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Fuel 101 (2012) 28

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Experimental research on the performance of CO2-loaded solutions of MEA


and DEA at regeneration conditions
Paula Galindo a,, Anke Schffer a, Kevin Brechtel a, Sven Unterberger b, Gnter Scheffknecht a
a
b

Institute of Combustion and Power Plant Technology, University of Stuttgart, Pfaffenwaldring 23, 70569 Stuttgart, Germany
EnBW Kraftwerke AG, Schelmenwasenstrasse 15, 70567 Stuttgart, Germany

a r t i c l e

i n f o

Article history:
Available online 18 February 2011
Keywords:
Post combustion CO2 capture
Amine scrubbing
Regeneration
Desorption
Stripper performance

a b s t r a c t
Amine-based post combustion CO2 capture is considered as one of the most advanced technologies to be
implemented in new and existing coal-red power plants for CCS. Although it has proven technically viable, it has not been installed on a large-scale application yet. The main drawback of the process is the high
energy requirement for the regeneration of the amine solution. Values around 4 MJ/kg of CO2 for the standard MEA-based process have been reported. The heat duty must be supplied by means of low-pressure
steam from the power plant, which causes a decrease in the power plant net efciency of up to
13%-points. Therefore, improvements in process technology and solvent development are important to
reduce the penalty in the power plant efciency.
Results from lab-scale research on the absorption and desorption of MEA and DEA at different concentrations are presented and discussed. Absorption and desorption capacities, as well as the regeneration of
the CO2-loaded solutions in a stripper column and the inuence of different operating parameters have
been experimentally investigated.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Among the diverse CO2 capture options, post combustion
capture with amine-based solvents is for many reasons one of
the most suitable technology for coal-red power plants: it can
be used for gases with low CO2 concentration; it is already commercially available in industrial application and it can be retrotted to existing power plants. The amine scrubbing process has
been already applied to power plants at pilot plant scale and much
effort is being made to promote the rst large-scale CCS demonstration plants. Still, the major disadvantage of this technology is
the inherent reduction of the power plant efciency, caused by
the consumption of low-pressure steam for solvent regeneration.
This energy consumption thus determines the cost of the CO2
capture process.
An aqueous solution of monoethanolamine (MEA) is the standard solvent for gas streams with relatively low CO2 content and
it is especially indicated for low pressure operation. The main
advantages of using aqueous MEA solutions are its high CO2
reactivity, its high absorption capacity and its low molecular
weight. The main drawback is its high heat of reaction with CO2
(85.6 kJ/molCO2), which leads to a high energy requirement for
stripping [1]. Aqueous solutions of diethanolamine (DEA) have also
Corresponding author. Tel.: +49 (0) 711 685 63487; fax: +49 (0) 711 685 63491.
E-mail address: paula.galindo@ifk.uni-stuttgart.de (P. Galindo).
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.02.005

been used for the removal of H2S and CO2 from renery gases. DEA
is also suitable for low pressure operations and has a lower heat of
reaction with CO2 (76.3 kJ/molCO2). Secondary amines, like DEA, are
much less reactive to sulphur components and their reaction products are not particularly corrosive. A disadvantage of DEA is that it
exhibits slow kinetics. However, its high absorption capacity
(0.71 molCO2/molDEA during the treatment of high-pressure natural gas), makes it an attractive option for CO2 capture [1]. Both primary and secondary amines react with CO2 to form a carbamate
and a protonated amine molecule, limiting the theoretical loading
to 0.5 molCO2/molamine. However the formation of bicarbonate,
especially in secondary amine solutions, results in CO2 loadings
over this theoretical value.
The desorption column operates by driving out the CO2 of the
rich amine solution by means of stripping steam. The production
of the steam takes place in the reboiler by evaporation of part of
the water contained in the solvent. The stripping steam must provide sufcient energy to reverse the amine-acid gas reaction, to
create the necessary driving force for desorption, and to warm up
the rich amine liquid feed to reboiler temperature. The reboiler
heat duty can be estimated as the sum of the energy used for these
three mentioned purposes. For MEA energy demands between 3.9
and 4.2 MJ/kg of captured CO2 have been reported as conventional
values [2,3]. Advanced solvent formulation or improved process
design have reduced this value to 3.2 MJ/kgCO2 and 2.9 MJ/kgCO2
[4,5].

P. Galindo et al. / Fuel 101 (2012) 28

Research on amine-based CO2 capture has mainly been focused


on improving the effectiveness and efciency of the CO2 absorption
process. Little attention has been paid however to stripper operation. The literature in this area and data from experimental plant
operation are rather limited in the open literature, if compared to
the work devoted to the absorption process. Data for other amines
than MEA at regeneration conditions are scarce. Only a few studies
deal with experimental regeneration in a stripping column.
Weiland et al. [6] presented an extensive set of measurements
and a model for mass transfer coefcients in desorption for the
CO2-MEA system. Sakwattanapong et al. [7] measured the reboiler
heat duty of diverse amines and their mixtures in a bench-scale
stripper. The obtained data were presented as a function of the
CO2 rich loading, the amine type and concentration and the composition of blended alkanolamines. Tobiesen et al. [8] developed
a simulation program capable of modelling the whole absorption/desorption process and validated against pilot plant data.
However, data for the stripper were collected during the study of
the absorber performance, which is not optimal for desorber model
validation. Oyenekan [9] evaluated the stripper performance using
MEA and K2CO3 with piperazine and using diverse stripper congurations. The model developed was validated with data obtained
from pilot plant experiments.
The objective of this study was to examine and compare the
performance of aqueous solutions of MEA and DEA under diverse
regeneration conditions. The nal goal was to study the contribution of process and solvent optimisation to the reduction of the energy demand for regeneration. The cyclic capacities of both
solvents at different concentrations were determined. The effects
of the temperature and CO2 partial pressure on the regeneration
capacity were investigated. The effects of diverse operational
parameters, such as reboiler energy input, solvent ow rate and
amine concentration on the regeneration energy for the different
amine solutions were studied.

2. Experimental setup and procedure


2.1. Absorption and regeneration experiments
The IFK contributes in diverse research projects to the development of CO2 capture by chemical scrubbing. Solvent screening and
characterisation is carried out in our laboratories as part of these
investigations. An important parameter to determine the applicability of a solvent for CO2 capture is its absorption capacity. The
setup and procedure to determine the equilibrium loadings of
amine solutions at diverse temperatures with synthetic ue gas
has been already described elsewhere [10,11].
In order to assess the desorption capacity of diverse solvents,
regeneration tests are carried out at different temperatures and
with a sweep gas, which simulates the effect of the stripping steam
in the desorber. The apparatus consists of a sample ask containing
50 g of loaded amine solution. The ask is equipped with a multiple distributor top, which facilitates the temperature measurement
and the continuous gas feed into the solution through a glass sintered diffuser. All experiments were done at atmospheric pressure
and the samples were continuously stirred. The regeneration temperature was set at 80, 90 and 100 C and was controlled with a
deviation of 1 K. Pure N2 and CO2, as well as synthetic ue gas
(15 vol.% CO2) were used as sweep gas. The gas ow rate was xed
at 0.5 lN/min and held constant with a mass ow controller. The
tests start by heating up the solution to the desired regeneration
temperature, then the sweep gas is bubbled through the loaded
solvent with durations of 15 and 30 min. In order to avoid the
interference of the evaporation of water, the loaded sweep gas
leaving the ask ows through a condenser, where water and

solvent vapours carried over with the gas are cooled down and
reuxed to the sample ask.
Prior to the experiments, the aqueous alkanolamine solution
was prepared by diluting the pure alkanolamine with distilled
water to a given concentration. The solution was then loaded
with CO2 until the desired loading was reached. All reagents were
commercial grade and used as received. The concentration of
alkanolamine and the CO2 loading in the samples were determined
before and after regeneration by titration with acid and gravimetric analysis.
2.2. Lab-scale stripper
The experimental setup for amine regeneration in a lab-scale
stripper is shown in Fig. 1. The desorber consists of a Vigreux glass
column with an internal diameter of 30 mm and 600 mm of length.
A condenser placed directly on top of the column assures the
recovery of most of the water and amine vapour. The reboiler is
a 250 mm long jacketed coil glass condenser tempered by heating
oil. The reboiler temperature is controlled from a thermostat. Both
desorber and reboiler were insulated in order to reduce heat losses.
The feed temperature of the rich amine solution was achieved by
letting the amine solution ow through a heated oil bath. The
CO2 gas ow rate was measured using a mass ow meter downstream the condenser. Temperatures were monitored at various
points along the column with a deviation of 1 K. The desorber
runs at atmospheric pressure. The experimental conditions are
summarized in Table 1.
Each experiment run began by introducing the rich solution
into the reboiler and desorber bottom and heating it up to reboiler
temperature. Once the reboiler and the pre-heater reached the desired set points, the rich amine solution was pumped continuously
at a given ow rate to the top of the stripper. The liquid level in the
column was kept constant by adjusting the ow of the lean stream.
After putting the plant into operation, it was allowed to operate
until steady state was reached. The steady state was achieved
when the gas stream leaving from the top of the stripper and the
pressure in the column were stable. Several samples from the outlet liquid stream were taken during the experiments for analysis of
CO2 and amine content.
3. Results and discussion
3.1. Absorption capacity
In order to estimate the theoretical cyclic capacity of the
different amine solvents, the equilibrium loading curves at 40 C
and 90 C were used. These temperatures approximately represent
both absorption (40 C) and regeneration (90 C) conditions. Figs. 2
and 3 show the resulting loading curves over the time for MEA and
DEA solutions, respectively. The concentrations of the amine,
represented as mass percentage, are molar equivalent at 3.25, 5
and 6.5 mol/l.
From Fig. 2 it can be seen that the cyclic capacity, calculated as
the difference between the 40 and 90 C loadings, is similar at different amine concentrations in the MEA system. Absorption loading capacities range from 0.53 to 0.57 molCO2/molMEA, whereas
the absorption capacity at 90 C falls in all cases between
0.410.42 molCO2/molMEA. The cyclic capacity of MEA results thus
in values around 0.15 molCO2/molMEA. In Fig. 3 the higher cyclic
capacity of the DEA solutions can be observed, which noticeably
decreases with increasing amine concentration. The absorption
capacity of the 34 wt.% DEA solution is comparable to that of
the MEA solutions, its loading at 90 C however is considerably
lower (0.2 molCO2/molDEA). The cyclic capacity of DEA results in

P. Galindo et al. / Fuel 101 (2012) 28

Fig. 1. Lab-stripper at the laboratories of IFK.

Table 1
Main stripper operating parameters.
Parameter

Value

Liquid ow rate (g/min)


Reboiler temperature (C)
Inlet liquid temperature (C)
Amine concentration (wt.%)
MEA
DEA
Rich solution loading (molCO2/molamine)
Condenser temperature (C)

1040
110130
7590
2040
34.4
0.5
20

Fig. 3. Equilibrium loading curves at 40 C and 90 C for DEA solutions.

Fig. 2. Equilibrium loading curves at 40 C and 90 C for MEA solutions.

approximately 0.23 molCO2/molDEA. The slower kinetics of DEA can


also be observed from these graphs, as it takes noticeably longer to
reach the equilibrium.
3.2. Regeneration capacity
Regeneration tests were performed in order to study the inuence of operating temperature and test duration, as well as the effect of a gas swept with different CO2 concentrations on the
regeneration capacity of the MEA and DEA systems. The regenera-

tion efciency, or regeneration ratio, is dened here as the difference between initial rich and achieved lean loadings divided by
the rich loading and expressed as a percentage value. As expected,
the regeneration efciency increased with increasing temperature
and with lower CO2 concentration in the sweep gas. The superior
regeneration capacity of DEA over MEA could also be conrmed.
An obvious decrease of the regeneration ratio with increasing
amine concentration in the solution was also recognized. This conrmed the pattern showed through the equilibrium loading experiments. The effect of the CO2 partial pressure was clearly stronger
for the MEA solutions, which states that DEA could be regenerated
with a higher CO2 partial pressure in the stripping steam. The time
variation showed little effect on the regeneration of the samples,
which indicates that the regeneration process is rather fast and,
if compared to the absorption, less dependent on the reaction
kinetics of the studied amine systems. Fig. 4 illustrates the obtained results.
The regeneration of the 34 wt.% DEA solution at 100 C with a
pure N2 purge showed the best result. Over 90% of the CO2 contained in the solution could be desorbed, reaching a lean loading
of 0.03 molCO2/molDEA. The equivalent MEA solution (20 wt.%) at
the same operating conditions had only 60% of its amine content

P. Galindo et al. / Fuel 101 (2012) 28

Fig. 4. Regeneration results.

regenerated (lean loading of 0.2 molCO2/molMEA). These results are


in good agreement with values presented by Sakwattanapong et al.
[7]. At this high temperature level the effect of the gas purge was
marginal due to the evaporation of water, which consequently reduced the CO2 partial pressure in the sample ask. Moreover it
could be observed that the DEA solutions started to liberate CO2
at a lower temperature than the MEA solutions. It can be inferred
that the temperature was the most inuencing parameter on the
regeneration of the samples.
3.3. Stripper performance
In the lab stripper, the regeneration operating conditions were
optimised in order to achieve the lowest energy demand possible
for an effective desorption. For a better understanding of the
desorption process, several experiments were performed under
various operating conditions, as well as using different amine concentrations. Previous experiments [12] already tested the capacity
of the column and identied the solvent ow rate with the minimal specic energy consumption for an aqueous 20 wt.% MEA solution. This optimal operating point (solvent ow rate of 23 g/min;
rich loading of 0.5 molCO2/molMEA; liquid inlet temperature of
85 C; reboiler heating temperature of 120 C) was selected as
the reference case. The reboiler heat duty was measured and analysed as a function of solvent ow rate, reboiler energy input, rich
loading, solvent feed temperature, amine concentration and amine
type.
3.3.1. Effect of solvent ow rate and amine concentration
As it can be observed in Fig. 5, the reboiler heat duty is rather
sensitive to the solvent ow rate (L). The measured specic energy
duty is represented as relative to the reference value. The reboiler
heat duty of aqueous MEA solutions with amine contents of 20, 30
and 40 wt.% are plotted as a function of the solvent ow rate.
At low solvent ow rate values, the vaporization of water required for CO2 stripping contributes most to the reboiler heat duty;
for the 20 wt.% solution the energy consumption at the lowest solvent ow rate increases by almost 60% with respect to the optimum. With a low liquid ow rate the solution had a longer
residence time in the stripper and more stripping steam than actually necessary was generated in the reboiler. The lean loading
achieved thus is at its minimum value (0.1 molCO2/molMEA). On
the other hand, as the liquid rate rises, the system requires proportionately higher rates of heat supply in order to raise the temper-

Fig. 5. Reboiler heat duty for MEA at different concentrations.

ature of the liquid to reboiler temperature. Since this heat is


provided by the condensation of steam, the driving force for
desorption is gradually reduced. The lean loading reached at the
optimum solvent ow rate was around 0.23 molCO2/molMEA. This
reduces the energy required to regenerate the solvent in the stripper. At the same time, there is more CO2 to be released, which reduces the specic energy duty. At even higher solvent ow rates,
the part of the energy required to provide sensible heat to the
amine solution becomes more important, as well as more steam
is necessary to establish the necessary driving force for CO2
desorption in the column. At 30 g/min the energy required to
regenerate the 20 wt.% MEA solvent is over 40% higher than the
optimum. The reached lean loading, with a value around 0.3 molCO2/molMEA, is too high to result favourable for absorber operation.
These results are in good agreement with those presented by different authors both from simulation and pilot plant data [2,13,14].
The energy duty for the solution with 30 wt.% MEA is roughly
30% lower than the 20 wt.% MEA at their corresponding minimum
values, whereof that of the 30 wt.% MEA solution is reached at an
elevated solvent rate, around 30 g/min. The higher the concentration of amine in the solution is, the more CO2 can be absorbed
and desorbed by the same liquid rate. Hence, the specic energy
requirement is lower. This fact was conrmed in our tests,
although slightly higher values can be observed at low ow rates
in Fig. 5 caused by the use of a somewhat lower rich loading. The
use of a more concentrated solution allows the system to work
with a smaller CO2 cyclic capacity (the difference between rich
and lean CO2 loading). The smaller CO2 cyclic capacity can be

P. Galindo et al. / Fuel 101 (2012) 28

translated into a higher lean CO2 loading, which requires less energy for solvent regeneration. That is, the same amount of CO2
can be released with a higher lean loading, which reduces the
amount of stripping steam required. The resulting loading using
a 30 wt.% MEA solution at 23 g/min was 0.26 molCO2/molMEA. With
the same specic energy duty as for the reference case, the amount
of CO2 released was up to 20% higher.
The performance of the lab stripper with the 40 wt.% MEA solution shows that the improvement in energy duty obtained by
increasing the amount of amine in the solution was limited. As
mentioned in Sections 3.1 and 3.2., the regeneration capacity decreases with the amine concentration. Whereas the 20 wt.% and
30 wt.% MEA solvents achieved regeneration ratios between 70%
and 45% depending on the solvent ow rate tested, the 40 wt.%
solution could only be regenerated to a lower level (2040%). As
the concentration in the solution increases, and with it the amount
of CO2 contained in the solvent, higher rates of heat supply are required for carbamate decomposition. The temperature level in the
column was observed to be lower than those of the less concentrated amine solutions at the same liquid ow rate. This fact points
out the insufcient stripping steam in the column for desorption to
take place, resulting in the mentioned low regeneration ratio.
Moreover, higher amine contents increase the boiling point of
the solvent, which makes the steam production in the reboiler
more energy demanding. Nevertheless, the results of the energy
demand over the solvent ow rate for the 40 wt.% MEA solution
still show a similar behaviour to that observed with the less concentrated solutions.
These curves reveal furthermore that at higher amine concentrations the exibility of the plant increases. That is, any change
in the solvent ow rate will have a minor effect on the energy consumption, if a more concentrated solution is used.

3.3.2. Effect of energy input


The energy input to the system was varied by changing the temperature of the heating oil in the thermostat. This can be an
approximation to the fact of changing the quality of the steam
drained from the power plant. The lowest heating oil temperature
(110 C) corresponds to energy input 1, the highest temperature
(130 C) to energy input 3. The measurements were carried out
for different solvent ow rates.
The tendency observed at the three cases is similar to that of the
reference case (energy input 2, 120 C). The highest energy input
shows higher heat duties and describes a steeper decline with
increasing solvent ow rates. With this conguration probably
stripping steam was produced in excess, especially at low solvent
ow rates, leading to a too high temperature level in the column.
With the lower energy input, heat duties similar to the reference
case are measured for the whole range of solvent ow rates. As a
result, a less energy demanding performance might be achieved
at a lower energy input. The low reboiler heating temperature still
guarantees the necessary energy amount to heat up the reboiler to
create stripping steam. However, the temperature level along the
column was remarkably lower, which indicates that the amount
of steam produced was in short supply. This can be conrmed in
Fig. 6. With the lowest energy input, the regeneration ratio is so
low that the lean loading hardly goes under 0.3 molCO2/molMEA.
High lean loadings have as a consequence a poor absorption performance or the necessity of increasing the solvent ow rate, in order
to achieve the desired absorption rate. On the contrary, by increasing the energy input a higher amount of stripping steam is produced in the reboiler. Consequently, a lower lean loading, down
to 0.1 molCO2/molMEA, was achieved. Thus, the optimal operating
parameters are those that attain low energy consumption but still
maintain a reasonable regeneration ratio.

Fig. 6. Reboiler duty and achieved lean loading with different energy inputs.

3.3.3. Effect of rich amine loading


The loading of the rich amine solution is an important factor in
the desorption equation. Depending on the operating conditions
(lean loading, liquid to gas ratio L/G, CO2 concentration in the ue
gas, amine concentration) and the absorber performance, MEA can
reach rich loadings ranging from 0.4 to 0.47 molCO2/molMEA in
industrial applications [8,15]. In this section it will be studied
how the rich loading affects the energy demand of the desorption
process. For these tests, the reference operating conditions were
used.
As expected, the CO2 loading of the rich amine solution has a
signicant impact on the reboiler heat duty. This effect is mainly
attributed to the differences in magnitude of equilibrium CO2 partial pressure at different rich CO2 loadings. Desorbing CO2 from
lower rich loadings requires more of stripping steam, so that the
driving force is large enough for desorption to take place. It can
be seen in Fig. 7 that the specic energy demand in the desorption
process reaches its lowest point for a rich amine loading of around
0.57 molCO2/molMEA. The decrease in the amount of steam required
at a high rich amine loading, achieves a less energy costly desorption. At loadings over the stoichiometrical maximum value
(0.5 molCO2/molMEA), part of the CO2 in the solution is present in
form of bicarbonate. Since bicarbonate is rather unstable in solution, desorption takes place with relative ease and without increasing the reboiler heat requirement. In all runs the lean loading
obtained was approximately 0.2 molCO2/molMEA. As a result, the
amine regeneration rate rises gradually as the rich amine loading
increases, until a maximum value of approximately 70% at a rich
loading of 0.6 molCO2/molMEA.
Any improvement in the absorber performance aiming for an
increase of the rich loading from 0.45 to 0.47 molCO2/molMEA

Fig. 7. Inuence of the solution rich loading on the reboiler heat duty.

P. Galindo et al. / Fuel 101 (2012) 28


Table 2
Effect of temperature on feed stage desorption.
Feed temperature (C)

a feed (molCO2/molMEA)

mCO2 (g/min)

74.4
85.1
93.6

0.46
0.41
0.36

0.12
0.28
0.40

reduces the energy demand by 13%. A larger increase to


0.5 molCO2/molMEA results in a reduction of 30% in the energy required for regeneration. In conclusion, it is recommended for an
efcient operation that the absorption achieves loadings as close
as possible to 0.5 molCO2/molMEA.
3.3.4. Effect of rich amine inlet temperature
The regeneration of a loaded amine begins by rising the solution
temperature, which already takes place in the rich/lean heat exchanger. Consequently, desorption can occur during the heating
of the solution prior to entering the column, especially at high rich
CO2 loadings. If there is CO2 being desorbed in the pre-heater, the
CO2 evolves from the rich liquid amine solvent, developing a gas
phase at the feed current, where the CO2 partial pressure just keeps
building up. This can improve the stripper performance to some
extent, since a portion of the solvent has already been regenerated
without using the stripping steam. To study the extent of CO2
desorption in the feed stage, samples were taken at the pre-heater
exit at different temperatures as shown in Table 2. The rich solvent
loading was 0.5 molCO2/molMEA.
Table 2 illustrates the effect of the heating over the amine loading and the amount of CO2 desorbed from the solvent before it is
fed to the desorber column. The hotter the feed current is, the higher the probability that it already is in the two-phase ow at the inlet to the desorber. A difference of 0.1 molCO2/molMEA in the feed
loading can be appreciated for a temperature increase in the feed
current of 19 K. In conclusion, the hotter the rich amine enters
the column, the more probable it is for ash distillation to occur.
Therefore the rich/lean heat exchanger must be designed so that
the temperature gradient is as low as possible.
Diverse experiments were performed to study the effect on the
reboiler heat duty. The operating conditions of the reference case
(solvent ow rate of 23 g/min; rich loading of 0.5 molCO2/molMEA;
reboiler heating temperature of 120 C) with different liquid inlet
temperature were used. From Fig. 8 it can be seen that the pre-heater temperature clearly affects the measured energy consumption.
A high feed temperature lowers the energy duty because of the
lower temperature difference between the stripper head and the
reboiler. A decrease of 10 K in the solvent feed temperature turns
into an increase of more than 38% in the reboiler energy duty.
Increasing the feed temperature over 90 C results in almost 4%
savings. In all three cases the same desorption ratio was achieved,
that is, the same lean loading (0.2 molCO2/molMEA) was reached.
This points out that the feed temperature has little effect on the
regeneration efciency, despite of the initial ash desorption. As
seen before, the hotter the feed amine solution is, the leaner it will
be when it enters the desorber. As explained in Section 3.3.3., a less
loaded rich amine current needs more energy for regeneration,
since more stripping steam is required to produce the required
desorption driving force. This fact limits the gain brought by heating up the solution, as can be observed in the change of slope in
Fig. 8 at feed temperatures over 85 C. This suggests a pinch in
the driving force occurring in the feed stage of the column.
3.3.5. Effect of alkanolamine type
It has been already pointed out that DEA has a lower reaction
enthalpy, a higher cyclic capacity and shows better regeneration

Fig. 8. Inuence of feed temperature on the reboiler duty.

efciency than MEA. This section reports on its performance in


the stripper column. Fig. 9 presents the resulting reboiler heat duty
for a 20 wt.% MEA solution and a 34.4 wt.% DEA solution. Both solvents have an amine concentration of 3.25 mol/l. Hence, both solutions can theoretically be loaded with the same amount of CO2. The
operating conditions are those of the reference case.
In order to compare different amine solvents on the same basis,
the concept of net capacity, dened as the amount of CO2 released
in mole per litre of solvent, has been used. The higher cyclic capacity evidenced for DEA in previous experiments is now conrmed in
the stripper, as it can be seen in Fig. 9. At its optimum, DEA
achieves a more effective desorption with a lower energy consumption. The lean loading reaches 0.1 molCO2/molDEA; an outstandingly low value, if compared with the 0.25 molCO2/molMEA
achieved with MEA. Several factors are responsible for this result.
On the one hand, the lower heat of reaction of DEA and its capability to desorb CO2 at a lower temperature. On the other hand, the
operating CO2 partial pressure needed to establish the driving force
for CO2 stripping, since MEA requires a lower CO2 partial pressure.
This suggests that a larger amount of steam must be produced to
regenerate MEA, leading to larger energy consumption. The effects
of these factors result in the possibility of operating the CO2 capture plant with DEA at higher removal efciency for the same
reboiler energy duty.
DEA offers another possibility, namely, to minimise the reboiler
heat duty by aiming to a higher lean loading and still maintain a
signicant regeneration ratio. This was tested in our lab by reducing the energy input, as had been done with MEA in Section 3.3.2.
All other experimental conditions were kept as in the reference
case. The results showed the expected reduction in the regeneration ratio from 90% to 70% in case of using low solvent ow rates

Fig. 9. Reboiler heat duty for MEA and DEA.

P. Galindo et al. / Fuel 101 (2012) 28

(10 g/min), and from 65% to 40% for high solvent rates (40 g/min).
This was the same regeneration level as achieved with MEA. The
behaviour of the reboiler duty over the net capacity was similar
to that of MEA showed in Fig. 9. By running the stripper with this
conguration, the reboiler temperature dropped to 90 C. As a result, the steam quality drawn from the turbine to be used as energy
input to the reboiler could be reduced and thus, the energy penalty
for the power plant could be signicantly lowered.

4. Conclusions
Amine screening plays a decisive role in the selection of new
absorbents for CO2 capture. Although the regeneration of the solution determines the viability of the use of a solvent, it used to be
relegated to a second-class condition in most characterisation
studies. After appropriate evaluation of absorption and desorption
capacities of different concentrated MEA and DEA solutions, the
regeneration of loaded 20 wt.% MEA and 34.4 wt.% DEA solutions
in a stripper column was analysed. The main focus was the study
of the relationships between the heat required for solvent regeneration and the stripper operating conditions. The reboiler heat duty
can account for up to 13%-points of the energy output of a power
plant and determines the costs of the CO2 capture plant. Hence,
the objective is to lower the energy consumption in the reboiler,
yet allowing for a signicant desorption efciency, in order to produce a fairly lean regenerated amine.
Several useful conclusions concerning the stripper operation
can be drawn from the presented experimental results. The
selection of both optimal solvent ow rate and energy input is a
trade-off situation between energy consumption and the lean loading to be achieved. High CO2 removal efciencies require low lean
loadings, which in turn involve high amounts of energy for regeneration. The desired CO2 uptake can be attained instead by increasing the solvent ow rate. This approach must assure a competent
lean loading, able to achieve the aimed absorption without unnecessarily increasing the reboiler heat duty. Another possibility to
improve the plant performance offers the use of more concentrated
solvents. Higher amine concentrations, up to a certain level,
require less energy for regeneration and require lower solvent ow
rates to achieve the desired removal efciency. However a lower
concentrated solvent could be more useful regarding corrosion
prevention. The rich amine loading strongly inuences the regeneration energy and should be the highest that the absorber can
accomplish (near 0.5 molCO2/molMEA). Nevertheless, this is a
parameter that mainly depends on the absorber capacity and the
loading of the recycled lean amine stream. The reboiler energy
duty can be reduced as well by improving the performance of
the rich/lean heat exchanger. However, this positive effect is
limited by the appearance of a pinch in the driving force at the
stripper rich end.
The experimental results showed the effects of using an aqueous 34.4 wt.% DEA solution compared with 20 wt.% MEA in post
combustion CO2 capture. Due to the chemical structure and reactions of DEA with CO2, the regeneration tests showed the higher
cyclic capacity of DEA and its lower dependence on CO2 partial
pressure for desorption. The performance in the lab-scale stripper
showed that the behaviour of DEA offers the possibility to operate
the column at a lower temperature level, which could imply
important savings regarding the integration of the CO2 capture system within the power plant.

It has been shown to what extent the choice of the operating


conditions determines the energy required for regeneration. Thus,
the selection of a new solvent to be used in a CO2 capture system
must be accompanied of an optimisation of the operating parameters (solvent ow rate, reboiler temperature, rich amine loading
and feed temperature).
The IFK currently works on extending the scope of this research
by addressing the performances of other alkanolamine systems.
The study of the solvent performance in both absorber and stripper
is necessary in the difcult task of reducing the energy penalty of
the regeneration step. The key will be to obtain the best compromise between absorption efciency, regeneration capacity and
reboiler energy duty.
Acknowledgment
The authors gratefully acknowledge the nancial support of this
work from EnBW Kraftwerke AG, Stuttgart, Germany.
References
[1] Kohl A, Nielsen R. Gas purication. 5th ed. Gulf Publishing Company; 1997.
[2] Tobiesen A, Mejdell T, Svendsen HF. A comparative study of experimental and
modelling performance results from the CASTOR Esbjerg pilot plant. In: 8th
international conference on greenhouse gas control technologies. Norway:
Trondheim; 1922 June, 2006.
[3] Chapel D, Mariz C, Ernest J. Recovery of CO2 from ue gases: commercial
trends. In: canadian society of chemical engineers annual meeting. Canada:
Saskatoon; 46 October, 1999.
[4] Reddy S, Scherfus J, Freguia J, Roberts CA. Fluor EFG+SM technology, an
enhanced amine based CO2 capture process, In: National energy technology
laboratory/department of energy, second national conference on carbon
sequestration. Alexandria, VA, USA; 58 May, 2003.
[5] Iijima, M. Coal red pilot plant and multipollutant control. In: IEA, 11th
meeting of the international post-combustion CO2 capture network. Vienna,
Austria; 2021 May, 2008.
[6] Weiland RH, Rawal M, Rice RG. Stripping of carbon dioxide from
monoethamolamine
solutions
in
a
packed
column.
AIChE
J
1982;28(6):96373.
[7] Sakwattanapong R, Aroonwillas A, Veawab A. Behaviour of reboiler heat duty
for CO2 capture plants using regenerable single and blended alkanolamines.
Ind Eng Chem Res 2005;44:446573.
[8] Tobiesen FA, Juliussen O, Svendsen HF. Experimental validation of a rigourous
desorber model for CO2 post-combustion capture. Chem Eng Sci
2008;63:264156.
[9] Oyenekan BA. Modeling of strippers for CO2 capture by aqueous amines. Ph.D.
dissertation. USA: University of Texas at Austin; 2007.
[10] Brechtel K, Unterberger S, Scheffknecht G. Laboratory investigations of
polyamine solvents for CO2-scrubbing from ue gases. In: IEA, 4th
international conference of clean coal technologies. Dresden, Germany; 18
20 May, 2009.
[11] Schffer A, Brechtel K, Scheffknecht G. Untersuchung von wssrigen Mehrkomponentenaminsystemen als Waschlsungen zur Abtrennung von CO2 aus
Rauchgasen. In: VGB, Chemie im Kraftwerk. Dresden, Germany; 2729
October, 2009.
[12] Galindo Cifre P, Brechtel K, Unterberger S, Scheffknecht G. Experimental
studies on CO2 desorption from amine solutions. In: IEA, 4th international
conference of clean coal technologies. Dresden, Germany; 1820 May, 2009.
[13] Notz R, Hoch S, Mangalapally H, Brechtel K, Galindo Cifre P, Scheffknecht G
et al. Gekoppelte simulation eines Kohlekraftwerks mit zugehriger MEAWsche zur CO2-Abtrennung und experimentelle Untersuchung neuer
Lsungsmittel in einer Technikumsanlage. ProcessNet-Jahrestagung,
Karlsruhe, Germany; 79 October, 2008.
[14] Meuleman E, Artanto Y, Jansen J, Osborn M, Pearson P, Cottrell A, Feron P. CO2
capture performance of MEA and blended amine solvents in CSIROs pilot plant
with ue gas from a brown coal-red power station. In: 35th international
technical conference on clean coal and fuel systems. The clearwater clean coal
conference. FL, USA; 610 June, 2010.
[15] Idem R, Wilson M, Tontiwachwuthikul P, Chakma A, Veawab A, Aroonwilas A,
et al. Pilot plant studies of the CO2 capture performance of aqueous MEA and
mixed MEA/MDEA solvents at the University of Regina CO2 capture technology
development plant and the Boundary Dam CO2 capture demonstration plant.
Ind Eng Chem Res 2006;45:241420.

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