Chemical Engineering Journal 230 (2013) 64–72

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Chemical Engineering Journal

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Effects of water vapour on CO2 capture with vacuum swing adsorption

using activated carbon
Dong Xu a, Penny Xiao b, Jun Zhang b, Gang Li b, Gongkui Xiao b, Paul A. Webley b,⇑, Yuchun Zhai c
a
Guodian New Energy Technology Research Institute, China Guodian Corporation, Beijing 100000, China
b
Department of Chemical and Biomolecular Engineering, The University of Melbourne, VIC 3010, Australia
c
School of Material and Metallurgy, Northeastern University, P.O. Box 119, Shenyang 110004, China

h i g h l i g h t s

 CO2 capture on activated carbon from wet flue gas streams.

 Fundamental isotherms and kinetic data obtained.
 Vacuum swing adsorption cycling conducted to determine effect on CO2 capture.

a r t i c l e i n f o a b s t r a c t

Article history: The capture of CO2 with adsorption processes is greatly complicated by the presence of high water levels
Received 12 February 2013 in most process and flue gas streams. One option is to use activated carbon of appropriate hydrophobic-
Received in revised form 17 June 2013 ity. The interaction of water and CO2 on carbon materials in VSA processes is therefore of great interest
Accepted 20 June 2013
and it is this feature which the current study addresses.
Available online 29 June 2013
The adsorption equilibrium isotherms of H2O, CO2 and N2 on activated carbon (coconut shell Acticarb
GC1200) were measured over the range 25–60 °C and 0–1 bar. The Type V isotherm exhibited by water
Keywords:
required a non-Langmuir type representation. In this case, Rutherford’s extended CMMS model was
Water vapour
CO2 capture
employed to describe water adsorption. Breakthrough experiments as well as one bed vacuum swing
Activated carbon adsorption studies were undertaken to investigate the impact of water on CO2 adsorption and its even-
Pressure swing adsorption tual impact on a separation process. Simulations were also conducted to help interpret the data. Our anal-
ysis showed that there was little effect of CO2 and water on each other’s adsorption on the carbon
material beyond the dilution effect on partial pressure of each component. The single bed vacuum swing
experiment showed almost identical recovery and purity of CO2 in the presence of water as in the dry
case. However, the presence of water required additional pumping energy and led to an increase in
CO2 capture energy of about 35%. There is a need to improve carbon materials to further exclude water
without substantially decreasing CO2 capacity and selectivity.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction
CO2 capture from power plants is considered a leading candi-
date for helping mitigate global climate change caused by anthro-
pogenic CO2 emissions [1]. Pressure/Vacuum Swing Adsorption
(PSA/VSA) is one of many new technologies under investigation
for CO2 capture from flue gas streams [2]. Over the last decade,
we have studied the technical feasibility of CO2 separation from
air–CO2 mixtures using commercial adsorbent zeolite 13X by VSA
technology [3–5], and also designed multi-layered VSA units for
CO2 capture from wet flue gas streams [6–8]. However, CO2
⇑ Corresponding author. Tel.: +61 3 90357873.
E-mail address: pwebley@unimelb.edu.au (P.A. Webley).
capture from real flue gas streams containing 8–10% water vapour
is still a large challenge for effective VSA operation using zeolite-
type adsorbents. The adsorption capacity of CO2 on zeolite 13X
declines significantly in the presence of water vapour [9]. To pre-
vent the water front from moving into the main layer of zeolite
13X, almost one third of the total bed length must be employed
as a water guard layer (alumina F-200 or silica based WS Sorbead).
In addition, sufficient vacuum must be provided to ensure that the
required purge to feed ratio is achieved. This additional bed length
exacerbates pressure drop and adds to bed volume. Furthermore,
process upsets may lead to temporary water breakthrough from
the guard bed, irreversibly contaminating the zeolite 13X layer
and compromising CO2 capture capacity. Therefore, it is preferable
for the adsorbent material to be tolerant of water. Adsorbents
which show hydrophobic characteristics and high adsorption

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.06.080
 D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72
capacity of CO2 are in great demand for stable, flexible VSA
operation.
Activated carbon is a common, useful adsorbent which has a
surface containing both hydrophobic and hydrophilic sites to vary-
ing extents according to its source material and preparation meth-
od. There have been numerous previous studies on the use of
activated carbon for capture CO2 from flue gas using pressure, tem-
perature, or electrical swing adsorption, starting with the studies
of Kikkinides et al. [10] in 1993. These studies have variously com-
pared performance to 13X under similar operating conditions [11],
developed improved PSA cycles to offset the somewhat inferior
performance of activated carbon compared to 13X [12,13], exam-
ined the use of heating of the activated carbon (either through
electrical means or indirect heating through purge gas) [14–16]
or used a combination of two VSA stages to enhance the recovery
and purity [17]. In all cases, however, the presence of water in
the flue gas was omitted. Recently however, Dutcher et al. [18]
examined the use of steam purge to regenerate the activated car-
bon beds.
Any hydrophilic surface sites which may be present on carbon
act as primary adsorption centres for water vapour. The adsor-
bent–adsorbate interactions are often of the nature of hydrogen
bonding to surface functional groups and cluster formation around
the functional groups at low surface coverage [19–22]. Upon
adsorption, water may further migrate and fill available microp-
ores [22]. The bonding between water vapour and the surface of
many activated carbons is sufficiently weak that adsorbed water
can be desorbed by reducing its partial pressure alone. From José’s
experiment [22], water vapour can even be completely desorbed
by dry-air when the temperature was held constant. The combined
hydrophobic and hydrophilic characteristics of activated carbon
results in a unique adsorption equilibrium isotherm for water va-
pour (Type V) [23]. By contrast, water is strongly adsorbed to zeo-
lite 13X even at very low relative humidity [24] and is difficult to
remove by reducing total pressure alone, as in the VSA processes.
The adsorption capacity of CO2 on activated carbon on the other
hand depends on the pore structure and the surface chemistry of
the activated carbon [25,26]. Unlike water adsorption on activated
carbon, CO2 is able to adsorb on both hydrophobic and hydrophilic
sites. Because of the acidic nature of CO2, basic groups on the sur-
face of activated carbon will benefit CO2 adsorption capability. The
absolute adsorption capacity of CO2 on most activated carbons is
considerably lower than that on zeolite 13X when the CO2 partial
pressure is less than 2 bar [27]. The working capacity however,
may not be substantially lower since the CO2 adsorption isotherm
is more nearly linear and hence may not require the very low vac-
uum pressures needed for CO2 desorption from 13X zeolite. The
presence of ultramicropores in carbons is especially useful for
CO2 adsorption as discussed by Presser et al. [28]. Furthermore,
the unique hydrophobic characteristics as discussed above for acti-
vated carbon may more than offset the slightly lower working
capacity of CO2 when used for high humidity flue gas streams in
VSA technology. We have undertaken this investigation and report
here on the fundamental aspects of water/CO2 adsorption on acti-
vated carbon for CO2 capture applications. A future study will re-
port on the performance of activated carbon in VSA systems. In
this study, the adsorption equilibrium of water vapour, CO2 and
N2 on activated carbon were measured. Binary breakthrough mea-
surements were conducted with a fixed bed of activated carbon.
The behaviour of water in the adsorption bed during a single bed
VPSA process was investigated and analysed. The VSA performance
for CO2 capture in the presence of water vapour was also simu-
lated. Our adsorption simulation tool was employed to simulate
the kinetics of adsorption and VSA cyclic processes. As a result of
these studies, we have designed and tested a more complex
multi-bed PVSA cyclic process with six adsorption beds for CO2
65
capture from wet flue gas streams - these results will be the sub-
ject of a future communication.
2. Experimental work
2.1. Adsorption equilibria of nitrogen and carbon dioxide on activated
carbon
The activated carbon used in our study (coconut shell Acticarb
GC1200, 8  12 mesh) was supplied by Activated Carbon Technol-
ogies Pty Ltd., Australia. The textural physical properties were
measured and are shown in Table 1. BET surface area, pore volume
and pore size of the activated carbon pellets, and adsorption iso-
therms of CO2 and N2 on the activated carbon were measured with
a volumetric adsorption analyser (Micrometritics, ASAP 2010). The
samples were degassed at 350 °C and a vacuum pressure of 7 Pa for
12 h.
2.2. Adsorption equilibrium of water vapour on activated carbon
The adsorption equilibrium of water vapour was measured with
our custom designed Isothermal Adsorption Unit (Fig. 1), as previ-
ously described [29]. An activated carbon sample was firstly heated
to 300 °C for 12 h under helium gas to remove adsorbed impurities
such as CO2 and H2O. Then the prepared sample was weighed and
quickly placed into the adsorption column. Helium was used as a
carrier gas. The operation procedures have been described clearly
in our previous study [7]. Pure water adsorption characteristics
were measured at 25, 30, 35, 49 and 62 °C.
2.3. Vacuum swing adsorption process experiments
The fundamental steps of the VSA process were investigated
with our single bed VSA unit (Fig. 2). This unit includes four parts:
a feed gas line, vacuum line, adsorption column and exhaust line
(vent). In the feed gas line, dry air was blended with a CO2 stream
directly or alternatively diverted through a water tank and then
mixed with the dry CO2 gas stream to form a feed gas stream con-
taining different CO2 concentrations. The liquid water in the water
tank was heated to different temperatures to achieve different
water contents in the feed gas stream. The inlet pipe was wrapped
with heating tape to maintain the feed gas at the required temper-
ature and avoid condensation. The vacuum pressure was achieved
with an oil rotary vane vacuum pump. To avoid water condensa-
tion in the vacuum pump (and damage of the oil-pump), two driers
filled with zeolite 3A were located in the line between the bed and
the vacuum pump to adsorb water vapour desorbed from the
adsorption bed. The adsorption bed (ID 49 mm  L 560 mm, stain-
less steel) was filled with activated carbon – heating tape was
wrapped around the outside of the bed and the entire column sys-
tem was insulated with rubber insulation material to maintain bed
temperature and reduce heat loss from the system to the environ-
ment. Eleven thermocouples (T type) were inserted into the bed at
the position of 20, 60, 100, 140, 180, 220, 260, 300, 387, 474, and
560 mm for monitoring the thermal excursion during the process.
Table 1
Physical properties of activated carbon Acticarb GC1200.
Property BET surface Total pore Average Bulk density
(m2/g) volume micropore sizea (kg/m3)
(cm3/g) (nm)
Activated 921.7 0.37 0.73 493
carbon
a
As determined by NLDFT (slit geometry) in the range 0–2 nm.
66 D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72
Fig. 1. Schematic diagram of H2O/CO2 single and binary isothermal adsorption unit.
Two humidity analysers were employed to monitor water concen-
trations at the entrance and the exit of the bed, respectively. Three
CO2 analysers were also installed to measure CO2 concentrations
from inlet, exhaust (vent) and CO2 product lines. Flow meters
and pressure transducers were placed in the system to monitor
flow rates and pressures.
A simple VSA cycle including adsorption, desorption and re-
pressurisation steps was designed for investigating the effect of
water vapour on VSA processes (Fig. 3).
Fig. 2. Single-bed VSA process schematic diagram for cyclic experiments.
Fig. 3. Vacuum swing adsorption cycle.
Step 1: Feed gas entered the adsorption bed from the bottom of
the bed. CO2 and water were adsorbed onto the activated car-
bon, and weakly adsorbed gas (mostly N2 and O2 from the air)
exited from the top of the bed.
Step 2: Adsorbed CO2 and water, together with co-adsorbed N2
and O2 as well as void gas was desorbed and released into the
vacuum line at the desired vacuum level.
Step 3: The bed was re-pressurised from the top of the bed to
atmospheric pressure using the exhaust gas.
2.4. Breakthrough experiments
The breakthrough adsorption bed (details in Table 2) contained
seven thermocouples (T1–T7) with an interval of 165 mm for mea-
suring the temperature changes. Because the adsorption loading of
CO2 and H2O is much larger than N2 and O2, the thermal waves
measured are mainly attributed to CO2 and H2O. Here, ‘binary
breakthrough’ is taken to denote breakthrough experiments done
using a mixture of CO2 and H2O balanced with air as a feed gas
 D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72 67

Table 2
of water with the functional group.Equilibrium constants (K0, K1 and
Experimental conditions for breakthrough and cyclic experiments.
BL) are dependent on temperatures as described below [31]:
VSA cycle Binary breakthrough  
Q0
Bed physical size (mm) ID 49  L 560 ID 76  L 1010 K 0 ¼ K 0T exp ð6Þ
Activated carbon load (kg) 0.52 2.30
RT
Feed gas temperature (°C) 60 60 60  
Feed gas pressure (kPa) 113 113 130 Q1
Water vapour (mol%) 0 4.60 4.83 K 1 ¼ K 1T exp ð7Þ
RT
CO2 concentration (mol%) 12 11.4 12
Flow-rates (sl/min) 50 50 100  
Velocity (m/s) 0.44 0.44 0.40 QL
BL ¼ BLT exp ð8Þ
Adsorption time (s) 35 35 RT
Desorption time (s) 100 100
Re-pressurisation time (s) 3 3 where Q0, Q1 and QL are enthalpies related to constants (J/mol), K0T, K1T
Vacuum pressure (kPa) 2.2 2.2 and BLT are slightly dependent on the temperature entropic factors. To
use the model in VSA process, relative water pressures in these equa-
and ‘single breakthrough’ means using a mixture of only CO2 or tions were converted into absolute pressures using the saturated
H2O balanced with air. pressure of water as a function of temperature as shown below.
The experimental conditions for the breakthrough experiment Since the temperature range over which the process operates is
and cyclic processes are shown in Table 2. In order to clearly inves- small, as a first approximation we use the integrated Clausius–Cla-
tigate the effect of high water vapour level on CO2 capture, both peyron equation for the water vapour pressure curve:
breakthrough and cyclic experiments were run with feed at    
P0 ðTÞ DH 1 1
60 °C. The stream is partially saturated by splitting the feed, satu- ln ¼  ð9Þ
P0;ref ðT 0;ref Þ R T 0;ref T
rating a portion, and blending it with the remaining dry fraction. In
this way the relative humidity can be controlled to a desired level. where P0,ref and P0 are water saturated pressures (kPa) at tempera-
tures of T01 and T (K) respectively, and DH is latent heat of vapouri-
3. Adsorption modelling sation (J/mol).
Therefore, Bla in Eq. (4) can be written by:
     
3.1. Adsorption equilibrium QL P QL P exp DRTH
BLT exp ¼ BLT exp

RT P0 RT P DH
The Dual-site Langmuir equation was employed to fit the iso- 0;ref exp RT
0;ref

therms of CO2 and N2 on activated carbon using standard non-lin-

 
BLT DH þ Q L
ear regression techniques: ¼
exp P
P exp DH RT
0;ref RT 0;ref
M B BP M D DP
n¼ þ ð1Þ Since T0,ref is fixed, P0,ref is a constant, hence BLT

can be
1 þ BP 1 þ DP DH
P0;ref exp RT 0;ref
where n represents adsorption amount (mol/kg), MB and MD repre- replaced by a new constant bLT (1/kPa) and DH + QL can be replaced
sent saturated adsorption amounts corresponding to site I and site II with qL (J/mol), and the same for K0a and K1a. Therefore:
(mol/kg) respectively, P represents equilibrium pressure (kPa) and B q

L
and D are: BL a ¼ blT exp P ð10Þ
  RT
QB q

B ¼ B0 exp ð2Þ
RT K 0 a ¼ k0T exp 0
P ð11Þ
RT
 
QD q

D ¼ D0 exp ð3Þ K 1 a ¼ k1T exp 1

P ð12Þ
RT RT
where B0 and D0 are coefficients (1/kPa), QB and QD are adsorption Eqs. (4) and (5) can therefore be replaced by the following ones
heats on sites I and II (J/mol), R is the universal gas constant with absolute water vapour pressure:
(8.3145 J/mol K) and T is temperature (K). q  q 
C sat k0T exp RT0
P C satL bLT exp RT
L
P
A number of models have been reported to describe water n¼ q  þ q  ð13Þ
k0T exp RT P þ w
0 2 1 þ bLT exp RT PL
adsorption equilibrium on activated carbon [30]. Rutherford’s ex-
tended CMMS model [31,32] was employed in this paper because rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!
1 q
h q
i2 q

it provided a satisfactory fit to the data as determined by standard

w¼ 1  k1T exp 1 P þ 1  k1T exp 1 P þ 4k0T exp 0 P
regression techniques. The water adsorption equilibrium is given by: 2 RT RT RT
C sat K 0 a C satL BL a ð14Þ
n¼ þ ð4Þ
K 0 a þ w2 1 þ BL a The isosteric heat of adsorption (Qn) at a constant adsorption
 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi capacity (n) can also be calculated with Clausius–Clapeyron
1
w¼ 1  K 1 a þ ð1  K 1 aÞ2 þ 4K 0 a ð5Þ equation:
2    
@ lnðPÞ T 2 @P
where Csat is the adsorption capacity of water on the graphitic micro- Q n ¼ R ¼R ð15Þ
@ lnð1=TÞ n P @T n
structure (mol/kg), a is the relative pressure (P/Po), K0 is the interac-
tion of water with the central unit on the primary adsorption site on
the graphene surface, w is given by Eq. (5). K1 is the interaction of 3.2. Simulation of adsorption dynamics and the VSA process
water with the side unit on the primary adsorption site on the
graphene surface, CsatL is the adsorption capacity of water bound Our simulator MINSA (Melbourne Integrated Numerical Simula-
to functional groups (mol/kg) and BL is the affinity for the interaction tion of Adsorption) developed for describing PSA (Pressure Swing
68 D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72
Adsorption) separation processes was used to help model and
understand the experimental results. The model is based on mass
and energy balance conservation together with constitutive rela-
tions for equilibrium isotherms and adsorption kinetics and the de-
tails have been reported earlier [33,4]. All species are assumed to
adsorb independently according to their partial pressure in the
gas mixture as given by the isotherm equations described above.
The extended Langmuir version of (1) was used for CO2 and N2
adsorption.
4. Results and discussion
4.1. Adsorption equilibrium of CO2, N2 and water vapour
The adsorption isotherms of CO2 and N2 on activated carbon are
shown in Fig. 4. The experiment data are well represented with the
Dual-site Langmuir model with the constants listed in Table 3. The
adsorption amount of O2 was too small for reliable measurement
and was considered as an inert gas in this study.
From Fig. 4, the CO2 adsorption decreased significantly over the
temperature range 20–60 °C. In typical flue gas streams resulting
from coal combustion, the CO2 concentration is approximately
12% at atmosphere pressure (equivalent to a partial pressure of
12 kPa), at which the CO2 loading is 0.4 mol/kg at 60 °C. The selec-
tivity of CO2 over N2 (69.5% concentration) is 0.4:0.1. This value is
much lower than that on zeolite 13X (CO2:N2 = 1.194:0.137) at the
same conditions [4]. Isotherms of water vapour on activated car-
bon at four temperatures are shown in Fig. 5. The extended CMMS
model represents the experimental data well and the parameters
for the model are listed in Table 4. The isosteric heat of water on
activated carbon calculated by the Clausius–Clapeyron equation,
ranges from 40 870 to 30 000 J/mol as the water loading increases
from 0 to 4 mol/kg (0–10% of water vapour at 60 °C and atmo-
sphere pressure).
At 62 °C, the adsorption capacity of water vapour is only
2.44 mol/kg at a water partial pressure of 10 kPa (equivalent to
Fig. 4. Isotherm data of CO2 and N2 at temperatures of 20 °C, 40 °C and 60 °C. Lines
– Dual-site Langmuir model, symbols – experimental data.
Table 3
Parameters in the Dual-site Langmuir model for CO2 and N2.
Item MB MD B0 D0 QB
(mol/kg) (mol/kg) (1/kPa) (1/kPa) (J/mol)
CO2 0.591 7.506 4.05E7 1.69E6 31,381
N2 1.832 0 3.06E6 16,518
Fig. 5. Isotherms of water vapour on activated carbon at various temperatures.
Lines – Rutherford Extended CMMS model and symbols – experimental data.
10% water at an atmosphere pressure). Thus, some of water may
leave with the vent (waste) gas when activated carbon is used as
an adsorbent in a pressure swing processes. This is desirable as it
reduces the loading on the vacuum pump. The characteristic shape
of the adsorption isotherms (Type V) for water shown in Fig. 5
makes it amenable to removal through pressure reduction, in con-
trast to the steep Type I isotherm exhibited by water on zeolite
13X. Indeed, desorption of water from activated carbon may be
even easier than from activated alumina (type II adsorption for iso-
therms of water) [34]. Therefore, even though the adsorption
capacity of CO2 and CO2:N2 selectivity on activated carbon is lower
than that on zeolite 13X, the unique hydrophobic characteristic of
activated carbons with the associated advantages in handling
water make this an interesting choice for CO2 capture applications.
4.2. Dynamics of binary adsorption of H2O and CO2 in a fixed activated
carbon bed
Fig. 6 shows the binary breakthrough of CO2 and water vapour
balanced with air at a flow-rate of 100 l/min (superficial bed veloc-
ity 0.40 m/s). The initial temperature of the adsorption bed was
45 °C as maintained by a jacketed heater. Fig. 7 shows the temper-
ature profiles at a distance of 100 mm (T7) from the bottom of the
adsorption bed.
The rate of mass transfer of water in the activated carbon was
described by a LDF model:
@ni  
¼ K Li ni  ni ð16Þ
@t
where ni is equilibrium adsorbent loading of component i (mol/kg)
and KLi (1/s) was be calculated by:
Di
K Li ¼ ki ð17Þ
r2
where r is pellet diameter (m), ki is an empirical mass transfer coef-
ficient of component i (=15) for H2O, CO2, N2 and O2 according to
Glueckauf LDF model [35]), and Di is the diffusion coefficient of
component i.
According to the adsorption equilibrium of water vapour (Fig. 5)
and CO2 (Fig. 4), the water loading is 1.35 mol/kg at its feed partial
pressure of 6.27 kPa at 60 °C (equivalent to 4.83% at 130 kPa in the
QD
(J/mol) binary breakthrough experiment) and the CO2 loading is only
0.42 mol/kg at its partial pressure of 14.46 kPa at 60 °C (12% at
19,843
130 kPa in the binary breakthrough experiment). Therefore, the
water front traverses the bed much slower than the CO2 front as
 D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72 69

Table 4
Parameters in the CMMS equation for water adsorption on activated carbon.

Item Csat (mol/kg) k0T (1/kPa) q0 (J/mol) k1T (kPa) q1 (J/mol) CsatL (mol/kg) bLT (1/kPa) qL (J/mol)
H2O 16.67 9.9E13 5.46E+04 8.3E09 4.47E+04 7.13 1.4E08 40,369

To analyse and understand the effect of thermal waves on bin-

1.20 CO2 breakthrough
experiment CO2 breakthrough ary adsorption, we compared the binary breakthrough curve
simulation
(experiment and simulation) and single component breakthrough
1.00
C/C0 (CO2 and H2O) [-]

data of only water or CO2 balanced with air (simulation). From

Fig. 8, the first temperature peak in the binary breakthrough
0.80 water breakthrough
experiment (100 s) between simulation and experiment agreed well but the
0.60 temperatures measured in the second peak was much lower than
water breakthrough
simulation those in simulation. We attribute this difference at least partly to
0.40 heat loss from the system because of the large temperature differ-
ence between the column and the environment at this point. It is
0.20 also likely that more complex water–CO2 interaction not fully cap-
tured in our simple isotherm models may lead to a different
0.00 adsorption thermodynamics which yield a lower isosteric heat of
0 500 1000 1500 2000 2500 adsorption and hence a lower temperature rise than calculated. It
Breakthrough time (s) will be recalled from our earlier discussion that our only represen-
tation of the interaction of water and CO2 is through the effect on
Fig. 6. Binary breakthrough of CO2 and H2O balanced with air at the exit of the
partial pressure of those species.
adsorption bed (T7 position) at a feed flow-rate of 100 l/min, 1.3 bar and 60 °C.
Symbols – experiment and lines – simulation. At position T7 (1000 mm from the bottom of the bed), CO2
achieved breakthrough at t = 48 s (Fig. 6), which matched with
the occurrence of the first thermal wave (Fig. 8).

T1
70 4.3. Single column VSA step analysis
T2
Our single column VSA process was conducted to cyclic steady
Temperature ( C)

T3 state for both dry and wet conditions. CSS was determined by
0

60 observation of steady cyclic thermal profiles as well as constant

T4 average purities and recoveries. For dry gas this occurred within
30 cycles. For wet gas this required more than 200 cycles. The pres-
T5 sure profile at the bottom of the adsorption bed for one cycle is
50 shown in Fig. 9. Pressures during an adsorption step were main-
T6 tained at 107–108 kPa at the bottom of the bed and a flow-rate
of 50 l/min (superficial velocity 0.2 m/s). Desorption to 2.2 kPa
T7 followed and then pressurisation to 1.05 bar.
40 The instantaneous concentration of water in the gas were mea-
0 100 200 300 sured at the bottom and top of an adsorption bed at cyclic steady
Breakthrough time (s) state (CSS) and are shown in Fig. 10a and b, respectively. The pro-
files of water and CO2 in the bed as predicted by simulation are
Fig. 7. Temperature profiles in the binary breakthrough experiment.

expected. The simulations were conducted for adiabatic condi-

tions. Fig. 7 shows the temperature profiles in the column during
Binary simulation
the breakthrough experiment (the feed as 60C and the initial bed 70
temperature was 40 °C). It is clear from the thermocouples (espe-
cially near the bottom of the bed) that the bed is not adiabatic. Single water simulation
Temperature ( 0C)

65
The adsorption loading of CO2 and H2O in the experiment are
therefore expected to be higher than those calculated by the sim-
ulation, as seen in Fig. 6. 60
Binary experiment
The CO2 breakthrough curve shows a characteristic ‘‘roll-up’’ as
expected [6]. Although the time to breakthrough for water is pre-
dicted well (based on the equilibrium loading), the shape of the 55 Single CO 2 simulation
mass transfer front is poorly predicted. The reasons could relate
to heat transfer, the use of a simple mass transfer model (LDF) as
50
well as interactions between H2O and CO2 not capture in the equi-
librium model. The multiple ‘‘steps’’ in the temperature profiles in 0 100 200 300 400 500
Fig. 7 correspond to adsorption of CO2 and H2O, respectively. As the
Breakthrough time (s)
CO2 front moves considerably faster than the water front, the two
peaks were easily separated with distance from the bottom of the Fig. 8. Temperature history at T7 position (near the exit of the bed) from simulation
bed (T4, T5, T6 and T7). and experiment.
70 D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72

120
40
a

Water vapor concentration (%)

90
30
Pressure (kPa)

60
20

30 10

0 0
0 30 60 90 120
0 30 60 90 120
Time (s)
Cycle time (s)

Fig. 9. Pressure history of one bed over one cycle at cyclic steady state. ‘–’ –
simulation result and ‘N’ – experimental data. 0.6
b

Water vapor concentration (%)

shown in Fig. 10c. Note that water frequently exhibits an adsorp-
tion hysteresis – this was not accounted for in the current study.
0.3
Fig. 10a and b shows reasonable agreement in trends between
experiment and simulation although the water concentration at
the bottom of the bed during pump down (35–135 s, Fig. 10a) is
over predicted by the simulation. In this case, we suspect that
the experimental data are too low. During the pump down stage, 0.0
the total flow rate drops quickly to the point where there is insuf-
ficient gas to flow to the moisture analyser leading to a drop in to-
tal pressure and correspondingly a drop in calculated water
concentration (the analyser responds to water partial pressure). -0.3
0 10 20 30
Although a water concentration of up to 30–40 wt% is expected
Time (s)
during the pump down stage in the vacuum line, condensation
does not occur as the total pressure is also falling rapidly. In addi-
tion to removing a large amount of water in the vacuum step, it is
interesting to observe that some water is emitted from the top of 12
c
the bed (Fig. 10b and c) due to the finite kinetics and length of
the mass transfer zone. During the desorption step, air from the CO2
environment slowly spread into the waste tank so that a small
Concentration (%)

9
amount of water vapour was adsorbed at top part of the bed during
waste gas re-pressurisation and also purged out during the begin-
ning of adsorption step with the exhaust gas, which led to a slightly
higher water percentage initially during the adsorption step 6
H2O
(Fig. 10b).
To assess the impact of moisture on CO2VSA separation perfor-
mance, both dry and wet experiments were conducted. The CO2 3
history at the exit of the column during the adsorption step at cyc-
lic steady state is shown in Fig. 11. Over the time scale shown, the
simulation predicts a far smaller and almost constant CO2 concen-
0
tration of 1% CO2 (not shown). 0.0 0.2 0.4 0.6
Fig. 11a shows that the CO2 concentration exiting the bed for Distance from bottom of the bed (m)
the dry gas and wet gas experiments in exiting streams were very
similar. As expected, the adsorption amount of CO2 in the bed for Fig. 10. Concentration of water history (a) at the bottom, (b) at the top of the
the binary experiment was lower than that for pure components dsorption bed and (c) water profile in the bed from simulation. Lines – simulation
and ‘j’ – experiment.
so that the CO2 in wet gas appeared early in exit. During the evac-
uation step, only the average CO2 concentration was measured (as
(experiment) compared to 49.16% (simulation). For the wet gas
accumulated in the downstream tank) and is shown in Fig. 11b.
run, the CO2 concentration was 42.0% (experiment) compared to
Measuring instantaneous CO2 concentrations in the vacuum line
40.74% (simulation). Recall from Fig. 10a, that the major fraction
was not practical because the very low flow-rate under vacuum
of the water vapour is pumped out with released CO2 in the
pressures provided insufficient gas flow to refresh the CO2
vacuum line. To compare the CO2 concentration between these
analyser. From our MINSA result, the simulation matched with
two runs, we recalculate the CO2 concentration on a dry basis.
experiment quite well suggesting a good correlation of the overall
For the wet run, the equivalent ‘‘dry’’ CO2 concentration
mass balance of CO2 and water between experiment and simula-   
C
tion. For the dry gas run, the average CO2 concentration 48.94% CCO2;dry ¼ CO2;wet
 is 48.23% in the simulation and 49.24% in the
ð1CH2O Þ
 D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72 71

6 a 0.15

Flow rate (mol/s)

Wet gas 0.10
4

0.05
2 Dry gas wet gas

0.00 dry gas

0
0 10 20 30 0 30 60 90 120
Time (s) Cycle time (s)

Fig. 12. Flow-rates for dry and wet gases at the bottom of the bed in one cycle.
Dry gas
60 b
these assumptions will be correct. We expect commercial scale
multiple stage vacuum units with efficiencies which depend on
vacuum pressure. Therefore, it is important not to take the abso-
40
lute power numbers as reliable predictors – rather, our goal here
is to compare the power between the wet and dry case to estimate
Wet gas
the additional work needed as a consequence of the presence of
water.
20
Fig. 9 shows that the feed pressures and flow-rates for dry and
wet gases were well maintained at the same values so that powers
consumed in a feed step were similar. Therefore we focus attention
here on the power consumption during the evacuation step. The
0
0 50 100 150 pump-down pressure history of the bed for both the dry and wet
Time (s) runs were virtually identical (not shown). It was difficult to mea-
sure flow-rates clearly during the vacuum conditions in this exper-
Fig. 11. CO2 concentrations (a) at the top (instantaneous) and (b) at the bottom of iment especially at the start of the pump down step since the very
the adsorption bed (average). large ‘‘spike’’ in flow rate cannot be reliably captured by the flow
meter. Consequently, the flow rates to be used in the power calcu-
lation here are taken from our simulation (Fig. 12).
experiment respectively, which were very close to the CO2 concen-
For the dry run, a total of 0.247 mol of gas was evacuated during
tration from the dry run. The agreement between experiment and
a cycle (containing 49% CO2). For the wet run, this increased to
simulation for the recovery of CO2 in this simple 1 bed, 3 step VSA

0.293 mol (40.2%CO2, 16.5%H2O). As a result, the energy consumed
CO CO
process Rec ¼ 2;inCO 2;out was very good. For the dry run, a recov- during the evacuation step increased from 2.43 kJ/cycle for the dry
2;in

ery of 89.1% (experiment) vs 87.5% (simulation) was obtained gas to 3.26 kJ/cycle for the wet gas – an increase of 34%. This extra
whereas the wet run gave recoveries of 87.5% (experiment) and energy was required for doing the separation of water vapour and
89.8% (simulation). Perhaps most importantly, there appears to represents the major impact of moisture on the VSA process for
be no significant effect of the water vapour on the recovery and CO2 capture.
purity attainable in the process for activated carbon adsorbent.
The only affect is the additional power consumption required to
5. Conclusions
perform the work of H2O separation, as discussion below.
For the three-step simple cycle employed in this study, power is
The impact of water vapour on CO2 capture from flue gas on
consumed in two steps: feed and evacuation. The total power in
activated carbon was assessed through experiments and simula-
this experiment was calculated by:
tion. Experimental adsorption equilibrium data were measured
for CO2, N2 and H2O and represented by appropriate isotherm
" k1 #
X
n¼i
k Q feed Pin Pin k X
i¼n
k equations. Breakthrough experiments were performed to explore
Power ðkJÞ ¼  1 Dt þ the impact of CO2 and H2O on each other – as expected, CO2 broke
n¼1
k  1 g P atm i¼1
k  1
" # through the bed before H2O. Both CO2 and H2O showed slightly
k1
Q Pv ac Patm k diminished loadings in the presence of each other compared to
 v ac  1 Dt their pure component loadings at the same partial pressure.
g Pv ac
A simple one bed, 3step VSA cyclic experiment showed that
where g (isentropic efficiency) = 0.7, k (specific heat ratio) is there was very little impact of water vapour on CO2 purity and
1.28 for CO2 and 1.4 for air, Qfeed represents an instantaneous flow recovery, but an increase of 35% in power consumption when
rate (m3/s) for feeding gas streams, Patm (atmospheric pressure) wet simulated flue gas was used as the feed.
equals 101.375 kPa, and Pin and Pvac (kPa) represent instantaneous In summary, although the selectivity of CO2 over N2 on
pressures for feed and vacuum gases. This power calculation as- activated carbon is lower than that on zeolite 13X, activated carbon
sumes a single stage, adiabatic compression (for feed and vacuum offers other advantages – in this case its water tolerance and rela-
separately) with a constant isentropic efficiency. In reality, none of tively minor impact on process performance as regards CO2 purity
72 D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72
and recovery. The ability to alter the hydrophobic characteristic of
activated carbon is a promising avenue for further VSA technology
investigation in the application to real wet flue gases. However,
absolute CO2 capture performance when using activated carbon
adsorbent is inferior to 13X and hence more detailed research is
needed to improve the CO2 adsorption properties as well as
improve the cycle design before implementation is possible.
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