Energy

Energy Procedia 4 (2011) 1035–1042

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Energy Procedia 00 (2010) 000–000
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GHGT-10

Investigating the dynamic response of CO2 chemical absorption

process in enhanced-O2 coal power plant with post-combustion CO2
capture
Adekola Lawala, Meihong Wanga,1*, Peter Stephensonb
a
Process Systems Engineering Group, School of Engineering, Cranfield University, Bedfordshire, MK43 0AL, UK
b
RWE npower, Windmill Park, Swindon, SN5 6PB, UK

Elsevier use only: Received date here; revised date here; accepted date here

Abstract

Studies have been carried out to show that there could be benefits in employing a hybrid of the post combustion
capture and oxyfuel processes. The former is suited for retrofit purposes but involves an energy intensive solvent
regeneration process. The oxyfuel process would result in high partial pressures of CO2 in the flue gas making
separation easier. However, the Air Separation Unit is also energy intensive and significant modifications would
have to be made on the power generation process. An enhanced-O2 coal power plant with post combustion CO2
capture would produce flue gas with reduced mass flow and higher CO2 partial pressures. The dynamic response of
the downstream CO2 capture plant was studied in this paper.

©
c 2010
⃝ Elsevier Ltd.
2011 Published All rights
by Elsevier Ltd.reserved

Keywords: CO2 Capture; Post-combustion; Chemical absorption; Dynamic modelling; Coal-fired power plant

1. Introduction

Post-combustion capture by chemical absorption using monoethanolamine (MEA) solvent is well suited for treating
flue gas streams with low CO2 partial pressures typical of coal-fired power plants. The drawback of this process is
the high energy requirement for solvent regeneration. However, it requires minimal modifications to the combustion
process and is thus well suited for retrofit options. The oxyfuel process produces a flue gas stream that has a high
CO2 partial pressure which makes CO2 separation considerably easier. However, the Air Separation Unit (ASU)
would require large quantities of energy to generate the amounts of oxygen needed for the conventional oxyfuel
process. In addition, significant modifications to the boiler are required when firing pulverized fuel in a concentrated
oxygen stream instead of air. Doukelis et al. (2009) show that there could be benefits in a combination of these two
types of CO2 capture technologies, resulting in a partial oxyfuel mode in the furnace and the post-combustion
solvent scrubbing. They suggested that this option may be particularly beneficial when retrofitting existing power

* Corresponding author. Tel.: +44-1234-754655; fax: +44-1234-754685.

E-mail address: meihong.wang@cranfield.ac.uk.

doi:10.1016/j.egypro.2011.01.152
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plants. This study investigates the operation of the chemical absorption process downstream an enhanced-O2 coal
power plant using dynamic modelling and simulation.

2. Operation of an enhanced-O2 coal power plant and CO2 chemical absorption plant

The schematic of the enhanced-O2 coal power plant with post-combustion CO2 capture is shown in Figure 1. It is
proposed that coal is combusted in an oxygen-enriched environment to increase the CO2 partial pressure in the flue
gas to an optimal level (Doukelis et al, 2009). Oxygen is produced in the ASU typically up to 95vol% purity (Wall
et al, 2009). This stream is mixed with secondary air prior to combustion. It is not advisable to increase the O2
partial pressure of the primary air since the stream is mixed with the pulverized fuel and increased O2 concentrations
could result in explosions. To keep temperatures down to acceptable levels, flue gas is recycled (and mixed with the
primary and secondary air stream) as shown in Figure 1. This also results in an increase in the CO2 partial pressure
in the flue gas.

FLUE GAS RECYCLE

NITROGEN

FLUE GAS REMOVAL OF

FROM NOX AND SOX
ASU FURNACE AND FLUE GAS
OXYGEN
COOLING

BOILER
SECONDARY AIR
AIR

FUEL TREATED
AMINE CO2 FLUE GAS
MILLS CAPTURE
PLANT
PRIMARY AIR

CO2
PRODUCT

Figure 1 Schematic of an enhanced-O2 coal power plant with post-combustion CO2 capture (adapted from Doukelis
et al, 2009)
The ratio of the flue gas recycle flow to the flow of flue gas from furnace is referred to here as the recirculation
fraction. The estimated compositional and flue gas flow changes observed with oxygen enrichment is shown in
Figure 2 for a 600MWe supercritical power plant. In this case, the O2 concentrations in the primary and secondary
air range from 21 vol% to 50 vol%. Though the oxygen stream is mixed with the secondary air, the percentage of
oxygen discussed is relative to the total of the primary air and secondary air flows to the furnace of the boiler. By
maintaining the primary air stream as air and keeping the primary air/fuel ratio, there is an upper limit of 50-60% in
the oxygen enrichment possible.

The methodology for calculating the flue gas flowrate and CO2 concentration in flue gas from the enhanced-O2 coal
plant is presented in Fleche (2009) and Huang et al. (2010). The estimates of the composition of the flue gas were
based on the assumption that the fuel specifications and fuel burn rates are kept constant and there is no leakage
along the path to the capture plant. The mass flow of CO2 in the flue gas is constant (based on the assumption of
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Lawal et al./ Energy Procedia 00 (2010) 000–000 3

constant fuel burn rates) while the flue gas total mass flow reduces with the recirculation rate. A steady increase in
the CO2 volume fraction in the flue gas is also observed.

CO2 volume fraction

Figure 2 Changes in flue gas mass flow, required recirculation rates and CO2 composition in flue gas with oxygen
enrichment

3. CO2 capture model development

Chemical absorption is a reactive absorption process. This phenomenon involves the combination of mass transfer
and chemical reaction of CO2 with a chemical solvent. Both processes are dependent on the concentration/partial
pressure of CO2 in the flue gas. Thus changes in this composition would significantly affect the performance of the
process (even with the same quantity of CO2 for capture). MEA solvent could be used to chemically absorb CO2 in
the flue gas from the power plant in an absorber and the solvent solution is regenerated in a regenerator column
using steam from the power generation process (Dugas, 2006).

The gPROMS advanced process modelling environment has been used to develop the required dynamic models. The
absorber and regenerator columns were modelled based on the Gas-Liquid Contactor model from Process Systems
Enterprise’s Advanced Model Library. Mass transfer rates were modelled based on the two-film theory using the
Maxwell-Stefan formulation while the reactions were assumed to attain equilibrium.

In developing this dynamic model, the following were assumed:

1 Linear pressure drop along the column
2 Phase equilibrium exists at interface between liquid and vapour films
3 There is negligible solvent degradation
4 There is negligible heat loss in the absorber column
5 There is no water wash section in the absorber

The model topology of the process in gPROMS is shown in Figure 3.

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Figure 3 Model topology in gPROMS

Five main control schemes are used in the process. PI controllers are used for temperature control of the regenerator
column by manipulating the condenser and reboiler heat duties. The reboiler level was controlled using a P
controller by manipulating the reboiler bottoms flow. This is the liquid lean MEA solvent flow from the reboiler to
the cross heat exchanger. Water balance is achieved by controlling the water mass fraction in the lean solvent with
the water makeup flow rate used as manipulated variable. Finally a capture level controller measures the captured
CO2 and controls it by manipulating the lean solvent flow to the absorber (Lawal et al, 2010).

The cross heat exchanger was sized to yield the reported regenerator feed temperature and a temperature approach
of over 15°C. The pressure of the partial condenser is also assigned to maintain the regenerator operating pressure.

4. CO2 capture model validation

The steady-state validation of the chemical absorption plant model was carried out using data from the one of the
cases of the Separations Research Program at the University of Texas at Austin (Dugas, 2006). The absorber and
regenerator columns of the pilot plant are both packed columns with diameters of 0.427m and total packing height
of 6.1m. It is shown that the models give good predictions of the shape of the temperature profiles for both absorber
and regenerator (referred to as the rate-based stand-alone model) (Lawal et al, 2009a). Further validation studies
have been carried out for the amine plant set-up (where the absorber and regenerator columns have been linked with
recycle referred to as the rate-based integrated model) (Lawal et al, 2009b; Lawal et al, 2010). Validation results are
shown for the absorber and regenerator in Figure 4.
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Lawal et al./ Energy Procedia 00 (2010) 000–000 5

Case 32 Absorber Temperature Profile Case 32 Regenerator Temperature Profile

345 400

340
Pilot Plant Measurements
390
335 Rate-Based Integrated
Model
330 380

Temperature (K)
Pilot plant Rate-Based Stand-alone
Model
Temperature (K)

Measurements
325
Rate-based Integrated 370
320 model

315 Rate-based Stand- 360

alone model
310
350
305

300 340
-2 0 2 4 6 8 10 -2 0 2 4 6 8 10
Height from bottom of packing (m) Height from the bottom of packing (m)

(a) (b)
Figure 4 (a) Absorber and (b) Regenerator temperature profile of columns for Case 32

The steady state predictions of the integrated model were found to be slightly better than the standalone models. In
the latter, estimates of the input to the column had to be made and errors in such guesses would affect overall
results. This suggests that the model predicts the interaction between the component parts of the plant (mainly the
two columns) fairly well. It should be noted that the pilot plant in the study used to validate these results did not
have a cross heat exchanger but used a combination of a heater and cooler (Lawal et al, 2010).

5. Dynamic analysis of ASU plant start-up

The enrichment of oxygen content in the primary and secondary air supplied to the furnace from atmospheric
concentrations of 21% by volume to about 50% by volume would result in changes in the flue gas composition as
discussed in Section 2. Similar compositional changes would occur despite the scale employed. Therefore, the
validated model for CO2 capture at pilot plant scale could be used to carry out the dynamic studies with the main
difference being the absolute flow rates involved. The CO2 mass flow to the absorber was fairly constant while the
total mass flow rate of the flue gas was correspondingly reduced (Figure 5). Water vapour content in the flue gas
was assumed to remain constant at 1.5wt%. Steady state conditions were maintained for two hours then a slow ASU
ramp rate of 1% increase per minute was assumed. Conditions were maintained for about 10 hours. In the first case
(Case 1), solvent circulation rates remained unchanged and in the second (Case 2), the rates were adjusted by a
controller to maintain CO2 capture levels at 96.7%.

CO2 mass fraction

N2 mass fraction
Flue gas mass
flow

Figure 5 Change in flue gas composition and mass flow rate with ASU start-up
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Figure 6 Effects of increasing O2 enrichment in furnace primary and secondary air on capture process

Figure 6 shows the effects of oxygen enrichment on the chemical absorption process without control of capture level
or Case 1 (a-c) and the corresponding results with control or Case 2 (d-f). With oxygen enrichment, CO2 partial
pressures in the flue gas are significantly increased, thus increasing driving forces for absorption thus significantly
increasing capture levels (Figure 6a). The observed dip in capture level is probably due to increased absorber
column temperature. This drop would not be observed with a steady state simulation. Figure 6c shows the
temperature profile variations with time. With O2 enrichment in the primary and secondary air, the partial pressure
of CO2 in the flue gas increases which causes more CO2 to react with MEA releasing more heat of reaction. In
addition, there is less quantity of flue gas to exchange heat with, so a sharp rise in temperature occurs which would
reduce CO2 solubility in the solvent and thus reduce absorption levels. As the capture levels begin to rise and
approach 100%, most of the absorption takes place close to the bottom of the packing and the temperature of the
solvent dominates in the column temperature profile. This effect is the case especially since it appears that without
control, excessive solvent is circulated for capture. Since more CO2 reacts with MEA, the rich solvent loading
increases and the heat requirement for capture reduces (Figure 6b). The heat requirement for capture before and after
the oxygen enrichment was relatively high (>3.9MJ/kg CO2) because of the relatively high level of capture that is
attained (96.7% as compared with the conventional 90%). As capture level targets increase (whilst all other factors
are constant), the heat efficiency of the capture process inadvertently drops. However, without capture level control,
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Lawal et al./ Energy Procedia 00 (2010) 000–000 7

excessive solvent is circulated, the capture efficiency tends to 100% and the heat requirement for capture begins to
rise again owing to the extra heat needed to heat up the excess solvent.

With the capture level controller active (Figure 6d), such excesses are avoided and the heat requirement for
absorption remains low – about 10% lower compared to the previous steady state (Figure 6e). The temperature in
the column generally increases with CO2 concentration and remains relatively high. This is because, as explained
earlier, more heat of reaction is released and there is less quantity of gas to exchange heat with. The temperature
bulge is roughly in the same position but the temperature profile is flatter than before the enrichment commenced
implying higher temperatures in more parts of the column. The performance of the system could possibly be
improved if absorber temperatures are minimized. This could be achieved by employing a split-flow configuration
where lean MEA solvent is supplied to the top and middle of the absorber column (Kohl and Nielson, 1997).

6. Conclusions

The dynamic response of the CO2 capture plant with enrichment of oxygen content in the primary and secondary air
supplied to the furnace from atmospheric concentrations to about 50% by volume was studied. The resulting flue gas
compositions with various degrees of O2 enrichment have been calculated. Using a rate-based dynamic model of the
chemical absorption process, two cases were studied –
x CO2 capture performance with O2 enrichment and a constant solvent circulation rate
x CO2 capture performance with O2 enrichment and a controlled circulation rate to maintain a constant
capture level.

It was shown that higher CO2 partial pressures in the flue gas led to reduced energy requirements for capture and
there may be room for improvement since absorber operating temperatures were also increased which may reduce
the efficiency of the absorption process.

Acknowledgements
This work is partly funded by RWE npower and its support is greatly appreciated.

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