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Chemical Engineering Journal 230 (2013) 64–72

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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
Guodian New Energy Technology Research Institute, China Guodian Corporation, Beijing 100000, China
Department of Chemical and Biomolecular Engineering, The University of Melbourne, VIC 3010, Australia
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
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 capture from real flue gas streams containing 8–10% water vapour
is still a large challenge for effective VSA operation using zeolite-
CO2 capture from power plants is considered a leading candi- type adsorbents. The adsorption capacity of CO2 on zeolite 13X
date for helping mitigate global climate change caused by anthro- declines significantly in the presence of water vapour [9]. To pre-
pogenic CO2 emissions [1]. Pressure/Vacuum Swing Adsorption vent the water front from moving into the main layer of zeolite
(PSA/VSA) is one of many new technologies under investigation 13X, almost one third of the total bed length must be employed
for CO2 capture from flue gas streams [2]. Over the last decade, as a water guard layer (alumina F-200 or silica based WS Sorbead).
we have studied the technical feasibility of CO2 separation from In addition, sufficient vacuum must be provided to ensure that the
air–CO2 mixtures using commercial adsorbent zeolite 13X by VSA required purge to feed ratio is achieved. This additional bed length
technology [3–5], and also designed multi-layered VSA units for exacerbates pressure drop and adds to bed volume. Furthermore,
CO2 capture from wet flue gas streams [6–8]. However, CO2 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
⇑ Corresponding author. Tel.: +61 3 90357873.
which show hydrophobic characteristics and high adsorption
E-mail address: (P.A. Webley).

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
D. Xu et al. / Chemical Engineering Journal 230 (2013) 64–72 65

capacity of CO2 are in great demand for stable, flexible VSA capture from wet flue gas streams - these results will be the sub-
operation. ject of a future communication.
Activated carbon is a common, useful adsorbent which has a
surface containing both hydrophobic and hydrophilic sites to vary-
2. Experimental work
ing extents according to its source material and preparation meth-
od. There have been numerous previous studies on the use of
2.1. Adsorption equilibria of nitrogen and carbon dioxide on activated
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-
The activated carbon used in our study (coconut shell Acticarb
pared performance to 13X under similar operating conditions [11],
GC1200, 8  12 mesh) was supplied by Activated Carbon Technol-
developed improved PSA cycles to offset the somewhat inferior
ogies Pty Ltd., Australia. The textural physical properties were
performance of activated carbon compared to 13X [12,13], exam-
measured and are shown in Table 1. BET surface area, pore volume
ined the use of heating of the activated carbon (either through
and pore size of the activated carbon pellets, and adsorption iso-
electrical means or indirect heating through purge gas) [14–16]
therms of CO2 and N2 on the activated carbon were measured with
or used a combination of two VSA stages to enhance the recovery
a volumetric adsorption analyser (Micrometritics, ASAP 2010). The
and purity [17]. In all cases, however, the presence of water in
samples were degassed at 350 °C and a vacuum pressure of 7 Pa for
the flue gas was omitted. Recently however, Dutcher et al. [18]
12 h.
examined the use of steam purge to regenerate the activated car-
bon beds.
Any hydrophilic surface sites which may be present on carbon 2.2. Adsorption equilibrium of water vapour on activated carbon
act as primary adsorption centres for water vapour. The adsor-
bent–adsorbate interactions are often of the nature of hydrogen The adsorption equilibrium of water vapour was measured with
bonding to surface functional groups and cluster formation around our custom designed Isothermal Adsorption Unit (Fig. 1), as previ-
the functional groups at low surface coverage [19–22]. Upon ously described [29]. An activated carbon sample was firstly heated
adsorption, water may further migrate and fill available microp- to 300 °C for 12 h under helium gas to remove adsorbed impurities
ores [22]. The bonding between water vapour and the surface of such as CO2 and H2O. Then the prepared sample was weighed and
many activated carbons is sufficiently weak that adsorbed water quickly placed into the adsorption column. Helium was used as a
can be desorbed by reducing its partial pressure alone. From José’s carrier gas. The operation procedures have been described clearly
experiment [22], water vapour can even be completely desorbed in our previous study [7]. Pure water adsorption characteristics
by dry-air when the temperature was held constant. The combined were measured at 25, 30, 35, 49 and 62 °C.
hydrophobic and hydrophilic characteristics of activated carbon
results in a unique adsorption equilibrium isotherm for water va- 2.3. Vacuum swing adsorption process experiments
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 The fundamental steps of the VSA process were investigated
remove by reducing total pressure alone, as in the VSA processes. with our single bed VSA unit (Fig. 2). This unit includes four parts:
The adsorption capacity of CO2 on activated carbon on the other a feed gas line, vacuum line, adsorption column and exhaust line
hand depends on the pore structure and the surface chemistry of (vent). In the feed gas line, dry air was blended with a CO2 stream
the activated carbon [25,26]. Unlike water adsorption on activated directly or alternatively diverted through a water tank and then
carbon, CO2 is able to adsorb on both hydrophobic and hydrophilic mixed with the dry CO2 gas stream to form a feed gas stream con-
sites. Because of the acidic nature of CO2, basic groups on the sur- taining different CO2 concentrations. The liquid water in the water
face of activated carbon will benefit CO2 adsorption capability. The tank was heated to different temperatures to achieve different
absolute adsorption capacity of CO2 on most activated carbons is water contents in the feed gas stream. The inlet pipe was wrapped
considerably lower than that on zeolite 13X when the CO2 partial with heating tape to maintain the feed gas at the required temper-
pressure is less than 2 bar [27]. The working capacity however, ature and avoid condensation. The vacuum pressure was achieved
may not be substantially lower since the CO2 adsorption isotherm with an oil rotary vane vacuum pump. To avoid water condensa-
is more nearly linear and hence may not require the very low vac- tion in the vacuum pump (and damage of the oil-pump), two driers
uum pressures needed for CO2 desorption from 13X zeolite. The filled with zeolite 3A were located in the line between the bed and
presence of ultramicropores in carbons is especially useful for the vacuum pump to adsorb water vapour desorbed from the
CO2 adsorption as discussed by Presser et al. [28]. Furthermore, adsorption bed. The adsorption bed (ID 49 mm  L 560 mm, stain-
the unique hydrophobic characteristics as discussed above for acti- less steel) was filled with activated carbon – heating tape was
vated carbon may more than offset the slightly lower working wrapped around the outside of the bed and the entire column sys-
capacity of CO2 when used for high humidity flue gas streams in tem was insulated with rubber insulation material to maintain bed
VSA technology. We have undertaken this investigation and report temperature and reduce heat loss from the system to the environ-
here on the fundamental aspects of water/CO2 adsorption on acti- ment. Eleven thermocouples (T type) were inserted into the bed at
vated carbon for CO2 capture applications. A future study will re- the position of 20, 60, 100, 140, 180, 220, 260, 300, 387, 474, and
port on the performance of activated carbon in VSA systems. In 560 mm for monitoring the thermal excursion during the process.
this study, the adsorption equilibrium of water vapour, CO2 and
N2 on activated carbon were measured. Binary breakthrough mea-
Table 1
surements were conducted with a fixed bed of activated carbon.
Physical properties of activated carbon Acticarb GC1200.
The behaviour of water in the adsorption bed during a single bed
VPSA process was investigated and analysed. The VSA performance Property BET surface Total pore Average Bulk density
(m2/g) volume micropore sizea (kg/m3)
for CO2 capture in the presence of water vapour was also simu-
(cm3/g) (nm)
lated. Our adsorption simulation tool was employed to simulate
Activated 921.7 0.37 0.73 493
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 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. 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.
Fig. 1. Schematic diagram of H2O/CO2 single and binary isothermal adsorption unit. Step 3: The bed was re-pressurised from the top of the bed to
atmospheric pressure using the exhaust gas.

Two humidity analysers were employed to monitor water concen- 2.4. Breakthrough experiments
trations at the entrance and the exit of the bed, respectively. Three
CO2 analysers were also installed to measure CO2 concentrations The breakthrough adsorption bed (details in Table 2) contained
from inlet, exhaust (vent) and CO2 product lines. Flow meters seven thermocouples (T1–T7) with an interval of 165 mm for mea-
and pressure transducers were placed in the system to monitor suring the temperature changes. Because the adsorption loading of
flow rates and pressures. CO2 and H2O is much larger than N2 and O2, the thermal waves
A simple VSA cycle including adsorption, desorption and re- measured are mainly attributed to CO2 and H2O. Here, ‘binary
pressurisation steps was designed for investigating the effect of breakthrough’ is taken to denote breakthrough experiments done
water vapour on VSA processes (Fig. 3). using a mixture of CO2 and H2O balanced with air as a feed gas

Fig. 2. Single-bed VSA process schematic diagram for cyclic experiments.

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  
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
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
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

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

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

ear regression techniques: ¼
exp P
P exp DH RT
0;ref RT 0;ref
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

and D are: BL a ¼ blT exp P ð10Þ
QB q

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

D ¼ D0 exp ð3Þ K 1 a ¼ k1T exp 1

P ð12Þ
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
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
w¼ 1  K 1 a þ ð1  K 1 aÞ2 þ 4K 0 a ð5Þ equation:
@ 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

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
Fig. 5. Isotherms of water vapour on activated carbon at various temperatures.
adsorption amount of O2 was too small for reliable measurement Lines – Rutherford Extended CMMS model and symbols – experimental data.
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 10% water at an atmosphere pressure). Thus, some of water may
from coal combustion, the CO2 concentration is approximately leave with the vent (waste) gas when activated carbon is used as
12% at atmosphere pressure (equivalent to a partial pressure of an adsorbent in a pressure swing processes. This is desirable as it
12 kPa), at which the CO2 loading is 0.4 mol/kg at 60 °C. The selec- reduces the loading on the vacuum pump. The characteristic shape
tivity of CO2 over N2 (69.5% concentration) is 0.4:0.1. This value is of the adsorption isotherms (Type V) for water shown in Fig. 5
much lower than that on zeolite 13X (CO2:N2 = 1.194:0.137) at the makes it amenable to removal through pressure reduction, in con-
same conditions [4]. Isotherms of water vapour on activated car- trast to the steep Type I isotherm exhibited by water on zeolite
bon at four temperatures are shown in Fig. 5. The extended CMMS 13X. Indeed, desorption of water from activated carbon may be
model represents the experimental data well and the parameters even easier than from activated alumina (type II adsorption for iso-
for the model are listed in Table 4. The isosteric heat of water on therms of water) [34]. Therefore, even though the adsorption
activated carbon calculated by the Clausius–Clapeyron equation, capacity of CO2 and CO2:N2 selectivity on activated carbon is lower
ranges from 40 870 to 30 000 J/mol as the water loading increases than that on zeolite 13X, the unique hydrophobic characteristic of
from 0 to 4 mol/kg (0–10% of water vapour at 60 °C and atmo- activated carbons with the associated advantages in handling
sphere pressure). water make this an interesting choice for CO2 capture applications.
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 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:

¼ K Li ni  ni ð16Þ
where ni is equilibrium adsorbent loading of component i (mol/kg)
and KLi (1/s) was be calculated by:

K Li ¼ ki ð17Þ
Fig. 4. Isotherm data of CO2 and N2 at temperatures of 20 °C, 40 °C and 60 °C. Lines where r is pellet diameter (m), ki is an empirical mass transfer coef-
– Dual-site Langmuir model, symbols – experimental data. 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.
Table 3 According to the adsorption equilibrium of water vapour (Fig. 5)
Parameters in the Dual-site Langmuir model for CO2 and N2. 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
Item MB MD B0 D0 QB QD
(mol/kg) (mol/kg) (1/kPa) (1/kPa) (J/mol) (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
CO2 0.591 7.506 4.05E7 1.69E6 31,381 19,843
N2 1.832 0 3.06E6 16,518
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
(experiment and simulation) and single component breakthrough
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).

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

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

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)

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
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


Water vapor concentration (%)

Pressure (kPa)


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

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.
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
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 (%)

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
(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-
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-   
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

2 Dry gas wet gas

0.00 dry gas

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-
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
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 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
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

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 #
k Q feed Pin Pin k X
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
k  1 g P atm i¼1
k  1
" # through the bed before H2O. Both CO2 and H2O showed slightly
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 [16] M.G. Plaza, S. García, F. Rubiera, J.J. Pis, C. Pevida, Post-combustion CO2 capture
with a commercial activated carbon: comparison of different regeneration
activated carbon is a promising avenue for further VSA technology
strategies, Chemical Engineering Journal 163 (2010) 41–47.
investigation in the application to real wet flue gases. However, [17] C. Shen, Z. Liu, P. Li, J. Yu, Two-stage VPSA process for CO2 capture from flue gas
absolute CO2 capture performance when using activated carbon using activated carbon beads, Industrial & Engineering Chemistry Research 51
adsorbent is inferior to 13X and hence more detailed research is (2012) 5011–5021.
[18] B. Dutcher, K. Krutkramelis, H. Adidharma, M. Radosz, Carbon filter process for
needed to improve the CO2 adsorption properties as well as flue-gas carbon capture on carbonaceous sorbents: field tests of steam-aided
improve the cycle design before implementation is possible. vacuum swing adsorption, Energy & Fuels 26 (2012) 2539–2545.
[19] E.A. Muller, K.E. Gubbins, Molecular simulation study of hydrophilic and
hydrophobic behavior of activated carbon surfaces, Carbon 36 (1998) 1433–
References 1438.
[20] A.J. Fletcher, Y. Yüzak, K.M. Thomas, Adsorption and desorption kinetics for
[1] J.D. Figueroa, T. Fout, S. Plasynski, H. McIlvried, R.D. Srivastava, Advances in hydrophilic and hydrophobic vapors on activated carbon, Carbon 44 (2006)
CO2 capture technology—The U.S. Department of Energy’s Carbon 989–1004.
Sequestration Program, International Journal of Greenhouse Gas Control 2 [21] S. Qi, K.J. Hay, M.J. Rood, M.P. Cal, Equilibrium adsorption and heat of
(2008) 9–20. adsorption for water vapor and activated carbon, Journal of Environmental
[2] A. Meisen, X. Shuai, Research and development issues in CO2 capture, Energy Engineering 126 (2000) 267–271.
Conversion and Management 38 (1997) S37–S42. [22] R.M. Jose, B. Jorge, C. Toma, J.R. Juan, Influence of water vapor on the
[3] A.L. Chaffee, G.P. Knowles, Z. Liang, J. Zhang, P. Xiao, P.A. Webley, CO2 capture adsorption of VOCs on lignin-based activated carbons, Separation Science and
by adsorption: materials and process development, International Journal of Technology 40 (2005) 3113–3135.
Greenhouse Gas Control 1 (2007) 11–18. [23] N. Qi, W.S. Appel, M.D. LeVan, J.E. Finn, Adsorption dynamics of organic
[4] P. Xiao, J. Zhang, P. Webley, G. Li, R. Singh, R. Todd, Capture of CO2 from flue gas compounds and water vapor in activated carbon beds, Industrial and
streams with zeolite 13X by vacuum–pressure swing adsorption, Adsorption Engineering Chemistry Research 45 (2006) 2303–2314.
14 (2008) 575–582. [24] J.H. Kim, C.H. Lee, W.S. Kim, J.S. Lee, J.T. Kim, J.K. Suh, Adsorption equilibria of
[5] J. Zhang, P.A. Webley, P. Xiao, Effect of process parameters on power water vapor on alumina, zeolite 13X, and a zeolite X/activated carbon
requirements of vacuum swing adsorption technology for CO2 capture from composite, Journal of Chemical and Engineering Data 48 (2003) 137–141.
flue gas, Energy Conversion and Management 49 (2008) 346–356. [25] M.M. Maroto-Valer, Z. Tang, Y. Zhang, Carbon dioxide capture and
[6] G. Li, P. Xiao, P. Webley, J. Zhang, R. Singh, M. Marshall, Capture of CO2 from sequestration, Fuel Processing Technology 86 (2005) 1487–1502.
high humidity flue gas by vacuum swing adsorption with zeolite 13X, [26] M.S. Shafeeyan, W. Daud, A. Houshmand, A. Shamiri, A review on surface
Adsorption 14 (2008) 415–422. modification of activated carbon for carbon dioxide adsorption, Journal of
[7] G. Li, P. Xiao, P. Webley, Binary adsorption equilibrium of carbon dioxide and analytical and applied pyrolysis 89 (2010) 143–151.
water vapor on activated alumina, Langmuir 25 (2009) 10666–10675. [27] R.V. Siriwardane, M.S. Shen, E.P. Fisher, J.A. Poston, Adsorption of CO2 on
[8] G. Li, P. Xiao, D. Xu, P.A. Webley, Dual mode roll-up effect in multicomponent molecular sieves and activated carbon, Energy Fuels 15 (2001) 279–284.
non-isothermal adsorption processes with multilayered bed packing, Chemical [28] V. Presser, J. McDonough, G.S. Yeon, Effect of pore size on carbon dioxide
Engineering Science 66 (2011) 1825–1834. sorption by carbide derived carbon, Energy & Environmental Science 4 (2011)
[9] J. Zhang, P. Xiao, G. Li, P.A. Webley, Effect of flue gas impurities on CO2 capture 3059–3066.
performance from flue gas at coal-fired power stations by vacuum swing [29] G. Li, P. Xiao, P.A. Webley, Binary adsorption equilibrium of carbon dioxide and
adsorption, Energy Procedia 1 (2009) 1115–1122. water vapor on activated alumina, Langmuir 25 (2009) 10666–10675.
[10] E.S. Kikkinides, R.T. Yang, S.H. Cho, Concentration and recovery of CO2 from [30] S. Furmaniak, P. Gauden, A. Terzyk, G. Rychlicki, Water adsorption on carbons
flue gas by pressure swing adsorption, Industrial & Engineering Chemistry – critical review of the most popular analytical approaches, Advances in
Research 32 (1993) 2714–2720. Colloid and Interface Science 137 (2008) 82–143.
[11] K.T. Chue, J.N. Kim, Y.J. Yoo, S.H. Cho, R.T. Yang, Comparison of activated carbon [31] S.W. Rutherford, Modeling water adsorption in carbon microspores: Study
and zeolite 13X for CO2 recovery from flue gas by pressure swing adsorption, water adsorption in carbon molecular sieves, Langmuir 22 (2006) 702–708.
Industrial & Engineering Chemistry Research 34 (1995) 591–598. [32] S.W. Rutherford, Application of cooperative multi-molecular sorption theory
[12] B. Na, H. Lee, K. Koo, H.K. Song, Effect of rinse and recycle methods on the for characterization of water adsorption equilibrium in carbon, Carbon 41
pressure swing adsorption process to recover CO2 from power plant flue gas (2003) 579–625.
using activated carbon, Industrial & Engineering Chemistry Research 41 (2002) [33] R.S. Todd, G.B. Ferraris, D. Manca, P.A. Webley, Improved ODE integrator and
5498–5503. mass transfer approach for simulating a cyclic adsorption process, Computers
[13] C. Shen, J. Yu, P. Li, C.A. Grande, A.E. Rodrigues, Capture of CO2 from flue gas by and Chemical Engineering 27 (2003) 883–899.
vacuum pressure swing adsorption using activated carbon beads, Adsorption [34] A. Serbezov, J.D. Moore, Y. Wu, Adsorption equilibrium water vapour on
17 (2010) 179–188. Selexsorb-CDX commercial activated alumina adsorbent, Journal of Chemical
[14] P. Hurst, Removal of CO2 from low pressure flue gas streams using carbon fibre and Engineering Data 56 (2011) 1762–1769.
composite molecular sieves and electric swing adsorption, in: Thomas, S.M. [35] E. Glueckauf, Theory of chromatograph: formula for diffusion into spheres and
Benson (Eds.), Carbon Dioxide Capture for Storage in Deep Geologic their application to chromatography, Transactions of the Faraday Society 51
Formations, Elsevier Ltd., 2005, p. 157. (1955) 1540–1551.
[15] C. Grande, A.E. Rodrigues, Electric swing adsorption for CO2 removal from flue
gases, International Journal of Greenhouse Gas Control 2 (2007) 194–202.