Front. Chem. Sci. Eng.

https://doi.org/10.1007/s11705-020-1964-3

RESEARCH ARTICLE

Integrated adsorption and absorption process for

post-combustion CO2 capture

Gongkui Xiao (✉)1, Penny Xiao2, Andrew Hoadley3, Paul Webley2

1 Department of Chemical Engineering, The University of Western Australia, Perth WA 6009, Australia
2 Department of Chemical Engineering, University of Melbourne, Victoria 3010, Australia
3 Department of Chemical Engineering, Monash University, Victoria 3800, Australia

© Higher Education Press 2020

Abstract This study explored the feasibility of integrat-
ing an adsorption and solvent scrubbing process for post-
combustion CO2 capture from a coal-fired power plant.
This integrated process has two stages: the first is a vacuum
swing adsorption (VSA) process using activated carbon as
the adsorbent, and the second stage is a solvent scrubber/
stripper system using monoethanolamine (30 wt-%) as the
solvent. The results showed that the adsorption process
could enrich CO2 in the flue gas from 12 to 50 mol-% with
a CO2 recovery of > 90%, and the concentrated CO2
stream fed to the solvent scrubber had a significantly lower
volumetric flowrate. The increased CO2 concentration and
reduced feed flow to the absorption section resulted in
significant reduction in the diameter of the solvent
absorber, bringing the size of the absorber from unecono-
mically large to readily achievable domain. In addition, the
VSA process could also remove most of the oxygen
initially existed in the feed gas, alleviating the downstream
corrosion and degradation problems in the absorption
section. The findings in this work will reduce the technical
risks associated with the state-of-the art solvent absorption
technology for CO2 capture and thus accelerate the
deployment of such technologies to reduce carbon
emissions.
Keywords vacuum swing adsorption, monoethanola-
mine, post-combustion, CO2 capture, integrated process
1 Introduction
Post-combustion CO2 capture (PCC) is an important
Received April 10, 2020; accepted May 27, 2020
E-mail: gongkui.xiao@uwa.edu.au
approach to reducing carbon emissions from power plants,
especially from low rank coal fired power stations [1,2].
Solvent scrubbing with ethanolamine based solvents, such
as monoethanolamine (MEA) and methyl diethanolamine,
are likely to be most ready technology for full scale CO2
capture from post combustion gases [3,4]. However,
several issues associated with solvent absorption technol-
ogies such as large absorber size, corrosion of the capture
plant and solvent degradation, need to be addressed to
enable these technologies to be widely deployed for full
scale post-combustion CO2 capture: the unusually large
absorber size presents considerable technical and eco-
nomic challenges for full scale coal-fired power plant PCC
applications [4,5], the corrosion of the absorber (and
associated piping) and degradation of the amines increase
the on-going maintenance cost [6,7] and may cause health
and environmental hazards [8,9].
The diameter of an absorber is mainly determined by the
volume of the gas flow, and for PCC the extreme volume of
gas is attributed predominantly to the N2 in the flue gas
because N2 takes up more than 70 mol-% of the flue gas.
The corrosion of the capture plant is mostly caused by the
presence of O2 in the feed gas because oxygen can
accelerate the corrosion of the carbon steel commonly used
in CO2 removal processes [10], especially in the CO2
regeneration column. The degradation of solvent is mainly
caused by the irreversible reactions of O2 and SOx with
amine [10,11]. The above-mentioned problems will be
alleviated if there were a process that could simultaneously
reduce the amount of N2 and impurities such as O2 and SOx
entering the scrubbing system. Previously, some studies
using a combined membrane and solvent scrubbing system
in a natural gas fired power plant1) [12] have shown that
such a hybrid process could achieve a simultaneous
decrease in N2, SOx, and NOx amount in the stream
entering the absorber, and thus produce a more competitive

1) Huibers M, Raats P, ten Asbroek N. Hybrid absorber-membrane CO2 capture, in IEAGHG PCCC1. Abu Dhabi, 2011
2 Front. Chem. Sci. Eng.
process1 [12–14]. Therefore, placing a process before the
MEA unit is desirable to tackle the absorber size and
corrosion issues.
Adsorption processes, especially vacuum swing adsorp-
tion (VSA) processes, could also be combined with solvent
scrubbing system to provide a synergetic removal of
carbon dioxide. Previous studies of VSA processes for
PCC have shown that CO2 can be enriched from a
relatively low level to more than 99 mol-% at moderate
recovery [15,16]. It is, however, costly in terms of energy
consumption to achieve such a performance because these
processes required vacuum pressure to be about 2–5 kPa in
absolute pressure. Meanwhile, lower purity and higher
recovery may be achievable with modest energy require-
ment with vacuum pressure > 10 kPa, which will reduce
the vacuum power requirement for the regeneration of
adsorbents. Another potential benefit of such a hybrid
process is that the increased CO2 partial pressure in the gas
entering the absorber could increase the equilibrium
capacity of solvent used in the absorber, for example, the
equilibrium loading of a 30 wt-% MEA solvent would
increase by 15%1) if the CO2 partial pressure increases
from 10 to 40–50 kPa. The increased solvent loading will
also minimise the requirement for management of large
amount of hazardous solvents and associated issues such as
detrimental degradation emissions and health concerns
[17,18].
In this work, we will examine the potential benefits of an
integrated adsorption (VSA) and MEA process for post-
combustion CO2 capture. This work aims to first use
adsorption processes to provide an initial enrichment of the
CO2 to moderate levels (so that the amount of N2, O2 and
SOx can be reduced) with high CO2 recovery and moderate
energy consumption, then make use of the intrinsic
capability of the solvent system to provide high purity
CO2 suitable for compression and storage. The integrated
process is expected to lower the cost and risk of MEA
Fig. 1 Schematic diagram of the integrated VSA/MEA process for CO2 capture.
1) Aronu U E, Ghondal S, Hessen E T, Haug-Warberg T, Hartono A, Hoff K A, Svendsen H F. Equilibrium in the H2O-MEA-CO2 system: new data and
modeling, in IEAGHG PCCC1. 2011: Abu Dhabi
process for post-combustion CO2 removal and accelerate
its deployment to fossil fuel power plants.
2 Experimental
2.1 Integrated process and conditions
The integrated adsorption and absorption process as shown
in Fig. 1 was explored for the removal of CO2 in this work.
VSA was placed in the first section, MEA was used in the
absorption section. As there is no adsorption unit operation
blocks in Aspen Plus, a custom Microsoft Excel model was
developed to represent the VSA process to interface with
the MEA absorption model so that a whole flowsheet
simulation and optimisation of the integrated process could
be performed. The custom Excel model was developed
from the data obtained by carrying out VSA simulations in
Aspen Adsorption.
The base case conditions were based on the flue gas
properties of a 500 MW pulverised coal fired power plant.
These gas conditions refer to the downstream of a direct
contact cooler which cooled flue gas to 40 °C. These feed
conditions are summarised in Table 1, which also shows
the desired CO2 product purity and recovery. The CO2
removal process aims to remove 90% of the CO2 fed to the
system with a CO2 product purity of 95 mol-% which is
suitable for compression, transportation and sequestration.
The feed gas stream was assumed to contain only CO2,
H2O, N2 and O2. No SOx was included in the simulations
as it is common practice that SOx is removed by
desulphurisation units in coal-fired power plants. The
water vapour was included in the simulation to provide a
more practical simulation of the adsorption process
because for most adsorption processes, the water will be
removed along with the CO2 in the CO2 rich stream.
 Gongkui Xiao et al. Integrated adsorption and absorption process for post-combustion CO2 capture 3

Table 1 Design basis—feed and product specifications unable to produce CO2 of purity greater than 95 mol-%
Parameters Values without excessively low vacuum pressures and multiple
CO2 product purity ≥95 mol-% VSA stages. This necessitates the use of adsorbents such as
CO2 recovery 90% zeolite 13X for standalone VSA processes1). However, in
the hybrid system, activated carbon is an excellent fit
Feed conditions
because the aim of the VSA process in the hybrid system is
P/kPa abs 100 to only moderately enrich the CO2 stream while tolerating
T/K 313.15 the full extent of moisture in the feed gas. The coconut
Molar F/(kmol∙h–1) 63232 (equivalent to 10000 TPD CO2) activated carbon as reported in a previous work [23] was
Volumetric F/(m3∙s–1) 456.62 used in this work.
The design of the three-bed VSA system as the first stage
Gas composition/mol-% CO2: 14.97, H2O: 6.47, N2: 74.82, O2: 3.74
was carried out considering the conditions in Table 1. The
diameter of adsorption towers was calculated based on the
upper limit of acceptable interstitial velocity (vf) and the
2.2 VSA process simulation capacity of largest liquid ring vacuum pump. The
maximum vf (1.5 m∙s–1 in this work) was specified as
The CO2 in the feed gas will be concentrated and recovered 80% of the lower limit of fluidisation velocity. The largest
with the VSA process utilising activated carbon as the single stage water ring vacuum pump has a suction flow
adsorbent. Activated carbon has been widely used for high rate of 1200 cubic meters per minute at the vacuum
pressure gas separations such as hydrogen purification and pressure of 16 kPa [26]. This gas intake rate was specified
the separation of CO2 from crude natural gas [19–22]. as the constant vacuum pump volumetric flow for all the
Although the application of activated carbon is limited for vacuum pressures studied in simulations. The performance
low pressure CO2 capture from flue gas, many studies have for the VSA process was simulated using Aspen Adsorp-
examined the use of carbon based adsorbents for this tion with the rigorous dynamic multi-bed approach.
application because of the cheap and ready availability of A simulation interface of the three-bed VSA is given in
carbon, and the tolerance to water and other impurities Fig. 2. The adsorption step sequence is given in Table 2.
[23–25]. In a standalone VSA process, activated carbon is The basic elements of the simulation flowsheet include

Fig. 2 Simulation flow sheet of the VSA process in Aspen Adsorption.

a)
Table 2 The sequence of steps in the 3-bed VSA cycle
Item I II III IV V VI VII VIII IX
A RP AD PE ↓ PE ↓ EV EV PE ↑ IDLE PE ↑
B PE ↑ IDLE PE ↑ RP AD PE ↓ PE ↓ EV EV
C PE ↓ EV EV PE ↑ IDLE PE ↑ RP AD PE ↓

a) RP = repressurization, AD = adsorption, PE = pressure equalisation, EV = counter-current evacuation, IDLE = idle. “↑” represents pressure increase; “↓” represents
pressure decrease.

1) Zhang J, Webley P, Xiao P. Experimental pilot-scale study of carbon dioxide recovery from flue gas streams by vacuum swing adsorption, in AIChE 2005
Annual Meeting. 2005: Cincinnati
4 Front. Chem. Sci. Eng.

boundary streams, void tanks, valves and vacuum pump.
The “Feed”, “Product” and “Waste” in Fig. 2 were used as
simulation boundaries. The pressures of these streams were
kept constant during the simulations. The “Feed” stream
temperature and composition were also defined, with the
“Waste” and “Product” stream compositions and tempera-
tures calculated in simulations. Void tanks (TB1–TB3 and
TT1–TT3) were used to represent the void volumes at the
ends of adsorption columns. These tanks, as well as other
tanks (T01–T04), also served as connection nodes to attach
multiple gas lines. Four valve types were used to mimic
valve action in the simulation, which were fully closed (no
flow); fully open (no resistance to flow); constant Cv (fixed
valve openness); and constant flow (specified mole flow).
The mode of each valve was fixed but Cv or specified flow
at different steps of the adsorption simulation was varied
via the in-built cycle organizer. The vacuum pump was
simulated as an isentropic single stage vacuum pump and
was set in a constant volumetric flow mode.
The governing equations underlying the numerical
adsorption model are provided in Table 3 and the
assumptions of these can be found in previous publications
[27,28]. It is worthy of noting that the axial dispersion term
was not included in the material balance equation because
including that term produced mass balance errors. The
reason for the mass balance error resulting from axial
diffusion is not clear at this stage, but plug flow was a valid
assumption due to the high values of the axial Peclet
number of these systems. The partial differential equations
in the model were solved using the Upwind Differencing
Scheme 1 and Implicit Euler method with 40 nodes per
adsorption tower. The simulations were stopped when the
solutions converged when there was£10–5 relative change
in a variable. If the relative changes of the total loading and
solid temperature at the end of a cycle were lower than this
set tolerance, the simulation was considered to have
reached cyclic steady state. The material balances of these
simulations were checked with overall and component
mass balance errors always less than 1%.
2.3 MEA absorption process
The second stage of the integrated separation system is a
conventional MEA absorption process. A 30 wt-% MEA
solution was used for CO2 absorption directly from the
feed gas or from the product stream of the VSA process.
Simulations of the 30 wt-% MEA absorption and
desorption were performed using the rate-based Radfrac
block in Aspen Plus v10. This modelling approach was
used because the such Radfrac model produces faithful
simulations over the conventional equilibrium and effi-
ciency based modelling [29]. The thermodynamic and
kinetic model parameters for post-combustion CO2 scrub-
bing with MEA were obtained from a simulation model
which had been validated against pilot plant data [30].
Therefore the model can be used as prediction and design

Table 3 Governing equations in the adsorption numerical model

Item Description Equation
Material balance Ideal plug flow ∂ðvg ci Þ
 ∂c ∂w (1)
þ εi þ ð1 – εi Þεp i þ b i ¼ 0
∂z ∂t ∂t
!
Momentum balance Pressure drop described by Ergun Equation ∂P 150  10 – 5 g ð1 – εi Þ2 1:75*10 – 5 Mw g ð1 – εi Þ 2 (2)
¼ v þ vg
ð2rp ψÞ ε3i ð2rp ψÞ2 ε3i
g
∂z 2

LDF kinetic model Adsorption uptake rate ∂wi   (3)

¼ ki w*i – wi
∂t
  
Isotherm model B.E.T. multilayer isotherm model IP1 bf 1 – ðIP4 þ 1ÞfIP4 þ IP4 fIP4 (4)
wi ¼ IP þ1
1–f 1 þ ðb – 1Þf – bf 4

 
IP3 P
b ¼ IP2 exp ,f ¼ i ,Pi ¼ ci RTs
Ts Psat

IP6
IP5 – IP þT
Psat ¼ IP8  10 7 s

Ideal gas equation Equation of state PVi ¼ ni RT (5)

0  1
Pump work Isentropic work   γ (6)
γ B Pout γ – 1 C
W ¼ ðRTin Þ@ – 1A
γ–1 Pin

ci: concentration of component i (kmol∙m–3); IP1–8: isotherm parameter of component i, units depend on isotherm; ki: mass transfer coefficient (s–1); Mw: mole weight
of bulk gas (kg∙mol–1); P: gas phase pressure (kPa); Pin: vacuum pump inlet pressure (kPa); Pout: vacuum pump outlet pressure (kPa); R: universal gas constant 8.3145
(kJ∙kmol–1∙K–1); rp: radius of adsorbent particle (m); Tin: temperature of inlet gas to the vacuum pump (K); Tg: gas phase temperature (K); Ts: adsorbent temperature
(K); t: simulation time (s); vg: velocity of gas phase (m∙s–1); Vi: gas phase volume in the column (m3); Wi: solid loading of component i (kmol∙kg–1); Wi*: solid loading
at equilibrium of component i (kmol∙kg–1); z: position along the column length (m); ɛi: inter-particle void fraction; ɛp: intra-particle void fraction; rb: bulk density of
adsorbent layer (kg∙m–3); µg: gas dynamic viscosity (Pa∙s); Υ: the ratio of specific heats; Y: particle shape factor.
 Gongkui Xiao et al. Integrated adsorption and absorption process for post-combustion CO2 capture 5

Table 4 Main parameters used in simulations

Column & adsorbent details Isotherm parameters
Item value Component i CO2 H2 O N2 O2
Column length/m 3 IP1 2.15E–03 5.85E–04 7.21E–03 2.58E–03
Internal diameter/m 8 IP2 6.52 0.06 1.04E–03 0.02
Bulk density/(kg∙m3) 548 IP3 94.25 1748.51 1854.84 5.26E–05
Inter-particle porosity 0.42 IP4 3.04 33.50 0.56 1.04
Intra-particle porosity 0.32 IP5 3.88 5.33 1.51 6.13
Particle radius/m 0.002 IP6 1203.36 2334.90 2.45E–06 5382.12
Shape factor 0.86 IP7 2.72E–09 5.09E–06 0.22 482.99
–1 –1
Ads heat capacity/(J∙kg ∙K ) 1000 IP8 3.75 5.56 0.22 0.73

tool to investigate the various scenarios of process
parameter change [30], and was used in this work to
couple with the surrogate VSA model to study the whole
flowsheet performance. When water wash was studied, an
independent ideal flash separator block was used to model
the vapour-liquid phase equilibrium because Aspen Plus
does not have such a built-in function.
3 Results and discussion
3.1 Surrogate model for the VSA process
Numerical simulations were performed for the VSA
section to map out the variation of product CO2 purity,
energy consumption and process productivity with the
change of waste stream CO2 content, desorption pressure
and feed gas pressure. The total electrical power (energy)
consumption including the compressor consumption and
vacuum pump consumption was calculated using the
Aspen Adsorption built-in isentropic pump option with an
assumption that the isentropic efficiency was 70%. And the
specific power was expressed in the form of total electrical
power consumption (MJe) divided by total mass (kg) of
CO2 recovered. The simulation results are shown in
Table 5.
Simulations for the VSA section were carried out
systematically that each independent variable was studied
at three levels: The feed pressure was studied at 110, 130
and 150 kPa, the vacuum pressure was examined at 5, 10
and 15 kPa, and the CO2 content in the waste stream was
targeted at 1, 2 and 3 mol-%. Table 5 clearly shows that the
product CO2 purity increased with the feed gas pressure
while the vacuum pressure and CO2 content in the waste
were held constant. This was expected because higher feed
pressure with the same desorption (vacuum) pressure
would produce a higher working capacity of the adsorbent,
which eventually led to more CO2 being captured and
desorbed. When the feed gas pressure and CO2 concentra-
tion in the waste were maintained constant, the CO2
percentage in the product decreased with the increasing
vacuum pressure in the range of 5–15 kPa. This was due to
the reduced working capacity of the adsorbent. These
simulations were not intended to exhaust all the operating
conditions for the VSA process, but to set the operational
boundaries. Performance of the process at all the other
possible conditions within the operational boundaries
could then be acquired from a surrogate model that was
derived from the performance data.
The correlations between specified parameters (feed gas
pressure, vacuum pressure and CO2 percentage in waste)
and performance variables (product CO2 purity, recovery
rate of CO2 and power consumption) were regressed with a
quadratic response surface method, and the regressed
coefficients together with those for H2O and N2 are shown
in Table 6. The surrogate model standing for the VSA
performance was incorporated into the Excel unit opera-
tion model in Aspen Plus® (Fig. 1) using the correlation
coefficients in Table 6. This Excel custom model could
rapidly calculate the VSA process performance for any
given the feed gas pressure, vacuum pressure and CO2
percentage in the waste stream, which afforded the
possibility of meaningful integrated simulation of VSA
and MEA absorption system. The surrogate model was
interfaced with the MEA absorption simulation model in
Aspen Plus, and used to study the synergy between the
adsorption and absorption process. The graphical layout of
the integrated simulation model followed the same
arrangement as shown in Fig. 1.
3.2 MEA absorber size
Typically, CO2 content in flue gases from a brown coal
fired power plant was in the range of 10–15 mol-% when
the gas was cooled down to about 40 °C. In this work,
15 mol-% was used as the CO2 concentration for feed to
the integrated system and the two standalone (VSA and
MEA) systems. With this feed composition and volumetric
flowrate to a standalone solvent scrubbing system, the
absorber diameter in a single train for a 500 MW power
plant needs to be about 20 m which currently is not
technically feasible.
6 Front. Chem. Sci. Eng.

Table 5 Simulation results for performance of the VSA section

CO2 waste (wet) CO2 product (wet) Electric power Productivity
Pfeed/kPa Pvac/kPa CO2 rec./%
/mol-% /mol-% /(MJe∙kg–1) /(kg CO2∙h–1∙kg–1 ads)
110 5 1.1 50.0 92.5 0.578 0.090
10 1.1 41.2 96.4 0.508 0.080
15 1.1 34.2 96.5 0.477 0.067
5 2.1 52.6 87.6 0.544 0.089
10 2.0 44.5 90.3 0.482 0.080
15 2.0 37.2 92.8 0.451 0.069
5 2.9 54.0 83.3 0.538 0.086
10 3.0 46.1 85.4 0.464 0.078
15 3.0 38.7 87.3 0.431 0.068
130 5 0.9 48.5 95.3 0.620 0.103
10 1.0 44.5 95.4 0.575 0.097
15 0.9 34.8 98.7 0.522 0.079
5 2.1 54.4 87.6 0.636 0.103
10 2.0 47.7 90.2 0.554 0.097
15 1.9 39.0 93.3 0.505 0.041
5 3.0 56.3 81.1 0.649 0.099
10 3.1 50.0 85.5 0.542 0.096
15 3.1 42.3 86.3 0.493 0.083
150 5 1.1 52.5 93.2 0.773 0.124
10 1.1 44.4 96.5 0.842 0.112
15 1.1 39.3 98.3 0.876 0.109
5 2.0 56.6 84.7 0.659 0.111
10 1.8 48.8 92.1 0.659 0.113
15 2.1 42.5 92.9 0.675 0.112
5 3.0 56.9 76.0 0.615 0.097
10 2.9 53.6 86.3 0.606 0.098
15 2.8 45.4 88.98 0.615 0.099

a)
Table 6 Regressed coefficients for the quadratic response surface method
CO2 H2O N2
Item Power
Purity Recovery Purity Recovery Purity Recovery
A 4.18E–02 –5.15E–04 5.37E–02 1.38E–01 –4.99E–02 –5.35E–02 3.00E–01
B 7.56E–03 1.40E–02 1.61E–03 1.18E–02 5.00E–03 1.77E–03 5.67E–03
C –1.65E–02 1.17E–02 2.28E–03 5.03E–02 1.95E–02 2.12E–02 –6.30E–03
D –1.01E–02 –5.93E–03 –2.49E–03 4.15E–03 8.05E–03 8.07E–03 2.32E–02
E –3.00E–05 –5.27E–05 –1.34E–06 –3.14E–05 –2.03E–05 –6.26E–06 –3.57E–06
F –3.16E–04 –5.97E–04 1.29E–04 –8.27E–05 1.18E–04 4.32E–04 3.94E–04
G 2.71E–04 –3.36E–04 –1.75E–04 –1.17E–03 –2.56E–04 6.38E–06 –2.70E–03
H 7.63E–05 2.53E–05 –7.62E–05 –3.37E–04 –3.32E–05 –1.05E–04 –1.54E–04
I –4.22E–04 1.11E–03 –1.13E–03 –6.07E–03 1.22E–03 –1.48E–03 6.07E–03

a) f(x, y, z) = A∙x + B∙y + C∙z + D∙x + E∙y + F∙z + G∙x∙y + H∙y∙z + I∙z∙x, here x is the waste stream CO2 concentration, y is the feed pressure, and z is the vacuum
2 2 2

pressure. The O2 purity and recovery is calculated from the overall mass balance since the values for CO2, H2O and N2 are known.
 Gongkui Xiao et al. Integrated adsorption and absorption process for post-combustion CO2 capture
The volume of the gas fed to the MEA absorber has to be
reduced to allow the use of economically sized contact
towers, which can be achieved through the operation of the
VSA section upstream the MEA process. Figure 3 shows
the variation of inlet flowrate and absorber diameter as a
function of the inlet CO2 percentage. It is clear from the
figure that both the inlet flow and the absorber diameter
decreased with the enhancement of CO2 concentration.
Especially, the absorber diameter decreased from the
required 20 to about 13 m when the CO2 concentration
was enriched from 15 to 62 mol-%. This significant
reduction in the diameter has brought the diameter of the
absorber to a range close to the recommended maximum
diameter of 12.2 m [31,32] so that the need for fabrication
of extremely large absorbers and associated heavy support
structures could be eliminated if the inlet flow to the
absorber is further reduced, which will dramatically lower
the technical and economic uncertainties in the application
of MEA technology for post-combustion CO2 capture.
Meanwhile, the partial pressure of CO2 in the gas could
also be increased to enhance the driving force for CO2
absorption [33], which will reduce the column height and
eventually decrease the overall energy requirement in the
absorption section [34].
Fig. 3 Variation of inlet flow and diameter as a function of CO2
percentage.
3.3 Reduction in solvent degradation
The degradation of amines in CO2 capture plants is a major
issue in delaying the wide deployment of an amine-based
chemical absorption for PCC because the costs associated
with degradation may amount to 10% of the overall CO2
capture cost [35]. Among all the degradation types,
oxidation of amines was identified as the main type as
concluded from a long term tests performed at the MEA
PCC pilot plant [11]. The oxidative degradation of MEA is
usually caused by the irreversible reactions with O2, SO2
and NOx that are commonly present after the combustion
of coal. In modern coal-fired power plants, SO2 and NOx
removal units already exist because of the regulations on
7
the emissions of these detrimental gases. However, there is
dedicated unit for O2 removal in these power plants.
Therefore, the MEA used in PCC is directly exposed to the
oxygen in the flue gas. The oxidation rate and extent of
MEA are linearly correlated with the O2 content and
inversely proportional to the CO2 concentration [11].
Therefore, increasing the CO2 content and reducing the O2
content in the flue gas will help to lessen the oxidative
MEA degradation, which could be up to 50% depending
on absorber conditions [36].
The VSA section can simultaneously increase the CO2
content and reduce the O2 content in the gas stream fed to
the MEA absorption system. Figure 4 shows that both the
oxygen flowrate and its percentage in the feed to the MEA
section decreased with the CO2 increase in the feed stream,
which was calculated from the VSA simulations. As
reported previously [36], this synergetic CO2 increase and
O2 decrease will alleviate the oxidative degradation in the
process, and thus lower the cost with respect to the
management of the degradation waste and solvent
replenishment and help to speed up the application of
MEA technology to PCC applications [11,36].
Fig. 4 Variation of O2 flowrate and concentration with the
enrichment of CO2 in the feed.
3.4 Solvent make-up
Solvent make-up is an indispensable operation in PCC
plants with MEA as the absorbent because of the escape of
MEA and its degraded products [37]. This has long been
proved a serious issue by pilot scale plant test results and
acid gas removal operations in natural gas. The require-
ment for additional MEA in the capture process not only
adds up the solvent costs but also increases the logistics
cost due the large amount of replenishment. Different
strategies have been employed to reduce the requirement
of solvent make-up [38]. Water wash was reported to be
effective in the containment of gaseous MEA emissions,
but it was not suitable for preventing the escape of MEA
degradation substances which were often in the submicron
size range [38]. However, with the increase of CO2
8 Front. Chem. Sci. Eng.
concentration in this work, the latter types of emissions
could be reduced because of the reduced amount of overall
solvent flowrate and enhanced CO2 loading on MEA. The
simulation results are shown in Fig. 5 for the cases with or
without water wash. It can be seen that the rate for MEA
replenishment for both cases decreased significantly with
the enrichment of CO2, and requirement for make-up in the
“with water wash” case was less severe than the case
without water wash. Therefore, adjusting the CO2 and O2
content in the feed gas could be employed as an effective
approach for controlling the rate of solvent replenishment.
Fig. 5 Effect of CO2 feed concentration on the MEA make-up
rate.
3.5 Overall energy requirement
The energy requirement as a function of the CO2 capture
percentage is shown in Fig. 6. The energy consumption
was calculated on the basis of recovering 90% of the CO2
fed to the VSA section and varying the capture percentage
by the MEA section. The overall capture percentage was
derived by combining the recoveries from the VSA and
MEA sections. The energy requirement is expressed as
specific thermal energy per tonne of CO2 captured. It has to
be noted that the electrical energy used by the VSA section
was converted to thermal energy with the assumption that
heat could be transformed into electricity at an efficiency of
35% [39]. Figure 6 shows that energy demand for both the
Fig. 6 Effect of overall CO2 recovery on the total energy
consumption.
standalone MEA process and the integrated process
increases gradually with increasing CO2 capture percen-
tage. However, the integrated process required higher
energy consumption than a single MEA process. The
increased energy demand was not surprising because the
final captured CO2 need to be desorbed twice: once in the
adsorbent section and once in the MEA section. The extra
energy consumption suggests that the integrated system is
not competitive with a standalone MEA system in terms of
the overall cost. However, the integration of VSA with the
MEA system for post-combustion CO2 capture may still be
an option that it can enable a rapid deployment of solvent
absorption technologies by using readily available solvent
scrubbing towers.
4 Conclusions
This study investigated the feasibility of integrating an
adsorption process with an MEA absorption process for
post-combustion CO2 capture. The results showed that pre-
enrichment of CO2 using an adsorption section preceding
the MEA section could reduce the size of the MEA tower
via reducing the volumetric flow and increasing the CO2
partial pressure in the gas fed to the MEA absorber. The
adsorption section could also alleviate the oxidative
degradation of MEA via the diminution of O2 to the
MEA system, which has a positive flow-on effect on the
reduction of hazardous emissions to the environment. The
increased CO2 concentration and eased degradation of
MEA also diminished the need to restock extra MEA for
solvent make-up, which benefited the overall capture cost.
However, because the specific thermal duty for releasing
CO2 from the MEA remained the same in the integrated
case and the extra power consumed by blowers and
vacuum pumps, the relative energy demand for the
integrated process was greater than the standalone MEA
process. Nevertheless, the integrated process could bring
the equipment, especially the absorber, in the MEA process
to the range of readily available sizes. This benefit alone
may justify the integration of the processes because such a
process could accelerate the wide deployment of MEA
absorption technology for full scale CO2 capture from
power plants.
Acknowledgements The authors wish to acknowledge financial assistance
provided to the CO2CRC by the Australian Government through its CRC
program and through Australian National Low Emissions Coal Research and
Development (ANLEC R&D). ANLEC R&D is supported by Australian
Coal Association Low Emissions Technology Limited and the Australian
Government through the Clean Energy Initiative.
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