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Fuel
journal homepage: www.elsevier.com/locate/fuel
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].
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
Table 1
Main stripper operating parameters.
Parameter
Value
1040
110130
7590
2040
34.4
0.5
20
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
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.
Fig. 6. Reboiler duty and achieved lean loading with different energy inputs.
Fig. 7. Inuence of the solution rich loading on the reboiler heat duty.
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
(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.