that the corrosion rate of the coupon increased rapidly
until the formation of the dense corrosion product layer where the
layer can inhibit further corrosion. On closer examination of the
product layer on the metal surface, it can be observed that the film
consists of larger crystals growing on smaller ones. The same
observations of film presence were recorded for the solutions with
sulfate and sulfite (Fig. 9b and c). However, in the presence of
0.05 M sulfite, the film appears less dense as the inner smaller
crystals are shown not to be completely covered by the larger
crystals indicating retardation in corrosion process for the system.
The EDS analysis results suggest that the main corrosion products
are likely iron carbonate with small traces of sulfur-based
compounds. Based on the results of XRD analysis as shown in
Fig. 9, siderite (FeCO3) was characterized to be the main corrosion
product along with the presence of iron (Fe).
4 Conclusions
The effects of sodium sulfate (Na2SO4) and sodium sulfite
(Na2SO3) salts have been evaluated as contaminants on the
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Corrosion of carbon steel in amine-based CO2 capture system 681
corrosion behavior of carbon steel in an MDEA-CO2 capture
system. Electrochemical measurements and weight loss
techniques revealed that sulfate can increase the corrosion
rate of carbon steel mainly due to its effect on increasing
conductivity and decreasing pH of the test solutions while
sulfite caused a reduction in the corrosion rate. This owes
largely to its oxygen scavenging behavior where it acts as a
reducing agent. Polarization resistance (Rp) decreased with
concentration for sulfate whereas it generally increased for
sulfite but the maximum value recorded for the 0.15 M
concentration suggests that though the Rp increases, there is
no direct relationship with concentration as the oxidation
reaction of SO2
3 with dissolved oxygen subsequently
produces enough SO2
4 which can influence the corrosiveness
of the system. The corrosion product layer analysis typically
consisted of FeCO3 formation for the systems with the test
contaminants.
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(Received: September 2, 2016) W9245

(Accepted: November 7, 2016)

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