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Ind. Eng. Chem. Res.

1999, 38, 3917-3924 3917

Corrosion Behavior of Carbon Steel in the CO2 Absorption Process


Using Aqueous Amine Solutions
Amornvadee Veawab, Paitoon Tontiwachwuthikul,* and Amit Chakma
Process Systems Laboratory, Faculty of Engineering, University of Regina, Regina,
Saskatchewan, Canada S4S 0A2

The present study provides comprehensive information on the effects of process parameter
variations on the corrosion behavior of carbon steel in CO2 absorption systems using aqueous
amine solutions. The process parameters of interest are amine type, concentration of the amine
solutions, solution temperature, CO2 loading, and oxygen content. An electrochemical testing
technique was used for determining the system corrosiveness in terms of polarization behavior
and corrosion rate. The experimental results suggest that the corrosion behavior is considerably
sensitive to the variations in the process parameters. Increases in amine concentration, solution
temperature, CO2 loading, and oxygen content accelerate the corrosion rate in the systems. In
addition, different amine types yield different degrees of the system corrosiveness. Comparisons
of the corrosiveness among single amine systems as well as between mixed amine systems and
their precursors are also presented.

Introduction $10 000 and $30 000 per day in terms of production
losses.8 Besides, the downtime also leads to a large
The CO2 absorption process using aqueous amine portion of expenditure necessary for restoring the cor-
solutions has been extensively used for the removal of roded systems and for treatments initiated to mitigate
CO2 from gas streams in many industries. Common the corrosion. As stated by Gerus,9 millions of dollars
industrial applications include natural gas processing, are annually spent on this particular purpose.
coal gasification, and manufacturing of hydrogen and In addition to the above direct impacts, the corrosion
ammonia. In these processes, purification of process gas problems also indirectly affect the plant’s economy by
streams is to meet the needed requirements of product limiting the operating ranges of the process. Generally,
quality and to minimize operational difficulties, which flexibility in varying the operating conditions is reduced
may occur when the gas streams are further used in due to excessive corrosion. Operating the process beyond
downstream processes. Other applications involve the the typical conditions may also cause a tremendous
production of CO2 for uses in food, beverage, and increase in the system corrosiveness.6,10 Because of such
petroleum industries. Besides such industrial applica- limitations, the capacity of existing plants may not be
tions, the CO2 absorption process is considered to be a easily increased at reasonable expenses.
potential technique for reducing greenhouse gas emis- In practice, corrosion could be controlled by several
sion from flue gas streams. approaches: (i) use of proper equipment design, (ii) use
Historically, the CO2 absorption process using aque- of highly resistant materials, and (iii) use of chemical
ous amine solutions has long encountered corrosion treatments. However, the effectiveness of the controlling
problems. On the basis of plant experiences,1-6 corrosion approaches could be affected by variations in the
seems to take place in several plant locations including operating conditions of the process. For instance, by
the bottom portion of the absorber, the rich-lean heat reducing the flow rate of the absorption solution, the
exchanger, the regenerator, and the reboiler. Both corrosion protection efficiency might be deteriorated due
uniform corrosion and localized attacks such as pitting, to increases in the degrees of process parameters such
galvanic, erosion, stress cracking, and intergranular as CO2 loading and solution temperature. This would
corrosion were commonly detected. In general, the ways result in excessive corrosion in the system. Therefore,
in which the process equipment was designed, fabri- understanding the corrosion behavior due to variations
cated, installed, and operated are key factors in deter- in the process parameters becomes necessary for pre-
mining the corrosion types and degrees of the system venting such excessive corrosion. In the present study,
corrosiveness. comprehensive information on the effect of process
According to Kohl and Nielsen,7 corrosion is consid- parameters on corrosion behavior is provided. The
ered to be one of the most severe operational problems process parameters studied include the type of amine,
in the CO2 absorption process. Chronic corrosion can amine concentration, solution temperature, CO2 loading,
lead to a direct impact on the plant’s economy since it and oxygen (O2) content. Ranges of the testing condi-
results in unplanned downtime, production losses, tions are provided in Table 1.
reduced equipment life, and even injury or death.6 The
unplanned downtime of a typical plant can cost between
Experiments

* To whom correspondence should be addressed. Phone: Experimental Setup. The experiments were carried
(306) 585-4726. Fax: (306) 585-4855. E-mail: paitoon@ out in a corrosion cell using an electrochemical tech-
uregina.ca. nique for corrosion analysis. The experimental setup
10.1021/ie9901630 CCC: $18.00 © 1999 American Chemical Society
Published on Web 09/08/1999
3918 Ind. Eng. Chem. Res., Vol. 38, No. 10, 1999

Table 1. Process Parameters and Testing Conditions


parameter testing condition
amine type monoethanolamine (MEA)
diethanolamine (DEA)
methyldiethanolamine (MDEA)
2-amino-2-methyl-1-propanol (AMP)
mixture of MEA and MDEA (1:1)
mixture of DEA and MDEA (1:1)
mixture of MEA and AMP (1:1)
at 3 kmol/m3, 80 °C, and CO2 saturation
at 3 kmol/m3, 80 °C, and 0.2 CO2 loading (mol/mol)
amine concentration 1-5 kmol/m3
at 80 °C and 0.2 CO2 loading (mol/mol) for MEA, DEA, and AMP
temperature 30-80 °C
at 2 kmol/m3 and 0.2 CO2 loading (mol/mol) for MEA, DEA, and AMP
CO2 loading 0.0-0.4 mol/mol
at 2 kmol/m3 and 80 °C for MEA, DEA, and AMP
oxygen content nil to 10% feed gas
at 2 kmol/m3 MEA, 80 °C, and 12% CO2 in the feed gas

Figure 1. Experimental setup for the electrochemical corrosion test.

consisted of two main components, the corrosion cell, are aqueous solutions of single amines. Four types of
model K47, and potentiostat, model 273 (EG&G Instru- amines including primary, secondary, tertiary, and
ments/Princeton Applied Research, NJ), as shown in sterically hindered amines were examined. Because of
Figure 1. The corrosion cell includes a set of a 1 L flask, their popularity, monoethanolamine (MEA), diethano-
high-density/nonpermeable graphite counter electrodes, lamine (DEA), methyldiethanolamine (MDEA), and
a calomel reference electrode, a reference electrode 2-amino-2-methyl-1-propanol (AMP) were chosen as
bridge tube, a purge/vent tube, and a leak-proof as- representatives of each amine type. In addition, aqueous
sembly for mounting the specimen. The potentiostat has solutions of mixed amines, which have currently gained
an accuracy of the applied potential and current mea- a great deal of attention by solvent developers, were as
surement of (0.2% of the reading. A computer with a well investigated. These include mixtures of MEA-
data acquisition program is connected to the poten- MDEA, DEA-MDEA, and MEA-AMP.
tiostat to record and analyze the produced corrosion
data. The prepared aqueous amine solutions can be clas-
Preparation of Specimens. The specimens for sified into two categories: (i) fresh solution containing
corrosion tests in this study were made of carbon steel no or little trace of CO2 and (ii) loaded solution contain-
1020. Their chemical compositions are C, 0.20; Mn, 0.51; ing certain amounts of CO2. The fresh solution was
P, 0.013; S, 0.039; Si, 0.17; and Fe, balance. The simply prepared by diluting the pure solvents with
specimens were cut into cylindrical shape: 1/2 in. (12.7 deionized water to a desired concentration. The concen-
mm) long, 3/8 in. (9.5 mm) diameter, drilled to a depth tration of the prepared solutions was determined by
of 1/4 in. (6.4 mm), and tapped to accept a 3-48 UNC- titration with a 1 N standard hydrochloric acid (HCl)
2A 5/16 in. (8 mm) thread depth. Within 1 h prior to solution using methyl orange as an indicator. For the
the tests, the specimens were prepared by wet grinding loaded solution, the preparation involved mixing a fresh
with 600 grit silicon carbide papers, degreasing with solution with a CO2 saturated solution previously
methanol, and drying with hot air, in accordance with prepared by purging CO2 gas into the fresh solution for
the ASTM standard E3-80.11 approximately 8 h. Amounts of the absorbed CO2 in the
Preparation of Absorption Solutions. The CO2 loaded solution represented as CO2 loading (mol of CO2/
absorption solvents primarily used in the present study mol of amine) were determined by chemical analysis
Ind. Eng. Chem. Res., Vol. 38, No. 10, 1999 3919

involving acidifying a given quantity of the liquid


sample by adding an excess amount of HCl solution.12
Experimental Procedure. Prior to the experiments,
the experimental technique and instrumentation were
validated to ensure reliability of the obtained data. The
validation was performed in accordance with the ASTM
G5-94 by conducting a potentiodynamic anodic polariza-
tion test on a stainless steel-430 specimen in a 1 N
sulfuric acid (H2SO4) solution at 30 °C.13 The generated
polarization curve was in good agreement with the
reference curves provided by the ASTM, thus validating
the experimental technique and instrumentation.
To begin the experiments, the corrosion cell was
immersed in a water bath where the temperature was Figure 2. Comparison of corrosion rates among single amine
set and controlled within an accuracy of (0.1 °C. A gas systems under 3 kmol/m3, 80 °C, and CO2 saturation.
stream of nitrogen (N2), N2-CO2 mixture, or N2-CO2-
O2 mixture was introduced into the corrosion cell to
maintain the prepared CO2 loading in the tested solu-
tion. The chemical analysis for the CO2 loading mea-
surement was performed periodically to ascertain that
the CO2 loading was kept at the desired level during
the experiment. Prior to the corrosion measurement, all
potentiostat cables were properly connected to three
points of the corrosion cell: the graphite counter elec-
trodes, the calomel reference electrode, and the speci-
men holder. The corrosion potential (Ecorr) of the speci-
men against the reference electrode was recorded at
equilibrium when a reading of the potential remained
constant for at least 5 min. The potentiodynamic
polarization was then initiated with a scanning rate of Figure 3. Polarization behaviors of carbon steel in single amine
systems under 3 kmol/m3, 80 °C, and CO2 saturation.
0.60 V/h. All experimental data including applied po-
tentials and produced currents were continuously re-
corded and stored in the computer program. To observe
the corrosion behavior of a given experimental run, a
polarization curve, a plot between specimen potential
and current density, was created. Then, the corrosion
rate was finally determined by the Tafel extrapolation
technique detailed in Baboian.14 It should be noted that
the corrosion data presented in this paper are the
average corrosion rates ((5% of replicated data).

Results and Discussion

Amine Type. The effect of amine type on corrosion


behavior was examined by conducting the experiments
in 3 kmol/m3 aqueous amine solutions under two dif-
ferent testing conditions: (i) 80 °C and CO2 saturation
and (ii) 80 °C and 0.2 CO2 loading. Results from the
former condition reveal corrosion behavior under a Figure 4. Comparison of corrosion rates among mixed amine
practical condition where CO2 loading in each amine systems and their precursors under 3 kmol/m3 with a mixing ratio
system could be varied depending upon its CO2 solubil- of 1:1, 80 °C, and CO2 saturation.
ity characteristic. For the latter condition, results
provide an indication of the actual influence of the ing of anodic and cathodic reactions. Metal dissolution
amine type under an exactly identical condition where is considered the anodic reaction while oxidizer reduc-
the interaction between the process parameters is tion is considered the cathodic reaction. Higher anodic
negligible. and/or cathodic current densities basically indicate
Under the CO2 saturation condition, the amine type higher rates of the metal dissolution and/or the oxidizer
has a great effect on the system corrosiveness. Corrosion reduction, thus leading to a higher corrosion rate.
rates for various amines are shown in Figure 2. MEA According to Figure 3, among MEA, DEA, and MDEA
had the highest corrosion rate at 136.4 mpy followed systems, the MEA system obviously yields the greatest
by AMP at 125.9 mpy. MDEA was the least corrosive anodic and cathodic current densities throughout the
with a corrosion rate of 67.6 mpy while DEA’s corrosion active region. When compared with the AMP, the MEA
rate was 89.1 mpy. system still induces a greater corrosion rate since it
A similar sequence of the system corrosiveness can produces significantly higher cathodic current density,
also be observed from the polarization curves. By despite the relatively smaller anodic current density.
nature, corrosion is an electrochemical process consist- This suggests that the MEA system is the most corrosive
3920 Ind. Eng. Chem. Res., Vol. 38, No. 10, 1999

Table 2. CO2 Loading in Aqueous Amine-CO2 System at


the Testing Condition of 3 kmol/m3, 80 °C, and CO2
Saturation
CO2 loading corrosion rate
amine type (mol/mol) (mpy)
MEA 0.565 136.4
DEA 0.442 89.1
MDEA 0.243 67.6
AMP 0.554 125.9
mixture of MEA and MDEA 0.435 77.6
mixture of DEA and MDEA 0.365 72.4
mixture of MEA and AMP 0.561 127.3

Figure 6. Comparison of corrosion rates among single amine


systems under 3 kmol/m3, 80 °C, and 0.2 CO2 loading.

the mixed amine systems and their precursors could be


different.
The corrosion behavior in the mixed amine systems
can also be seen from polarization results shown in
Figure 5. The hybrid polarization behavior is found in
the cases of the MEA-MDEA and the DEA-MDEA
systems, both the cathodic and anodic current densities
of which are between those produced in the precursor
systems. This obviously indicates the hybrid corrosion
rates in the mixed amine systems. Unlike the above,
the MEA-AMP system presents the hybrid polarization
behavior only at the cathodic side even though its
corrosiveness is a combination of the precursors.
Figure 5. Polarization behaviors of carbon steel in mixed amine
systems and their precursors under 3 kmol/m3, mixing ratio 1:1, The influence of the amine type on the corrosion
80 °C, and CO2 saturation: (a, top) mixture of MEA and MDEA, behavior is probably caused by differences in the
(b, middle) mixture of DEA and MDEA, (c, bottom) mixture of MEA amounts of CO2 absorbed into the tested solutions under
and AMP. the CO2 saturation condition. The greater the CO2
loading, the higher the corrosion rate. This trend can
environment. In addition, Figure 3 also indicates that be seen from Table 2, containing data of saturated CO2
the MDEA system is the least active environment; i.e., loading and corrosion rate in single and mixed amine
it generally generates the smallest current densities systems. It is conceivable that the CO2 loading is a
among the other systems. primary contributor to the effect of amine type on
Corrosiveness in the mixed amine systems was also corrosiveness in both single and mixed amine systems.
investigated for MEA-MDEA, DEA-MDEA, and MEA- As previously mentioned, the corrosion experiments
AMP mixtures. Total amine concentration was kept at were conducted under the testing condition of 3 kmol/
3 kmol/m3, and the experiments were conducted at 80 m3, 80 °C, and 0.2 CO2 loading. The experimental
°C and under CO2 saturation. From Figure 4, it can be results shown in Figure 6 indicate that the amine type
seen that the corrosiveness in a particular mixed amine itself also has an affect on the system corrosiveness even
system appears to be a combination of those in its though the influence of the CO2 loading is eliminated.
precursor systems. For instance, a mixed MEA-MDEA From the figure, corrosion rates in the MEA and the
system (a mixing ratio of 1:1) yields a corrosion rate of DEA systems seem to be comparable while the corrosion
77.6 mpy while the MEA and the MDEA systems induce rate in the AMP system is apparently superior to those
the rates of 136.4 and 67.6 mpy, respectively. Similar in the other two systems. This is perhaps due to
trends of such behavior are also found in the mixed differences in the amounts of active components, par-
systems of DEA-MDEA and MEA-AMP. However, it ticularly bicarbonate ion (HCO3-), in the solutions.
should be noted that the corrosion rates in the mixed At the identical CO2 loading, temperature, and amine
amine systems presented in this study were generated concentration, the AMP system tentatively contains a
on the basis of only a mixing ratio of 1:1. With different greater amount of the HCO3- than the MEA and the
mixing ratios, the corrosiveness relationship between DEA systems. Consider the main CO2 absorption reac-
Ind. Eng. Chem. Res., Vol. 38, No. 10, 1999 3921

Figure 8. Effect of MEA concentration on polarization behavior


Figure 7. Effect of amine concentration on corrosion rate under under 80 °C and 0.2 CO2 loading.
80 °C and 0.2 CO2 loading.

tions taking place in the aqueous amine-CO2 systems


as follows:

formation of carbamate15

2RNH2 + CO2 a RNHCOO- + RNH3+ (1)

hydrolysis of carbamate16
RNHCOO- + H2O a RNH2 + HCO3- (2)
Figure 9. Effect of solution temperature on corrosion rate under
2 kmol/m3 and 0.2 CO2 loading.
RNH2, RNHCOO-, RNH3+, and HCO3- denote amine,
carbamate ion, protonated amine ion, and bicarbonate
ion, respectively. For the MEA and the DEA systems, 1), and HCO3- (reaction 2). The increasing amount of
formation of carbamate (reaction 1) is a major reaction HCO3- thus causes a greater corrosion rate in the
while hydrolysis of carbamate (reaction 2) hardly takes system.
place. On the contrary, both reactions 1 and 2 play An increase in the corrosion rate with amine concen-
major roles in CO2 absorption in the AMP system. This tration can also be observed from the polarization curves
is basically due to low stability of the carbamate as shown in Figure 8. Apparently, changes in the amine
compound.16 As a consequence, the greater amount of concentration have an impact on the current densities
the HCO3- species is expected to be present in the AMP especially on the anodic side. The higher concentration
system rather than in the MEA and the DEA systems. leads to the greater anodic current density, thus in-
creasing the rate of corrosion.
HCO3- is basically considered a corroding agent in a
typical aqueous solution containing dissolved CO2. A Second, the corrosion rate seems to retard and
corrosion reaction between iron and HCO3- can be decrease gradually as the amine concentration in-
written as17 creases. This behavior is found in the AMP system with
the concentration beyond 3 kmol/m3 as shown in Figure
7. The decreasing corrosion rate is probably caused by
Fe + HCO3- f FeCO3 + H+ + 2e- (3) the hydrolysis of RNHCOO- shown in reaction 2. Once
the AMP concentration increases, available water in the
liquid solution tends to decrease. Therefore, the amount
According to reaction 3, the greater the amount of of HCO3- resulting from the hydrolysis reaction is
HCO3-, the higher the amount of iron dissolved. This diminished due to the limited water. This basically leads
results in a higher corrosion rate. With this principle, to a reduction in the amount of the corroding oxidizer,
the corrosion rate in the AMP system is therefore thus decelerating the corrosion rate.
generally greater than those in the MEA and the DEA
Solution Temperature. According to the experi-
systems.
mental results shown in Figure 9, a variation in the
Amine Concentration. Amine concentration ap- temperature of the liquid solution has a significant effect
pears to have a considerable effect on the system on the corrosion rate in the amine-CO2 systems.
corrosiveness. According to Figure 7, the corrosion Increasing the liquid temperature considerably acceler-
behavior affected by the amine concentration is mani- ates the rate of corrosion. For instance, in a 2 kmol/m3
fested in two distinct manners. MEA solution, the corrosion rate rises from 2.6 to 16.2
First, the corrosion rate increases as the amine mpy when the liquid temperature increases from 30 to
concentration increases. This is found in the MEA, DEA, 80 °C. A similar behavior is also found in the DEA and
and AMP systems with the concentration below 3 kmol/ the AMP systems. It should be noted that the relation-
m3. At a constant CO2 loading, increasing the amine ship between liquid temperature and corrosion rate is
concentration generally leads to an increase in the total shown in exponential form.
amount of CO2 absorbed into the amine solution, result- The increasing corrosiveness resulting from the varia-
ing in higher amounts of RNHCOO-, RNH3+ (reaction tion in solution temperature could be explained by
3922 Ind. Eng. Chem. Res., Vol. 38, No. 10, 1999

Figure 10. Effect of liquid temperature on pH under 2 kmol/m3


MEA and 0.2 CO2 loading.
Figure 12. Effect of CO2 loading on corrosion rate under 2 kmol/
m3 and 80 °C.

Figure 11. Effect of solution temperature on polarization behav- Figure 13. Effect of CO2 loading on pH under 2 kmol/m3 MEA
ior under 2 kmol/m3 MEA and 0.2 CO2 loading. and 80 °C.

reactions 1 and 2 together with other reactions occurring


in the amine-CO2 systems as written below.15

dissociation of protonated amine ion


RNH3+ a RNH2 + H+ (4)

dissociation of bicarbonate ion


HCO3- a CO32- + H+ (5)

where CO32- denotes carbonate ion. In general, tem-


perature is an essential parameter for the kinetics of
the absorption system. Increasing the temperature could
disturb the equilibrium among chemical species in the
system. According to a correlation between the equilib- Figure 14. Effect of CO2 loading on polarization curve under 2
rium constant (K) and temperature,18 equilibrium con- kmol/m3 MEA and 80 °C.
stants for reactions 2, 4, and 5 increase with the solution
temperature, thus reflecting the greater amounts of H+ the amine-CO2 systems. Increasing the CO2 loading in
and HCO3- present in the system. Under this circum- the system generally leads to a greater corrosion rate.
stance, the equilibrium between the metal dissolution As shown in Figure 12, by increasing the CO2 loading
and the oxidizer reduction is disturbed. To maintain the from fresh (0.0) to 0.4 mol/mol, the corrosion rate in the
equilibrium, more metal (iron) is dissolved into the MEA system (2 kmol/m3 at 80 °C) increases from a
solution and subsequently generates more electrons for negligible value to 24 mpy.
the oxidizer reduction, thus accelerating the corrosion The influence of the CO2 loading on the corrosion rate
rate. The increase in the amount of H+ as the liquid can be simply explained by reactions 1-5. An increase
temperature increases can be confirmed in terms of pH in CO2 loading yields higher amounts of HCO3- and
reduction as illustrated in Figure 10. RNH3+, which in turn dissociates and finally produces
The effect of liquid temperature on the corrosion more hydrogen ion (H+). The increase in the H+ amount
process is also indicated by polarization curves. The due to the increasing CO2 loading can be confirmed by
polarization results suggest that the variation in the the pH reduction reported in Figure 13. As mentioned
liquid temperature obviously affects the corrosion be- previously, increasing the amounts of H+ and HCO3-
havior. According to Figure 11, an increase in the liquid drives the corrosion process to proceed faster, thus
temperature causes anodic and cathodic current densi- causing a higher corrosion rate.
ties to rise, resulting in an acceleration of the corrosion Figure 14 demonstrates the effect of CO2 loading on
process through both metal dissolution and oxidizer the corrosion polarization behavior. The polarization
reduction. curves indicate that the variation in the CO2 loading
CO2 Loading. CO2 loading is apparently an impor- has a significant effect on the cathodic current density
tant process parameter influencing the corrosiveness in but a small effect on the anodic current density. This
Ind. Eng. Chem. Res., Vol. 38, No. 10, 1999 3923

CO2 loading condition, the corrosion rate still varies


with amine type.
Two different corrosion behaviors are observed as a
result of the amine concentration variations. First,
increasing the amine concentration accelerates the
system corrosion rate. Second, the corrosion rate de-
creases gradually as the amine concentration increases.
Variations in the liquid temperature, the CO2 loading,
and the oxygen content have significant impact on the
system corrosiveness. Increasing each parameter leads
to a greater corrosion rate.

Acknowledgment
Figure 15. Effect of oxygen content on corrosion rate under 2
kmol/m3 MEA and 12% CO2 in feed gas. Financial support from the Faculty of Graduate
Studies and Research of the University of Regina, the
behavior suggests that an increase in the CO2 loading Natural Sciences and Engineering Research Council of
primarily enhances the rate of oxidizer reduction, caus- Canada (NSERC), and Saskferco Products Inc. is grate-
ing a more corrosive environment. fully acknowledged.
Oxygen Content. The effect of oxygen content on the
system corrosiveness is illustrated in Figure 15. The Literature Cited
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