Ind. Eng. Chem. Res.

2009, 48, 10169–10179 10169

Corrosion Behavior of Carbon Steel in the Monoethanolamine-H2O-CO2-O2-SO2

System: Products, Reaction Pathways, and Kinetics
Nattawan Kladkaew,† Raphael Idem,*,‡ Paitoon Tontiwachwuthikul,‡ and Chintana Saiwan†
Petroleum and Petrochemical College, Chulalongkorn UniVersity, Bangkok 10330, Thailand, and
International Test Centre for CO2 Capture, UniVersity of Regina, Regina, SK, Canada S4S 0A2

This work investigates the effect of operating parameters on corrosion products, reaction pathways, and kinetics
for the corrosion of carbon steel in the monoethanolamine-H2O-CO2-O2-SO2 system. Corrosion experiments
were conducted using a 273A potentiostat unit under conditions in which monoethanolamine (MEA), O2,
and SO2 concentrations and CO2 loading were in the range of 1-7 kmol/m3, 0-100%, 0-204 ppm, and
0-0.5 mol CO2/mol MEA, respectively, at corrosion temperatures of 303-353 K to mimic the
absorption-regeneration sections. Analysis, performed for this system for the first time, shows that corrosion
products generated from the effect of SO2 include FeSO4 and Fe2O3 · H2O. Also, a higher concentration of
SO2 in simulated flue gas stream induces a higher corrosion rate because of the increase in the hydrogen ion
concentration generated by reactions of SO2 and H2O as well as SO2, O2, and H2O. A power-law model
developed to correlate corrosion rate with the parameters in the MEA-H2O-CO2-O2-SO2 system shows
that corrosion rate of carbon steel increases with an increase in O2 and SO2 concentrations in simulated flue
gas stream, as well as MEA concentration, CO2 loading, and operating temperature. It was observed that CO2
loading had the highest impact on the corrosion rate, while SO2 and O2 show only slight effects on the
corrosion rate.

1. Introduction experimental analytical results have been reported to quantify

Coal-fired power plants represent a major source of CO2
emission as well as varying amounts of sulfur dioxide (SO2).
Chemical absorption with aqueous amine solutions such as
monoethanolamine (MEA) has been found to be an effective
CO2 capture technique especially for low-pressure flue gas
streams. However, the disadvantage is that aqueous amine-based
CO2 capture systems can be prone to corrosion problems. The
corrosion rate of this system increases with increasing amine
(e.g., MEA) concentration, CO2 loading, process temperature,
oxygen concentration,1-4 and solution velocity.3,4 Heat-stable
salts also increase the corrosiveness of carbon steel in MEA
solution-CO2 environment to various degrees depending on the
type and concentration of the salt.5,6 Sulfur dioxide (SO2), also
an acid gas, in flue gas can give rise to plant equipment damage.
In a previous study,7 the effects of various operating parameters
on corrosion of carbon steel in simulated CO2 capture process
in the presence of SO2 were investigated. It was found that
corrosion rate of carbon steel in a MEA-H2O-CO2-O2-SO2
system varies significantly with the operating parameters. O2,
SO2, and MEA concentrations, CO2 loading, and operating
temperature can induce corrosion. However, this work did not
identify the products that are formed and the possible pathway
for SO2 related corrosion or its interaction with corrosion caused
by other variables such as CO2 loading, MEA concentration,
O2 concentration, and process temperature.
In the literature, Rooney and DuPart8 reported that some
corrosion products in CO2 absorption with aqueous amine
solutions such as iron carbonate and iron hydroxide, which are
often insoluble and precipitate, are found in various places in
the plant. There are also other soluble products in the corrosion
system as well, such as Fe(HCO3)2. However, no direct
these products. In order to understand how these corrosion
products are produced, some corrosion mechanisms or pathways
have been postulated. Generally, corrosion can be explained in
terms of electrochemical reactions involving the transfer of
electrons which results in material deterioration. More specif-
ically, when a metal is immersed in a given solution, electro-
chemical reactions occur at the surface of the metal, causing
the metal to corrode. The corrosion process involves two or
more reactions at the electrodes: the oxidation of the metal
(anodic partial reaction) and the reduction of an oxidizing agent
(cathodic partial reaction). The oxidation reaction leads to the
production of electrons whereas the consumption of electrons
signifies a reduction reaction.9,10 For example, the corrosion of
zinc in an acid environment proceeds according to the following
reactions:
Overall reaction
Zn + 2H+ T Zn2+ + H2 (1)
Oxidation reaction
Zn T Zn2+ + 2e- (2)
Reduction reaction
2H+ + 2e- T H2 (3)
According to Veawab and Aroonwilas,11 several corrosion
mechanisms in an aqueous amine-CO2 system have been
postulated in the amine treating plant. In this work, five different
types of iron dissolution reactions were suggested.
The evolved CO2 reacts directly with carbon steel to form
iron carbonate (FeCO3) as shown in reaction 4.12

Fe + CO2 + H2O T FeCO3 + H2 (4)

* To whom correspondence should be addressed. E-mail:
Raphael.idem@uregina.ca. Fax: (306)585-4855.
†
Chulalongkorn University. The second one is corrosion involving the reduction of the
‡
University of Regina. hydrogen ion13
10.1021/ie900746g CCC: $40.75  2009 American Chemical Society
Published on Web 11/02/2009
10170 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009
Fe + 2H+ T Fe2+ + H2 (5)
Bicarbonate ion (HCO3-) in the solution functions as an
oxidizing agent in the reduction reaction14
Fe + 2HCO3- T FeCO3 + CO32- + H2 (6)
Corrosion due to the reduction of undissociated carbonic acid
(H2CO3)15
Fe + H2CO3 T FeCO3 + H2 (7)
In addition to the above reactions, Kossein et al.16 consider that
there is the corrosion mechanism involving the amine itself.
Fe + 2RR′NH2+ T Fe2+ + H2 + 2RR′NH (8)
where RR′NH2+ and RR′NH denote protonated amine ion and
amine, respectively. However, this has not been used in any
other work.
In the present work, the products that are formed and the
possible pathway for corrosion caused by SO2 and its interaction
with corrosion caused by other variables such as CO2 loading,
MEA concentration, O2 concentration, and process temperature
are identified and quantified. This work also attempts to postulate
possible pathways to account for these products. Analytical
techniques were used to obtain information on the organic anions
in the tested solution as well as the corrosion products on the
metal surface and those that dissolved in the solution. Inductively
coupled plasma-mass spectrometry (ICP/MS) was used to
determine the amount of dissolved iron in the solution, while
capillary electrophoresis (CE) was used to determine the organic
anions present in the tested solution. Corrosion products on the
metal surface were evaluated by using both scanning electron
microscopy and energy dispersive spectrometry (SEM/EDS).
In addition, an empirical kinetic evaluation to determine the
effects of the process variables on corrosion rate in the presence
of SO2 was formulated. The results of these analyses and
evaluation are presented and discussed in this paper.
2. Experiments
2.1. Equipment and Chemicals. The electrochemical experi-
ments were carried out using aqueous monoethanolamine (Fisher
Scientific, ON, Canada) as the absorption solvent. It was diluted
with deionized water to the desired concentration, which was
accurately determined by titration with 1.0 N hydrochloric acid
(HCl) solution using methyl orange as the titration indicator.
The desired concentration of aqueous MEA solution was then
preloaded with carbon dioxide to obtain the desired CO2 loading
(mol CO2/mol MEA) by purging a stream of CO2 gas (Praxair,
research grade, ON, Canada) into the solution. The CO2 loading
procedure followed the AOAC method.17 The desired CO2
loading was determined by titrating with a 1.0 N HCl solution
using a Chittick apparatus.
Carbon steel C1020 (Metal Samples Company, Munford, AL)
was used to study the corrosion in the MEA-H2O-CO2-
O2-SO2 system. The chemical composition of C1020 in
percentage was as follows: C, 0.19; Cr, 0.01; Cu, 0.01; Mn,
0.56; Mo, 0.01; N, 0.0036; Ni, 0.01; P, 0.009; S, 0.007; and
Fe, balance. The tested specimens are cylindrical in shape with
3/8 in. diameter, 1/2 in. length with a 3-48 threaded hole at
one end. The specimens were prepared in accordance with
ASTM G1-90.18 The specimens were wet ground with 240 grit
silicon carbide paper, wet polished with 600-grit silicon carbide
paper, rinsed with deionized water, dried with air, and kept in
a desiccator before use. The surface areas of the specimens were
determined by measuring all dimensions with a vernier caliper.
Electrochemical techniques are used to study corrosion and
corrosion behavior of carbon steel C1020 in the MEA-H2O-
CO2-O2-SO2 system. The experiment setup for this technique
is shown in Figure 1. It consists of an ASTM corrosion cell,
potentiostat, water bath with temperature controller, condenser,
gas supply set, and data acquisition system. An ASTM corrosion
cell model K47 (London Scientific, Ltd., London, ON, Canada),
is a 1 L flat bottom flask with ground glass joints. It is composed
of one working electrode mounted with specimens, two high-
density carbon graphite rods used as counter electrodes, one
reference electrode which is a mercurous sulfate electrode
(MSE), one bridge tube, and a glass inlet and outlet for
transferring gas to and from the corrosion cell. A potentiostat
model 273A (London Scientific, Ltd., London, ON, Canada)
was used to control the potential and to read the current
accurately. PowerCORR version 2.47 (London Scientific, Ltd.,
London, ON, Canada) was used to acquire and analyze the
experimental data. A water bath with a temperature controller
was used to control the operating temperature. A condenser was
connected to the corrosion cell to maintain the temperature of
the solution in order to keep the correct concentration in the
cell, while avoiding evaporation during the experiment. The gas
supply set was gaseous mixtures of SO2-O2-N2 that were
similar to actual flue gas stream conditions.
ASTM G5-9419 was used in evaluating the accuracy of a
given electrochemical test apparatus. It was performed by
running the experiment with potentiodynamic anodic polariza-
tion technique on a 430 stainless steel in a 1 N sulfuric acid
(H2SO4) solution at 30 °C. The reliability of experiment is
ascertained when the obtained polarization plot appears within
the reference band. All the electrochemical experiments were
carried out in accordance with ASTM G5-94.
2.2. Typical Experimetal Run. 2.2.1. MEA-H2O-CO2-
O2 System: The Effect of Oxygen Concentration. The corrosion
cell containing about 1 L of 5 kmol/m3 MEA and a CO2 loading
of 0.4 mol CO2/mol MEA was immersed in a water bath with
a temperature controller. The temperature of the solution was
kept constant at 353 K. Oxygen concentration in a stream of
simulated flue gas was varied as 0, 6, 21, and 100% and
introduced into the corrosion cell at a flow rate of 150 mL/min
for 1.5 h. The carbon rods counter electrodes were placed in
the test cell. Then, the salt bridge was filled with the test solution
and placed in the corrosion cell. The prepared surface was
mounted on the electrode holder rod. Consequently, the speci-
men was degreased with methanol and rinsed in distilled water
just prior to immersion in the test cell. The salt-bridge probe
tip was adjusted close to the specimen electrode. All the lines
between the corrosion cell and the model 273A potentiostat had
been connected before the corrosion potential (ECORR) versus
the MSE reference electrode of the test system were measured
for at least 1 h to ensure that the corrosion potential value
remained constant. Finally, the electrochemical experiment was
started. During the running of each experiment, the applied
potential and the measured current were continuously recorded.
2.2.2. MEA-H2O-CO2-O2-SO2 System: The Effect of
SO2 Concentration. The procedures were the same as described
in the effect of oxygen concentration, but a stream of simulated
flue gas with varying SO2 concentrations 0, 5, 10, and 204 ppm
with 6% oxygen was introduced into the corrosion cell at a flow
rate of 150 mL/min for 1.5 h.
 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10171

Figure 1. Experimental setup for electrochemical corrosion experiment.

2.2.3. MEA-H2O-CO2-O2-SO2 System: The Effect of

CO2 Loading. Just as described for the MEA-H2O-CO2-
O2-SO2 system, about 1 L of 5 kmol/m3 MEA, preloaded CO2
loadings of 0, 0.2, 0.4, and 0.5 mol CO2 loading/mol MEA were
studied with a stream of simulated flue gas of 204 ppm SO2
and 6% O2. The procedures followed here were the same as
those described above for the effect of SO2 concentration.
2.2.4. MEA-H2O-CO2-O2-SO2 System: The Effect of
MEA Concentration. Just as in the case of the MEA-H2O-
CO2-O2-SO2 system, about 1 L of MEA solution with varying
concentrations of 1, 3, 5, and 7 kmol/m3, CO2 loading of 0.4
mol CO2/mol MEA were studied. The procedures were the same
as described in the effect of CO2 loading.
2.2.5. MEA-H2O-CO2-O2-SO2 System: The Effect of
Operating Temperature. Just as in the case of the MEA-H2O-
CO2-O2-SO2 system, the experimental conditions were set at
1 L of 5 kmol/m3 MEA and a CO2 loading of 0.4 mol CO2/mol
MEA. The temperature was adjusted at 303, 328, and 353 K.
The procedures were the same as described in the effect of CO2
loading.
2.3. Corrosion Measurement Technique: Tafel Plot.9,20 In
our previous work,7 we used two techniques (Tafel plot and
potentiodynamic) to evaluate corrosion rates. Both techniques
provided very similar trends of information. The corrosion rates
obtained from Tafel plot and potentiodynamic techniques were
almost identical. In this work, we decided to use the Tafel plot
technique. A Tafel plot was generated by beginning the scan
from -250 to +250 mV vs corrosion potential (ECORR). The
resulting data is plotted as the applied potential vs the logarithm
of the measured current. The corrosion current (iCORR) was
obtained from the intersection at ECORR and, then, was used to
calculate the corrosion rate using eq 9.
0.13iCORR(EW)
CR(mpy) )
Ad
where CR is the corrosion rate in mils per year (mpy), iCORR is
the corrosion current in microampere (µA), EW is the equivalent
weight of the corroding species in grams (g), A is the surface
area of the specimen in squared centimeters (cm2), and d is the
density of the specimen in grams per cubic centimeter (g/cm3).
2.4. Analysis of Corrosion Products. 2.4.1. Inductively
Coupled Plasma-Mass Spectrometry (ICP/MS) Technique.
The Varian ICP/MS (Varian, Inc., Mississauga, ON, Canada)
was used to determine the amount of dissolved iron (Fe) in the
tested solution. The acquired data were used to confirm the fact
Figure 2. Effect of O2 concentrations in simulated flue gas stream on
polarization curves obtained with the Tafel plot technique for a system
prepared with 5 kmol/m3 MEA and a CO2 loading of 0.4 mol CO2/mol
MEA at 353 K.
that higher amounts of dissolved iron represent higher corrosion
rates for each studied system. Furthermore, corrosion products
are generally composed of dissolved iron.
2.4.2. Capillary Electrophoresis (CE) Technique. A CE
instrument equipped with a diode array detector (DAD, HP 3D
CE, Hewlett-Packard Canada, Ltd., Montreal, QC, Canada) was
employed for the detection of inorganic anions in the tested
solution. There are six different anions considered in this work,
namely bicarbonate, carbonate, sulfite, bisulfite, sulfate and
thiosulfate, which were chosen based on the possible formation
of these anions in the studied system.
2.4.3. Scanning Electron Microscopy-Energy Dispersive
Spectrometry (SEM-EDS) Technique. SEM (JSM-5600, JEOL
USA, Inc., Peabody, MA) was used to examine the surface area
of the tested specimen. Then, an EDS (EDAX Genesis 7000,
(9)
EDAX, Inc., Mahwah, NJ) detector was used to characterize
the elemental distribution on the surface of the images taken
by SEM. This analytical technique can be used to determine
the composition of the corrosion product on the metal surface.
3. Results and Discussion
3.1. Corrosion Rate. 3.1.1. Oxygen Concentration.
3.1.1.1. Experimental Results. Figure 2 shows the polarization
curves of the effect of oxygen concentration in the simulated
flue gas stream on the corrosion rate of carbon steel in the tested
system from the experiments. The small changes of corrosion
10172 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009

Figure 3. Effect of O2 concentrations in simulated flue gas stream on

corrosion rate for system prepared with 5 kmol/m3 MEA and a CO2 loading
of 0.4 mol CO2/mol MEA at 353 K.

Figure 5. Effect of O2 concentrations in simulated flue gas stream on the

carbonate/bicarbonate concentrations in tested solution for a system prepared
with 5 kmol/m3 MEA and a CO2 loading of 0.4 mol CO2/mol MEA at
353 K.

Figure 4. Effect of O2 concentration in simulated flue gas stream on the

amout of dissolved iron in solution for a system prepared with 5 kmol/m3
MEA and a CO2 loading of 0.4 mol CO2/mol MEA at 353 K.

current density with oxygen concentration in Figure 2 were

determined using the PowerCORR program which requires a
large number of data points. This was made possible because
each graph consists of a large number of raw data. The results
obtained from the PowerCORR program are plotted in Figure
3, which demonstrates that the corrosion rate increases with
increasing oxygen concentration.
Figure 6. SEM image of the tested specimen surface before the experiment.
3.1.1.2. Corrosion Products Analysis. The ICP/MS technique
examines the amount of dissolved iron in the tested solution.
The amount of iron obtained in the tested solution as a function
of oxygen concentration in the simulated flue gas stream is
shown in Figure 4. It is seen from the figure that the amount of
dissolved iron present in the tested solution increases as the
oxygen concentration in simulated flue gas stream increases.
This is confirmation that a high oxygen concentration is
detrimental to the absorption process in terms of a higher
corrosion rate.
Only carbonate and bicarbonate inorganic anions were
detected together by the CE technique in the tested solution.
The amount of carbonate/bicarbonate obtained in the tested
solution as a function of oxygen concentration in the flue gas
is shown in Figure 5. The figure shows that there is no significant
change in the amount of carbonate/bicarbonate anions in the
tested solution for different oxygen concentrations. This is
Figure 7. SEM image of the tested specimen surface after the experiment.
because each of the tested solutions contained the same amount
of dissolved carbon dioxide. It is well-known that the carbonate
or bicarbonate are typically derived from dissolved carbon
dioxide and not from dissolved oxygen, thus explaining why The representative EDS spectrum (elemental mapping) shown
the amount of carbonate/bicarbonate ions are independent of in Figure 8 reveals the elemental compositions of these
the oxygen concentration in the flue gas. microscope images. Iron (Fe), carbon (C), oxygen (O), and
Generally, the tested specimen surface is changed from shiny sulfur (S) are indicated to be the composition of the corrosion
to tarnished metal because the specimen surface is covered by products. Therefore, only these elements are considered. The
some corrosion products. Figures 6 and 7 respectively show amounts of each element on the metal surface are shown in
representative SEM images of the tested specimen surface in Figure 9. The first bar represents the amounts of the elements
microscopic scale before and after the experiment. on the specimen surface before the experiments. These amounts
 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10173

Figure 10. Effect of SO2 concentrations in simulated flue gas stream on

polarization curves obtained with the Tafel plot technique for a system
prepared with 5 kmol/m3 MEA and a CO2 loading of 0.4 mol CO2/mol
MEA with simulated flue gas stream of 6% O2 at 353 K.

Figure 8. EDS spectrum of the tested specimen. The general anodic reaction is the dissolution of iron or the
oxidation of iron to the ferrous (Fe2+) ion given in reaction 11.

Fe T Fe2+ + 2e- (11)

Then, the reduction-oxidation reaction among iron, dissolved
oxygen, and water occurs as in reaction 12
2Fe + O2 + 2H2O T 2Fe(OH)2 (12)

The produced ferrous hydroxide component (Fe(OH)2) is

unstable in systems containing oxygen and thus is oxidized to
the ferric salt (Fe(OH)3) or rust21 as
Figure 9. Effect of O2 concentration in simulated flue gas stream on the
amount of elements on the tested specimen for a system prepared with 5 2Fe(OH)2 + 1/2O2 + H2O T 2Fe(OH)3 (13)
kmol/m3 MEA and a CO2 loading of 0.4 mol CO2/mol MEA at 353 K.
The corrosiveness of the system is due to the amount of
are compared with those after the experiments for the second,
dissolved oxygen in the tested solution leading to the oxidation
third, and fourth bars for 0, 6, and 100% oxygen, respectively.
of iron.
The amount of Fe on the surface of the tested specimen
3.1.2. Sulfur Dioxide Concentration. 3.1.2.1. Experimental
decreases as the oxygen concentration in simulated flue gas
Results. Figure 10 shows the obtained Tafel plot of the effect
stream increases. On the other hand, the amount of O increases
of sulfur dioxide concentration in the simulated flue gas stream
as the oxygen concentration increases, whereas there is no
on corrosion rate. The slightly higher current densities are shown
change in the amount of S. This is probably due to the small
in this figure based on the Tafel plot technique. As explained
amount of sulfur in the system relative to those of Fe and O.
in the oxygen concentration case, the small changes of corrosion
The amount of C increases slightly from its original value.
current density with SO2 concentration were determined using
Therefore, the products that are formed based on O and C on
the PowerCORR program which requires a large number of data
the tested surface are more measurable than those formed from
points. This was made possible because each graph consists of
S. These products include Fe(OH)2, Fe(OH)3, and FeCO3. We
a large number of raw data. The results obtained from the
have attempted to use the XRD technique to determine and
PowerCORR program are plotted in Figure 11. This figure
verify the corrosion product formed on the specimen surface
shows the effect of sulfur dioxide concentration in the flue gas
but could not get any meaningful result from this technique. It
stream on corrosion rate and shows that the corrosion rate
is possible that the corrosion products are either not in a
increases slightly with the SO2 concentration.
crystalline form or are present in very minute amounts. As such,
3.1.2.2. Corrosion Products Analysis. Increasing the SO2
the use of the XRD technique appears not to be appropriate for
concentration in the system results in a higher amount of
this system.
dissolved iron (as determined by ICP-MS) being present in the
3.1.1.3. Mechanisms. The effect of varying the oxygen
solution. This is shown in Figure 12. This shows clearly that
concentration on corrosion of carbon steel in an MEA-H2O-
SO2 in the flue gas induces corrosion in the amine-based CO2
CO2-O2 system is due to the difference in the amount of
absorption system.
dissolved oxygen. The higher the oxygen concentrations, the
The amount of carbonate/bicarbonate anions in the tested
higher the dissolved oxygen present in the tested solution
solution against the SO2 concentration is plotted in Figure 13.
resulting in the dissolution of iron by the reaction of dissolved
It is seen that there is no significant difference in the amount of
oxygen as follows:
carbonate/bicarbonate in the systems by varying the SO2
Reduction of dissolved oxygen21 concentration. On the other hand, only for the high-concentration
(204 ppm) SO2 system, about 20 ppm of sulfate/bisulfite/sulfite
O2 + 2H2O + 4e- T 4OH- (10)
anions were obtained using the CE technique.
10174 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009
Figure 11. Effect of SO2 concentrations in simulated flue gas stream on
the corrosion rate of system prepared with 5 kmol/m3 MEA and a CO2
loading of 0.4 mol CO2/mol MEA with simulated flue gas stream of 6%
O2 at 353 K.
Figure 12. Effect of SO2 concentration in simulated flue gas stream on the
amout of dissolved iron in solution for a system prepared with 5 kmol/m3
MEA and a CO2 loading of 0.4 mol CO2/mol MEA with simulated flue gas
stream of 6% O2 at 353 K.
Figure 13. Effect of SO2 concentration in simulated flue gas stream on the
carbonate/bicarbonate concentrations in solution for a system prepared with
5 kmol/m3 MEA and a CO2 loading of 0.4 mol CO2/mol MEA with
simulated flue gas stream of 6% O2 at 353 K.
The EDS spectrum which shows the amounts of elements
on the metal surface from the effect of SO2 concentration is
given in Figure 14. The first bar represents the amounts of the
elements on the specimen surface before the experiments. These
amounts are compared with those after the experiments for the
second, third, and fourth bars for 5, 10, and 204 ppm SO2,
respectively. The amount of Fe on the surface of the tested
specimen decreases with increasing SO2 concentration while O
and C slightly increase from the original amounts. S and O
increase with increasing SO2 concentration because of the
formation of products that are composed of O, S, and C on the
tested surface. These products include Fe(OH)2, Fe(OH)3,
2Fe2O3 · H2O, FeCO3, and FeSO4.
Figure 14. Effect of SO2 concentrations in simulated flue gas stream on
the amount of elements on the tested specimen for a system prepared with
5 kmol/m3 MEA and a CO2 loading of 0.4 mol CO2/mol MEA with
simulated flue gas stream of 6% O2 at 353 K.
3.1.2.3. Mechanisms. The results presented show that a
higher sulfur dioxide concentration in the simulated flue gas
stream induces more corrosiveness due to the increase in the
solubility of SO2, and generally, the formation of hydrogen ion
(H+) as shown in reactions 14-16.22-24
SO2 + H2O T H+ + HSO3- (14)
HSO3- T H+ + SO32- (15)
SO2 + 1/2O2 + H2O T 2H+ + SO42- (16)
Generally H+ or the hydronium ion (H3O+) are the reducible
ions, the basic reduction reaction of H+ is shown in reaction 3,
and the oxidation-reduction reaction of iron and the hydrogen
ion is the same as in reaction 5, while the reduction of H3O+ is
shown in reaction 17.
2H3O+ + 2e- T 2H2O + H2 (17)
Then, the oxidation-reduction of iron and hydronium ion occurs
as in reaction 18.
Fe + 2H3O+ T Fe2+ + 2H2O + H2 (18)
SO2 may react with water and oxygen and, then, cause the
corrosion of the carbon steel directly as shown in reactions
19-21.25
Fe + SO2 + O2 f FeSO4 (19)
4FeSO4 + O2 + 6H2O f 2Fe2O3 · H2O + 4H2SO4
(20)
4H2SO4 + 4Fe + 2O2 T 4FeSO4 + 4H2O (21)
3.1.3. CO2 Loading. 3.1.3.1. Experimental Results. Figure
15 illustrates the effect of CO2 loading on the polarization curves
obtained from the Tafel plot technique. It shows that higher
CO2 loadings result in both higher anodic and cathodic current
densities, implying higher corrosion rates. As stated earlier, the
effect of CO2 loading on the corrosion rate is illustrated in Figure
16. The corrosion rate increases dramatically with an increase
in CO2 loading.
3.1.3.2. Corrosion Products Analysis. There is an increase
in the amount of dissolved iron with increasing CO2 loading as
shown in Figure 17. The plot of CO2 loading against the amount
of carbonate/bicarbonate anions is shown in Figure 18. This
plot indicates that these anions increase with increasing CO2
loading. This is attributed to the increase in the amount of
dissolved CO2 in the system. The amounts of carbonate/
 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10175

Figure 15. Effect of CO2 loadings on polarization curves obtained with

the Tafel plot technique for a system prepared with 5 kmol/m3 MEA with
simulated flue gas stream of 204 ppm SO2 and 6% O2 at 353 K.
Figure 18. Effect of CO2 loadings on the carbonate/bicarbonate concentra-
tions in solution for a system prepared with 5 kmol/m3 MEA with simulated
flue gas stream of 204 ppm SO2 and 6% O2 at 353 K.

Figure 16. Effect of CO2 loadings on the corrosion rate of system prepared
with 5 kmol/m3 MEA with simulated flue gas stream of 204 ppm SO2 and
6% O2 at 353 K.
Figure 19. Effect of CO2 loadings on the amount of elements on the tested
specimen for a system prepared with 5 kmol/m3 MEA with simulated flue
gas stream of 204 ppm SO2 and 6% O2 at 353 K.

3.1.3.3. Mechanism. The effect of CO2 loading on corrosion

of carbon steel in MEA-H2O-CO2-O2-SO2 system is due
to an increase in the concentration of carbonic acid (H2CO3)
and bicarbonate (HCO3-) that can induce the corrosion of iron.
The formation of carbonic acid and bicarbonate are explained
on the basis of reactions 22-24.26

H2O + CO2 f H2CO3 (22)

2H2CO3 + 2e- T H2 + 2HCO3- (23)

Figure 17. Effect of CO2 loadings on the amout of dissolved iron in solution
for a system prepared with 5 kmol/m3 MEA with simulated flue gas stream
of 204 ppm SO2 and 6% O2 at 353 K. 2HCO3- + 2e- T H2 + 2CO32- (24)
bicarbonate anions are dominant in this system causing a
significant difference in corrosion rates of these systems. The reduction-oxidation of iron with carbonic acid and
The amounts of elements on the tested specimen surface as bicarbonate ion are given in reactions 25 and 26.
a function of CO2 loading were obtained from the EDS
technique. The results are shown in Figure 19. The first bar Fe + 2H2CO3 T H2 + Fe(HCO3)2 (25)
represents the amounts of the elements on the specimen surface
before the experiments. These amounts are compared with those
after the experiments for the second, third and fourth bars for Fe + 2HCO3- T H2 + FeCO3 + CO32- (26)
0.2, 0.4, and 0.5 mol CO2/mol MEA, respectively. The amount
of Fe on the surface of the tested specimen decreases as the
It is also found that the amounts of bicarbonate and
CO2 loading increased, while O and S do not change much. C
hydronium ions generally increase, as shown by reactions
increases with increasing CO2 loading because of increasing
27-29.27
amounts of dissolved CO2 in the solution. Corrosion products
are composed of O, S, and C on the tested surface. These
products include Fe(OH)2, Fe(OH)3, 2Fe2O3 · H2O, FeCO3, and Formation of carbamate
FeSO4. 2RR′NH + CO2 T RR′NCOO- + RR′NH2+ (27)
10176 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009

Hydrolysis of carbamate
RR′NCOO- + H2O T RR′NH + HCO3- (28)

Dissociation of protonated amine

RR′NH2+ + H2O T H3O+ + RR′NH (29)

The reductions of these reducible ions are also shown in

reactions 3, 17, 23, and 24; also, the redox reactions are shown
in reactions 5, 18, 25, and 26. A higher concentration of these
ions implies a higher reduction rate, and consequently, a higher
corrosiveness of the system.
3.1.4. MEA Concentration. 3.1.4.1. Experimental Results.
Based on Tafel plot technique, it is seen in Figure 20 that a
higher MEA concentration resulted in higher anodic and Figure 22. Effect of MEA concentrations on the amout of dissolved iron
cathodic current densities. The implication is that MEA in solution for a system prepared with an MEA solution and CO2 loading
of 0.4 mol CO2/mol MEA with simulated flue gas stream of 204 ppm SO2
concentration has a significant effect on the corrosion rate as and 6% O2 at 353 K.
shown in Figure 21 because the corrosion rate of carbon steel
in the tested system increases sharply as MEA concentration
increases.
3.1.4.2. Corrosion Products Analysis. The corrosion rate
increases as MEA concentration increases. This could be
confirmed from Figure 22. Higher MEA concentrations result
in larger amounts of dissolved iron being present in the solution.
There is also an increase in the amount of carbonate/bicarbonate
anions with higher MEA concentrations. This is illustrated in
Figure 23. This could be explained on the basis of an increase
in the amount of absorbed CO2 with increasing MEA concentra-
tion. The increase in carbonate/bicarbonate anion concentration
is responsible for the increased corrosiveness of these systems.
The amounts of different elements on the tested specimen
surface were obtained from the EDS technique. The results are

Figure 23. Effect of MEA concentrations on the carbonate/bicarbonate

concentrations in solution for a system prepared with a MEA solution, a
CO2 loading of 0.4 mol CO2/mol MEA with simulated flue gas stream of
204 ppmSO2 and 6% O2 at 353 K.

Figure 20. Effect of MEA concentrations on polarization curves obtained

with the Tafel plot technique for a system prepared with an MEA solution
and CO2 loading of 0.4 mol CO2/mol MEA with simulated flue gas stream
of 204 ppm SO2 and 6% O2 at 353 K.

Figure 24. Effect of MEA concentrations on the amount of elements on

the tested specimen for a system prepared with an MEA solution and CO2
loading of 0.4 mol CO2/mol MEA with simulated flue gas stream of 204
ppm SO2 and 6% O2 at 353 K.

Figure 21. Effect of MEA concentrations on the corrosion rate for a system
prepared with an MEA solution and CO2 loading of 0.4 mol CO2/mol MEA
with simulated flue gas stream of 204 ppm SO2 and 6% O2 at 353 K.
shown in the bar chart in Figure 24. The first bar represents the
amounts of the elements on the specimen surface before the
experiments. These amounts are compared with those after
the experiments for the second, third, and fourth bars for 3, 5,
and 7 kmol/m3 MEA, respectively. The amount of Fe on the
surface of the tested specimen decreases as the MEA concentra-
tion increases. In contrast, C and S increase with increasing
MEA concentration. On the other hand, there was no change
in the amount of O with MEA concentration. The products
 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009 10177

Figure 27. Effect of operating temperatures on the amount of dissolved

Figure 25. Effect of operating temperatures on polarization curves obtained
with the Tafel plot technique for a system prepared with 5 kmol/m3 MEA
and CO2 loading of 0.4 mol CO2/mol MEA with simulated flue gas stream
of 204 ppm SO2 and 6% O2.
iron in solution for a system prepared with 5 kmol/m3 MEA and CO2 loading
of 0.4 mol CO2/mol MEA with a simulated flue gas stream of 204 ppm
SO2 and 6% O2.

Figure 26. Effect of operating temperatures on the corrosion rate for a

system prepared with 5 kmol/m3 MEA and CO2 loading of 0.4 mol CO2/
mol MEA with simulated flue gas stream of 204 ppm SO2 and 6% O2).

responsible for the elemental distribution described include

Fe(OH)2, Fe(OH)3, 2Fe2O3 · H2O, FeCO3, and FeSO4. Figure 28. Effect of operating temperatures on the carbonate/bicarbonate
3.1.4.3. Mechanisms. According to reactions 22-29, the concentrations in solution for a system prepared with 5 kmol/m3 MEA and
higher the MEA concentration, the higher the total amount of CO2 loading of 0.4 mol CO2/mol MEA with simulated flue gas stream of
CO2 absorbed into the amine solution, resulting in higher 204 ppm SO2 and 6% O2.
amounts of reducible ions, HCO3- and H3O+. These ions
enhance the reduction rate, which induces a more rapid corrosion
process. These oxidation-reduction processes are described in
eqs 5, 17, 24, and 25.
3.1.5. Operating Temperature. 3.1.5.1. Experimental Re-
sults. The effect of temperature on polarization curves is shown
in Figure 25, which reveals that systems kept at higher
temperature have higher anodic and cathodic current densities,
resulting in an increase in the corrosion rate. It is illustrated in
Figure 26 that a higher temperature increases the corrosion rate
of carbon steel in the studied system.
3.1.5.2. Corrosion Products Analysis. The significance of the
operating temperature comes on the basis of the amount of
dissolved iron in solution. This is shown in Figure 27. As the Figure 29. Effect of operating temperatures on the amount of elements on
temperature increases, a larger amount of dissolved iron is the tested specimen for a system prepared with 5 kmol/m3 MEA and CO2
present in the solution. Also, a not so significant amount of loading of 0.4 mol CO2/mol MEA with simulated flue gas stream of 204
carbonate/bicarbonate anions are observed with increasing ppm SO2 and 6% O2.
operating system temperature as shown in Figure 28. The
amounts of different elements on the tested specimen surface of corrosion. O, C, and S increase with increasing operating
are obtained by the EDS technique. The results are shown in temperature which results from the products of corrosion that
Figure 29. The first bar represents the amounts of the elements cover the specimen surface, including Fe(OH)2, Fe(OH)3,
on the specimen surface before the experiments. These amounts 2Fe2O3 · H2O, FeCO3, and FeSO4. The reason for the increase
are compared with those after the experiments for the second, in corrosiveness with operating temperature can be explained
third, and fourth bars for 303, 328, and 353 K, respectively. on the basis of reaction kinetics that temperature generally
The amount of Fe on the surface of the tested specimen accelerates the rate of any reaction.28 All reactions mentioned
decreases as the temperature increases because of higher rate in the previous section can go faster. The dissolved oxygen,
10178 Ind. Eng. Chem. Res., Vol. 48, No. 23, 2009
H+ or H3O+, H2CO3, and HCO3- enhance the reduction rate,
and then, more metal is dissolved into the solution, thus leading
to a higher corrosion rate.
3.2. Corrosion Rate Correlation. An empirical power law-
type model (eq 30) for the liquid phase has been used to correlate
corrosion rate with all the parameters in the MEA-H2O-
CO2-O2-SO2 system.
CR ) Ae(-Ha)/T[SO2]a2[O2]a3[CO2]a4[MEA]a5 (30)
where CR is the corrosion rate (mpy), A is the pre-exponential
constant, Ha represents the temperature sensitivity of the
electrochemical reaction (K-1), T is the operating temperature
(K), [SO2], [O2], [CO2], and [MEA] denote the concentrations
of SO2, O2, CO2, and MEA (kmol/m3) in the solution phase,
respectively, and a2, a3, a4, and a5 are the partial reaction orders
with respect to SO2, O2, CO2, and MEA, respectively. It should
be noted that in the gas phase Ha is equivalent to Ea/R. The
SO2 concentration in the liquid phase was calculated from SO2
concentration in the gas phase based on its solubility in water
at various temperatures. The O2 concentrations in the gas phase
were used to calculate the dissolved oxygen in the liquid phase
at a given pressure and temperature as shown in eq 31.29
[O2] ) -2.545 + 0.807 × 10-2T - 84.14p +
2.096 × 10-4pT2 + 2.322 × 104p/T + 1.027p2 -
3.911 × 102p2 /T (31)
where [O2] is concentration of oxygen in millimoles per liter,
T is temperature in kelvin, and p is pressure in megapascals.
By using a nonlinear regression program (NLREG version
6.3), it was possible to determine all the constants in eq 30.
The final corrosion rate correlation was thus obtained as eq 32.
CR ) 1.77 × 109 exp{ [ -5955
T ]}
× Meeting, Calgary, Canada, Aug 21-24; NACE: Calgary, Canada, 2005; p
{[SO2]0.0011[O2]0.0006[CO2]0.9[MEA]0.0001} (32)
The regression results show good regression statistics, with
a coefficient of correlation (R2) of 0.97. Also, a comparison of
the experimental results with the corrosion rate model in terms
of accuracy of the percentage average absolute deviation (%
AAD) was 15.48%. Thus, this coefficient shows that the
corrosion rate model adequately fits the corrosion rate data for
the MEA, O2, SO2 concentrations, CO2 loading, and temperature
ranges studied in this work, namely MEA concentration range
of 1-7 kmol/m3, O2 concentration range of 0-100%, SO2
concentration range of 0-204 ppm, CO2 loading range of 0-0.5
mol CO2/mol MEA, and a temperature range of 303-353 K.
The regression results show that CO2 loading has the strongest
effect on the corrosion of carbon steel in MEA-H2O-CO2-
O2-SO2 system. On the other hand, the MEA concentration
has a small effect on corrosion since MEA itself is not corrosive
to carbon steel.30 Also, since small amounts of dissolved SO2
and O2 are present in the aqueous solution, the consequence is
slight contributions of these two parameters to corrosion.
4. Conclusions
• We have shown for the first time that a higher concentra-
tion of SO2 in a simulated flue gas stream will induce a higher
corrosion rate because of the increase in hydrogen ion
concentration generated by SO2 and H2O as well as SO2, O2,
and H2O. Also, iron may also react directly with SO2 and O2
to cause corrosion of carbon steel. Furthermore, analysis done
for the first time shows that corrosion products generated
from the effect of SO2 include FeSO4 and 2Fe2O3 · H2O.
• The corrosion products obtained experimentally based
on CE and SEM/EDS techniques for the MEA-H2O-CO2-
O2-SO2 system include Fe(OH)2, Fe(OH)3, 2Fe2O3 · H2O,
FeCO3, and FeSO4.
• A power-law model developed to correlate corrosion rate
with the parameters in the MEA-H2O-CO2-O2-SO2
system shows that corrosion rate of carbon steel increases
with an increase in O2 and SO2 concentrations in simulated
flue gas stream, as well as MEA concentration, CO2 loading,
and operating temperature. The CO2 loading had the strongest
impact on the corrosion rate, while SO2 and O2 show only
slight effects on the corrosion rate.
Acknowledgment
The authors acknowledge the financial support from the
Thailand Research Fund (TRF) through the Royal Golden
Jubilee Ph.D. Program (Grant PHD/0204/2547) and from the
Natural Science and Engineering Research Council of Canada
(NSERC).
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Accepted October 17, 2009
IE900746G