Applied Energy 111 (2013) 731741

Contents lists available at SciVerse ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Carbon dioxide capture by single droplet using Selexol, Rectisol

and water as absorbents: A theoretical approach
Wei-Hsin Chen a,, Shu-Mi Chen b, Chen-I Hung b
a
b

Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan, ROC
Department of Mechanical Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC

h i g h l i g h t s
 A theoretical method for carbon dioxide capture is developed.
 Selexol, Rectisol, and water are taken into account as absorbents.
 The absorption time is more sensitive to the operating temperature.
 Rectisol has the highest capacity to capture CO2 among the three absorbents.
 The absorption rate of Rectisol is larger than the others by an order of magnitude.

a r t i c l e

i n f o

Article history:
Received 12 January 2013
Received in revised form 16 May 2013
Accepted 18 May 2013

Keywords:
Greenhouse gas
Carbon dioxide (CO2) capture
Gas absorption
Selexol and Rectisol
Theoretical analysis
Droplet

a b s t r a c t
A theoretical method is developed to analyze carbon dioxide capture by a stationary single droplet for
evaluating the fundamental mass transfer behavior. In the method, the gas-phase diffusion is predicted
using a similarity method and the technique of separation of variable is employed to approach the liquidphase diffusion. At the interface, a nite difference method is applied to connect the CO2 diffusion
between the two phases. The individual capture processes of CO2 by three different absorbents of Selexol,
Rectisol and water, are taken into account. The operating pressure and temperature of Selexol and water
are in the ranges of 3060 atm and 303333 K, respectively, and they are 3060 atm and 240270 K for
Rectisol. The analysis indicates that an increase in temperature decreases the CO2 capture amount and
absorption time by Selexol and Rectisol droplets. The absorption time is more sensitive to the operating
temperature than the capture amount. As a result, the CO2 absorption rates by the droplets are increased
when the temperature increases. Among the three absorbents, Rectisol has the highest capacity to capture CO2 and its absorption time is in a comparable state to the other two absorbents. This results in that
its absorption rate is larger than the others by an order of magnitude.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Burning fossil fuels is the main source of carbon dioxide
emissions from anthropogenic activities and it accounts for
approximately 95% of the total global annual carbon dioxide
emissions [1]. Currently carbon capture and storage (CCS) is considered to be technically feasible at commercial scale to reduce
anthropogenic carbon dioxide emissions into the atmosphere
[26]. A number of carbon dioxide separation methods, such as
solution absorption, membrane separation, adsorption separation
[7,8], and cryogenics [1,9], can be employed. When one is
concerned with solution absorption, it can be classied into
chemical absorption and physical absorption. Monoethanolamine
(MEA), 2-amino-2-methyl-1-propanol (AMP), aqua ammonia,
Corresponding author. Tel: +886 6 2757575x63600; fax: +886 6 2389940.
E-mail address: weihsinchen@gmail.com (W.-H. Chen).
0306-2619/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.05.051

dual-alkali, and the proprietary solvent marketed by Mitsubishi

Heavy Industries, KS-1, have been employed as chemical solvents
[10] for a variety of applications in industries. With regard to
physical absorption, the gas treating solvents of Selexol (dimethylether polyethylene glycol), Rectisol (chilled methanol), Fluor
(propylene carbonate), and Purisol (N-methyl-2-pyrollidone) are
becoming increasingly popular, especially in the application of
coal gasication [11].
When physical absorption is practiced, CO2 is absorbed into a
absorbent obeying Henrys law, and the gas capture amount by
the absorbent depends on the partial pressure of CO2 and the temperature of absorbent [12]. In general, CO2 removal using physical
absorption allows consuming energy on a reasonable level for its
application in large industrial scale. For example, physical absorption may be a suitable process to remove CO2 from metallurgical
fuel gases, such as blast furnace gases and Corex gases [13]. The
solubility of CO2 in an absorbent is higher at the higher partial

732

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

Nomenclature
c
D
Dm
H
0
H
m
p
pc
R
r
rs
t
T
Ts
Tc
Tr
u
x
X
M
Vi

DH

average molar concentration (M)

diffusion coefcient (m2 s1)
mass diffusion number
nondimensional Henrys law constant
Henrys law constant (M atm1)
nondimensional solute absorption amount
pressure (atm)
critical pressure (atm)
gas constant (=0.082 atm M1 K1)
radial coordinate (m)
aerosol radius (m)
time (s)
temperature (K)
temperature at standard condition (=298.15 K)
critical temperature (K)
reduced temperature
nondimensional concentration
nondimensional radial coordinate
molar fraction
molecular weight (g mol1)
molar volume of CO2 at its normal boiling temperature
(cm3 mol1)
enthalpy of solution (atm K1)

pressures of the gas and lower ambient temperatures. The required

operating conditions of various absorbents are different. For example, the operating pressure and temperature of Selexol are over
30 atm and approximately at 313 K, respectively [14,15]. The operating pressure and temperature of Rectisol are in the ranges of 30
80 atm and 213263 K, respectively [11,16,17]. These conditions
reveal that the operating temperature of Rectisol is much lower
than that of Selexol. When CO2 captured by Rectisol (chilled methanol) and water are compared with each other, the former has a
higher removal capability, especially at low temperatures. Specically, the CO2 solubility in methanol at a normal temperature is larger than in water by a factor of approximately 5, and 815 times
when the temperature of methanol is below 273 K [16].
The integrated gasication combined cycle (IGCC) is a crucial
system for the application of CCS [1820] where the synthesis
gas (or syngas) and power are generated. If the produced syngas
undergoes water gas shift reactions in association with CCS, carbon
free fuel can be produced. In this aspect, the research of CO2 capture via absorption in IGCC systems has been reported in some
studies. Strube and Manfrida [21] focused on two different CO2
capture congurations using Selexol as a physical solvent. In the
rst conguration CO2 and H2S were individually captured,
whereas they were simultaneously captured in the other conguration. They found that the efciency of CO2 capture was higher
in the individual capture system. Chen and Rubin [22] developed
a model to analyze the performances and costs of IGCC plants
where a GE quench gasier along with water gas shift reactors in
the presence/absence of a Selexol system for CO2 capture was employed. They pointed out that the CO2 avoidance cost was lowest
when the total CO2 removal efciency was approximately 90%,
indicating that it was the optimal CO2 capture efciency for the designed plant.
In respect of the application of Rectisol, Li and Robin [23] used
Rectisol as an absorbent to study CO2 removal from syngas in a
polygeneration system. Two congurations, including a singlestage wash process and a two-stage wash process, were analyzed

Greek letters
g
viscosity (cP)
h
polar angle
Rv
diffusion volume (m3 mol1)
s
nondimensional time
/
association factor
w
azimuthal angle
x
acentric factor
Subscript
air
c
g
i
l
qss
ss
s
SL
t
1
vp

air
diffusive characteristic time
gas phase or continuous phase
absorbent i
liquid phase or discrete phase
quasi-saturated state
saturated state
droplet surface or interface
saturated liquid
total pressure
innity
vapor phase

and simulated in Aspen Plus for the process comparison. They reported that the two congurations could fulll CO2 separation,
but they were different in the aspect of process power and energy
demand. Another application of CO2 removal using Rectisol is the
indirect coal liquefaction (ICL). Zhou et al. [17] analyzed CO2 removal in an ICL process utilizing three absorbents of dimethyl carbonate (DMC), MEA, and Rectisol. They discovered that Rectisol
was the most economic option for capturing CO2 in the ICL process.
Although many studies have been published on CO2 capture by
physical solvents, such as Selexol and Rectisol, the theoretical analyses of CO2 capture by these absorbents are still absent so far. In
industry, a variety of devices, such as Venturi scrubbers, spray towers, stirred tanks, packed columns, and bubble columns, have been
adopted to remove CO2 from ue gases [2426]. When one is concerned with spray towers, the basic mass transfer unit is CO2 uptake by single liquid droplets [27]. To evaluate the capture
characteristics of CO2 in spray towers through physical absorption,
the mass transfer behavior of CO2 by three different absorbents,
Selexol, Rectisol, and water, in the form of droplet will be explored
theoretically. The absorption processes at various operating temperatures and pressures will be examined. Finally, the difference
in the capture phenomena of the three absorbents will be
addressed.
2. Mathematical formulation
2.1. Physical description
This study focuses on CO2 capture by a single droplet and three
absorbents of Selexol, Rectisol, and water are considered. A theoretical method is developed and the following assumptions are
adopted to simplify the physical problem: (1) the droplet is in a
quiescent environment; (2) the droplet and its surrounding are isothermal so that no vaporization or condensation occurs; (3) the
uid properties such as the densities and diffusivities of the gas
and liquid phases are constant; (4) phase equilibrium prevails at

733

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

Fig. 1. A schematic of droplet absorption conguration and the equations of two phases in dimensional form.

the interface and the absorption obeys Henrys law; and (5) mass
diffusion in the two phases abides by Ficks law.
Carbon dioxide absorption by droplet is related to the mass
transfer between the gas phase and the liquid phase. The mass diffusion equations in the two phases as well as the initial and boundary conditions are shown in Fig. 1. A two-stage transformation is
developed to solve the equations. In the rst stage, the equations
shown in Fig. 1 are nondimensionalized in terms of a set of nondimensional parameters. The nondimensionalized parameters and
equations are tabulated in Table 1. In the second stage, two parameters of

v g x1  ug

and

v l xul

are dened and substituted into the equations in Table 1. The diffusion equation as well as the initial and boundary conditions of the
gas phase and the liquid phase are given in Table 2.
2.2. Theoretical approach
2.2.1. Gas phase
To solve the gas-phase equation shown in Table 2, a similarity
parameter [28] is dened as

Table 1
A list of dimensionless parameters, diffusion equations as well as initial and boundary conditions (the rst transformation).
Dimensionless parameters
t
tgct ; sl R2 t=D ttlc ; ug
x Rrd ; sg R2 =D
d

cg r;t
cg0 ; ul

clcr;t
H; H1 H0 RT
g0

Description

Gas phase

Governing equation

@ug
@ sg

Initial condition
Boundary conditions

ug x; 0 1;

@ 2 ug
@x2

Liquid phase
2 @ug
x @x

@ul
@ sl

x>1

ug x; sg 1;

ul x; 0 0;

x!1

gs
ug 1; sg cg1
;

Interface conditions
@u

l
@@xu2l 2x @u
@x

l
@xg = @u

Dm
@x x1
ugs uls

sg > 0

@ul 
@x x0

0;

06x61

sl > 0
sl > 0

ls
ul 1; sl ccg1
H;

734

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

Table 2
A list of diffusion equations as well as initial and boundary conditions (the second
transformation).
Description

Gas phase

Governing equation

@v g
@ sg

Initial condition
Boundary conditions

v g x; 0 0; x > 1
v g x; sg 0; x ! 1
v g 1; sg 1  cc 1  ugs sg ; sg > 0

@2 v g
@x2

gs

g1

Description

Liquid phase

Governing equation

@v l
@ sl

Initial condition

v l x; 0 0; 0 6 x 6 1
v l 0; sl 0; sl > 0
v l 1; sl cc H uls sl ; sl > 0

Boundary conditions

the interface are invoked to link ug and ul. The mass ux conservation of the dimensionless concentrations is written as

(T1)




@ug @ul
Dm
@x
@x x1

(T2)
(T3)
(T4)

where Dm(=Dl/DgH) represents the mass diffusion number [31,32].

Meanwhile, the Henrys law is converted into the continuity of
the dimensionless concentrations. That is

11

ugs uls
(T5)

@@xv2l

ls

g1

(T6)
(T7)
(T8)

12

At the interface, Eqs. (8) and (10) give





@ug
1
1  ugs 1 p
@x x1
psg

13

and

x1

g p
2 sg

Eq. (T1) thus becomes an ordinary differential equation and the

counterparts of Eqs. (T1)(T4) are given by
2

d vg
dv g
2g
0
dg2
dg

v g 0 1  ugs

v g g 0; g ! 1

The solution of Eqs. (3)(5) is

vg A B

en dn

where

A 1  ugs ;

2
and B p ugs  1

Therefore, the dimensionless gas-phase concentration ug is obtained

as





1  ugs
x1
 erfc p
ug 1 
2 sg
x

In the above equation, erfc is the complimentary error function [29].

2.2.2. Liquid phase
For the liquid phase, the technique of separation of variable is
P
adopted. Dening v l 1
n1 v n sl sinnpx and substituting it into
Eq. (T5) shown in Table 2, the solution of Eq. (T5) in conjunction
with the conditions of Eqs. (T6) and (T7) is given by [30]

Z sl
1
X
2 2
2 2
1n npen p sl sinnpx 
en p k uls kdk

v l 2

n1

1
2X
2 2
1n npen p sl sinnpx 
x n1

14

Theoretically, ugs and uls can be obtained when Eqs. (12)(14) are
substituted into Eq. (11). However, ul shown in Eq. (10) is piecewise
continuous so that one is unable to differentiate it term by term
[30], as shown in Eq. (14). In other words, a fully analytical solution
is impossible [31]. Instead, a semi-analytical method is developed
to resolve the difculty encountered. At the gasliquid interface,
Eq. (11) is discretized as the following
ugx ugs
x1 xs
uls ulx
xs x2

ugx us
D xg
us ulx
Dxl

Dm

15

where ugx is the gaseous concentration at x1(=xs + Dxg) and ulx is the
liquid-phase concentration at x2(=xs  Dxl). x1 and x2 designate the
grid locations adjacent to the interface in the gas phase and the liquid phase, respectively. With the condition of ugs = uls = us, the
interfacial concentration becomes

us

Dxl ugx ulx Dm Dxg

Dxl Dm Dxg

16

Seeing that the interfacial concentrations of the two phases are the
function of time, an iterative procedure is required to nd us. As
long as us is obtained, ug and ul can be obtained. The criterion of
convergence is 108. That is, when the relative errors of the interfacial concentrations are less than the aforementioned value, the next
time step calculation proceeds. The spatial and temporal concentration distributions of CO2 in the gas phase and in a water droplet in
terms of the theoretical analysis have been compared to the numerical predictions in a previous study [33]. The theoretical results
were in good agreement with the numerical predictions, ascertaining the validity of the conducted method.
2.3. Properties

Hence, the dimensionless liquid-phase concentration is expressed

by

ul 

 
Z sl
1
X
@ul
2 2
2 2
2 np2 en p sl 
en p k uls kdk
@x x1
0
n1

Z sl

2 2
en p k uls kdk

10

2.2.3. Interface
An exact solution and an analytical one in the gas phase and the
liquid phase are obtained, respectively. The dimensionless concentrations of the gas phase and the liquid phase are expressed in
terms of the interfacial concentrations ugs and uls, respectively, as
shown in Eqs. 8 and 10. When the two-phase solutions are simultaneously solved, the mass ux conservation and Henrys law at

The phenomena of gaseous carbon dioxide uptake by single

water droplets at various environmental pressures and temperatures are considered, hence the variations of gaseous mass diffusivity, aqueous mass diffusivity and Henrys law constant at various
conditions are taken into account.
2.3.1. Gas diffusivity
The gas diffusivity of CO2 in air is estimated by [34]

Dg;CO2

0:00143T 1:75
pt M 1=2
air;CO2

1=3
v air

1=3 2
v co2 

 104 

101:325
100

17

where Mair;co2 21=Mair 1=Mco2 1 ; (Rv)air and Rv co2 are

the diffusion volumes of air (=19.7  106 m3 mol1) and CO2,

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

respectively. The values of Mair;co2 and Rv co2 are 17.47 g mol1 and
28.12 m3 mol1, respectively.
2.3.2. Liquid diffusivity
The liquid diffusivity of CO2 in a solvent i is evaluated by [34]

Dl;i

7:4  108 /Mi 1=2 T

V 0:6
co2 gi

 104

18

where Mi, gi, and / are the molecular weight, viscosity, and association factor, respectively, and the value of V co2 is 37.34 cm3 mol1.
The association factor of water and Rectisol are 2.6 and 1.9, respectively. Because Selexol is unassociated, its association factor is 1.0
[34].
2.3.3. Viscosity
The viscosities of water and Rectisol are calculated by [34]

gi

1 DDP r =2:118A
gSL
1 C xDpr

19

where Dpr = (p  pvp)/pc; gSL and x are the viscosity of the saturated
liquid at vapor pressure (pvp) and the acentric factor, respectively. In
Eq. (19), A, C, and D are the functions of Tr and they are expressed as

A 0:999  4:674  104 =1:052T 0:03877

 1:051
r

20

D b0:362=1:004  T r2:573

0:291

21

c  0:209

22

where Tr = T/Tc and Tc is the critical temperature. The values of pc, Tc,
and x of Rectisol and water are listed in Table 3. The viscosity of
Selexol is obtained from the work of Li et al. [35].
2.3.4. Henrys law constants
The Henrys law constants for CO2 absorbed by Selexol and Rectisol at various temperatures can be found in the studies of Xu et al.
[36] and Lunsford and Mcintyre [37], respectively. With regard to
CO2 in water, it can be predicted by the Henrys law as the
following

cl H0 pCO2

23

where H0 is the Henrys law constant and pCO2 stands for the partial
pressure of CO2 in the gas phase. The inuence of temperature on
the constant is estimated by [38]

H0 H0s  exp




DH 1 1

R Ts T

R 2p R p R rs
cl

cl r2 sin hdrdhdw
4pr 3s =3

25

where rs is the droplet radius. In a CO2 capture process, the quasisaturated time (tqss) is identied when the absorption time reaches
the moment of cl;qss 0:99cl;ss where the subscripts qss and ss denote the quasi-saturated state and the saturated state, respectively.
Meanwhile, the absorption rate of a droplet per unit volume is dened as cl;qss =t qss .
3. Results and discussion
Three different absorbents of Selexol, Rectisol, and water in the
form of single droplet for capturing carbon dioxide are adopted.
According to the practical applications of Selexol and Rectisol, their
operating pressure ranges from 30 to 60 atm [11,1417]; the
absorbing temperatures of Selexol and Rectisol are in the ranges
of 303333 K and 240270 K, respectively. To provide a comparison with Selexol, the operating temperature of water is between
303 and 333 K. The CO2 concentration in the ue gas is generally
between 4 and 24 vol% [3942] and the droplet radius in a spray
is in the range of approximately 660 lm [43]; hence the CO2 concentration of 15 vol% and the droplet radius of 30 lm serve as the
basis of this work.
3.1. Properties of absorbents

C 0:079 2:162T r  13:404T 2r 44:171T 3r  84:829T 4r

96:121T 5r  59:813T 6r 15:672T 7r

735

24

H0s means H0 at the standard condition of Ts = 298.15 K. The values of

H0s and DH/R for CO2 in water are 3.4  102 M atm1 and 2400 K,
respectively.

The properties of an absorbent play an important role in determining the CO2 capture process and the absorption amount. For instance, the CO2 ux from the gas phase into an droplet is
proportional to the gas diffusivity and the liquid diffusivity, and
the nal or saturated absorption amount of the solute in the droplet depends on the Henrys law constant. Because of this, the values
of gas diffusivity, liquid diffusivity, and Henrys law constant of Selexol and Rectisol are displayed in Figs. 2 and 3, respectively. For the
two absorbents, Figs. 2a and 3a suggest that their gas diffusivities
(Dg) are sensitive to the operating pressure and they increase as the
operating pressure decreases. On the other hand, an increase in
operating temperature raises the gas diffusivity, regardless of
which solvent is utilized. In contrast, their liquid diffusivities (Dl)
are independent of the operating pressure, but they increase when
the operating temperature rises, as shown in Figs. 2b and 3b. The
Henrys law constant is the function of temperature alone. The constant decreases from 0.093 to 0.056 M atm1 for Selexol [36] when
the operating temperature increases from 303 and 333 K (Fig. 2c);
it also decreases from 0.267 to 0.499 M atm1 for Rectisol [37] as
the operating temperature is lifted from 240 to 270 K (Fig. 3c).
From the curves shown in Figs. 2 and 3, the CO2 capture process
and amount can be preliminarily gured out and a higher temperature lessens the CO2 absorption amount by the two absorbents.
The Henrys law constant of Selexol is lower than that of Rectisol
within their temperature ranges, implying that more CO2 can be
captured by the latter at the saturated or steady state.

2.4. Physical scale

3.2. Transient CO2 capture process by Selexol
In the following discussion, the mean CO2 concentration in a
droplet is dened by

Table 3
Values of critical pressure (pc), critical temperature (Tc), and acentric factor (x) [25].
Solvent

pc (atm)

Tc (K)

x ()

Rectisol
Water

79.91
217.75

512.46
647.14

0.656
0.344

Fig. 4 shows the temporal distributions of mean CO2 concentration (cl ) in the Selexol droplet at four operating temperatures of
303, 313, 323, and 333 K and the operating (total) pressure of
30 atm. Corresponding to the operating temperatures of 303,
313, 323, and 333 K, the nal CO2 concentrations in the droplet
are 0.419, 0.354, 0.295, and 0.253 M, respectively. This reects that
a lower temperature renders a higher nal CO2 concentration at
the saturated state. The inuence of operating pressure on CO2
capture process is examined in Fig. 5 where two operating temperatures of 303 (Fig. 5a) and 333 K (Fig. 5b) are considered. Contrary

736

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

(a)

(a)

1E-06
9E-07

T=303K
T=313K
T=323K
T=333K

8E-07

T=240K
T=250K
T=260K
T=270K

6E-07

7E-07

5E-07

Dg (m2/s)

Dg (m2 /s)

7E-07

6E-07

4E-07

5E-07
3E-07

4E-07
3E-07
25

30

35

40

45

50

55

60

2E-07

65

P (atm)

30

35

40

45

50

55

60

65

P (atm)

(b) 1.6E-09

(b) 2.2E-09

1.4E-09

2E-09
1.8E-09

D l (m2 /s)

1.2E-09

Dl (m2 /s)

25

1E-09
8E-10

1.6E-09
1.4E-09
1.2E-09

6E-10
4E-10
30

1E-09
35

40

45

50

55

8E-10

60

P (atm)

(c)

0.1

0.09

0.08

0.07

0.06

0.05
300

305

310

315

320

35

40

45

50

55

60

P (atm)

Henry's law constant (M/atm)

Henry's law constant (M/atm)

(c)

30

325

330

335

340

T (K)

0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
235

240

245

250

255

260

265

270

275

T (K)

Fig. 2. Distributions of (a) gas diffusivity, (b) liquid diffusivity, and (c) Henrys law
constant for Selexol absorption.

Fig. 3. Distributions of (a) gas diffusivity, (b) liquid diffusivity, and (c) Henrys law
constant for Rectisol absorption.

to the impact of temperature, a higher operating pressure intensies the CO2 capture process, as a result of higher nal CO2 concentration. In the initial period, the mean concentration of CO2 grows
faster at a higher operating pressure and a lower temperature. It
follows that the absorption rate of CO2 by the droplet is higher at
the aforementioned conditions.
The proles of mean CO2 concentration at the quasi-saturated
time cl;qss ) are shown in Fig. 6a. Upon inspection of the proles

of cl;qss at the quasi-saturated time shown in Fig. 6a, the value of

cl;qss is the function of the operating temperature and pressure. In
contrast, the value of tqss is hardly affected by the operating pressure, as shown in Fig. 6b. This can be explained by the independence of liquid diffusivity from the operating pressure (Fig. 2b).
By examining the absorption rate of the droplet, Fig. 6c depicts that
the environment with higher operating temperature and pressure

737

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

P t =30atm,

0.5

X g, CO = 0.15
2

_
cl,ss =0.419 (M)

0.4

(a) 0.9
0.8
0.7

0.295

cl,qss (M)

0.253

0.5

0.2

cl (M)

0.3

0.4
0.3

0.1

cl (M)

T=303K
T=313K
T=323K
T=333K

0.2

0.4

0.6
0.5
0.4

0.2
0.1

0.3

0
-0.1

-0.1

P=30atm
P=40atm
P=50atm
P=60atm

0.354

0.6

0.05

0.8

0.1

t (s)

1.2

0.15

0.2
300

0.2

305

310

315

1.4

320

325

330

335

340

325

330

335

340

325

330

335

340

T (K)

t (s)
Fig. 4. Temporal distributions of mean CO2 concentration in Selexol droplet at the
operating pressures of 30 atm.

(b) 0.6
0.5

(a) T=303K,

X g, CO = 0.15
2

tqss (s)

0.9
0.8

0.4

0.7

cl (M)

0.6

0.3

0.5

0.9
0.8

0.4

0.7

0.2
300

0.6

0.2
0.1
0

0.2

0.4

P=30atm
P=40atm
P=50atm
P=60atm

cl (M)

0.3

0.5

305

310

315

320

T (K)

0.4
0.3
0.2

(c)

0.1
0
0

0.6

0.05

0.8

0.1
t (s)

0.15

0.2

1.2

1.8

0.55

Absorption rate (M/s)

t (s)

(b) T=333K, Xg,CO = 0.15

2

0.5
0.45
0.4

cl (M)

0.35

1.4
1.2
1
0.8

0.3

0.6

0.25

0.6
300

0.5

0.4

305

310

315

320

T (K)

0.3

cl (M)

0.2
0.15

Fig. 6. Proles of (a) the mean CO2 concentration in the liquid phase at the quasisaturated time, (b) the quasi-saturated time, and (c) the absorption rate of the
Selexol droplet.

0.2

0.1

0.1

0.05
0

1.6

0.05

0.1

0.15

0.2

t (s)

0.2

0.4

0.6

t (s)
Fig. 5. Temporal distributions of mean CO2 concentration in Selexol droplet at the
operating temperatures of (a) 303 and (b) 333 K.

enhances the CO2 capture process. A higher operating temperature

lowers the mean CO2 concentration (Fig. 6a) and, thereby, the CO2
capture amount, but it intensies the gas and liquid diffusivities so
as to reduce the quasi-saturated time (Fig. 2a and b). The role
played by the diffusivities in the absorption rate prevails over the

738

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

3.5

1.422

cl,qss (M)

0.8

2.5
2

2.5

1.5

0.2

0.5

0.5
0

1.5

cl (M)

T=240K
T=250K
T=260K
T=270K

0.4

1.2

1.202

0.4

0.6

0.05

0.1
t (s)

0.8

0.15

0
235

0.2

240

245

250

Fig. 7. Temporal distributions of mean CO2 concentration in Rectisol droplet at the

operating pressures of 30 atm.

260

265

270

275

260

265

270

275

260

265

270

275

0.35

0.3

tqss (s)

(a) T=240K, Xg,CO2 = 0.15

255

T (K)

(b) 0.4

t (s)

P=30atm
P=40atm
P=50atm
P=60atm

1.741

1.6

5
4.5

_
cl,ss =2.243 (M)

cl (M)

(a)

P t =30atm, Xg,CO = 0.15

2.4

0.25
4
0.2
3

cl (M)

0.15
235

P=30atm
P=40atm
P=50atm
P=60atm

0.2

245

250

(c)

2
1
0

255

14
13

0.4

0.05

0.1
t (s)

0.6

0.15

0.2

0.8

t (s)

(b) T=270K, X g,CO = 0.15

2

2.5

240

T (K)

12

Absorption rate (M/s)

cl (M)

11
10
9
8
7
6
5
235

1.5
3

cl (M)

250

255

Fig. 9. Proles of (a) the mean CO2 concentration in the liquid phase at the quasisaturated time, (b) the quasi-saturated time, and (c) the absorption rate of the
Rectisol droplet.

2
1.5

cl (M)

245

T (K)

2.5

240

0.5

0.5
0

0.05

0.1
t (s)

0.15

0.2

0
0

0.1

0.2

0.3

0.4

t (s)
Fig. 8. Temporal distributions of mean CO2 concentration in Rectisol droplet at the
operating temperatures of (a) 303 and (b) 333 K.

CO2 capture amount. This is the reason that the absorption rate
rises with increasing operating temperature.
3.3. Transient CO2 capture process by Rectisol
Fig. 7 displays the temporal distributions of cl in the Rectisol
droplet at four operating temperatures of 240, 250, 260, and
270 K and the operating pressure of 30 atm. As a whole, the trend

739

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

(a) 0.5

3.9

Selexol
Water
Selexol/Water

3.8

cl,qss (M)

0.4

3.7
3.6

0.3

3.5
3.4

0.2

Ratio (-)

3.3
3.2

0.1

3.1
0
3
295 300 305 310 315 320 325 330 335 340

T (K)

(b) 0.7

3.3

0.6

3.2

tqss (s)

0.5

3.1

0.4
3
0.3

Ratio (-)

in the curves of cl shown in Fig. 7 is similar to that in Fig. 4. However, the distributions of the curves shown in Fig. 7 are higher than
those in Fig. 4, stemming from the larger Henrys law constant of
Rectisol (Fig. 3c) when compared to that of Selexol (Fig. 2c). For
example, the value of cl at the saturated state shown in Fig. 7 is
in the range of 1.2022.243 M, whereas it is between 0.253 and
0.419 M in Fig. 4. It is thus recognized that the CO2 capture amount
by Rectisol is higher than that by Selexol. When the temporal distributions of cl at various operating pressures under the temperatures of 240 (Fig. 8a) and 270 K (Fig. 8b) are examined, it is not
surprising that a higher operating pressure or a lower operating
temperature is conducive to the CO2 capture process.
Fig. 9 shows the distributions of cl;qss , tqss, and the absorption
rate of CO2 by the Rectisol droplet. Within the investigated temperature and pressure ranges, the values of cl;qss in the Selexol and Rectisol droplets are in the ranges of 0.250.83 M (Fig. 6a) and 1.19
4.44 M (Fig. 9a), respectively. This reveals that the Rectisol droplet
provides a higher capacity for capturing CO2 than the Selexol droplet. For the Rectisol droplet, the CO2 capture process is achieved
within 0.4 s (Fig. 9b). A higher operating temperature leads to a
shorter absorption time. Similar to the Selexol droplet, increasing
temperature or pressure facilitates the absorption rate (Fig. 9c).
However, the inuence of operating temperature on the absorption
rate of the Rectisol droplet is not as signicant as that of the Selexol
droplet (Fig. 6c). A comparison to the Selexol droplet (Fig. 6), both
the CO2 absorption amount and the absorption rate of the Rectisol
droplet (Fig. 9) are higher the Selexol droplet to a certain extent.
The CO2 concentration in the ue gas from oxyfuel combustion
typically ranges from 63 to 87 vol% [39,4447]. Seeing that the
CO2 partial pressure has a pronounced inuence on the CO2 capture amount and absorption rate (Figs. 6 and 9), the performance
of CO2 absorption by Selexol or Rectisol droplets can be further improved if they are employed to capture CO2 in oxyfuel combustion
processes.

2.9

0.2

2.8

0.1

0
2.7
295 300 305 310 315 320 325 330 335 340

T (K)

(c) 1.1

1.5

0.12
Selexol
Water

Henry's law constant (M/atm)

0.1

1.4

1.3

0.9

1.2
0.8

Ratio (-)

Water is a common absorbent to capture gas solutes. To give an

insight into the difference of CO2 capture between a Selexol droplet
and a water droplet with the radius of 30 lm, their Henrys law
constants are presented in Fig. 10. For the operating temperature
range of 303333 K, the Henrys law constant of Selexol is by far

Absorption rate (M/s)

3.4. A comparison between Selexol and water

1.1

0.7

0.9
0.6
295 300 305 310 315 320 325 330 335 340

T (K)
0.08
Fig. 11. Proles of (a) the mean CO2 concentration in the liquid phase at the quasisaturated time, (b) the quasi-saturated time, and (c) the absorption rate of the
Selexol and water droplets and their ratios at the operating pressure of 30 atm.

0.06

0.04

0.02

0
300

310

320

330

340

T (K)
Fig. 10. A comparison of the Henrys law constants of Selexol and water at various
operating temperatures.

larger than that of water. This means that Selexol used for CO2 capture is more feasible that water. The proles of cl;qss , tqss, and the
absorption rate of the Selexol droplet and the water droplet at
the operating pressures of 30 and 60 atm are shown in Figs. 11
and 12, respectively. It can be seen that the value of cl;qss in the Selexol droplet at the quasi-saturated state is larger than in the water
droplet by factors of 3.123.84 (Figs. 11a and 12a). Alternatively,
the time required for the Selexol droplet reaching the quasi-saturated state is also longer than the water droplet by factors of
2.73.3 (Figs. 11b and 12b). It is of interest that the trend in the
absorption rate of the Selexol droplet is different from that of
the water droplet (Figs. 11c and 12c). Specically, increasing

740

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

(a)

1
0.9

3.8

0.8

3.7
3.6

0.6

3.5

0.5

3.4

0.4

Ratio (-)

cl,qss (M)

0.7

Table 4
A summary of CO2 capture by Selexol, Rectisol, and water.

3.9

Selexol
Water
Selexol/Water

3.3

0.3
0.2

3.2

0.1

3.1

3
0
295 300 305 310 315 320 325 330 335 340

T(K)

(b) 0.7

3.3

0.6

3.2
3.1

0.4
3
0.3

Ratio (-)

tqss (s)

0.5

2.9

0.2

2.8

0.1

2.7
0
295 300 305 310 315 320 325 330 335 340

T(K)

(c) 2.1

1.5
1.4

1.9
1.3

1.8

1.2

1.7
1.6

Ratio (-)

Absorption rate (M/s)

1.1

1.5
1

1.4
1.3
295

0.9
300 305 310 315 320 325 330 335 340

T (K)
Fig. 12. Proles of (a) the mean CO2 concentration in the liquid phase at the quasisaturated time, (b) the quasi-saturated time, and (c) the absorption rate of the
Selexol and water droplets and their ratios at the operating pressure of 60 atm.

temperature raises the absorption rate of the Selexol droplet, but it

slightly diminishes the absorption rate of the water droplet. As a
result, an increase in operating temperature signicantly enlarges
the absorption rate ratio between the Selexol droplet and the water
one. However, for the operating temperature of 303 K, the absorption rate of the former is lower than that of the latter, regardless of
the operating pressure of 30 or 60 atm.
Finally, the physical scales of cl;qss , tqss, and absorption rate using
the three absorbents to capture CO2 are summarized in Table 4 for
comparison. The value of cl;qss in water is the lowest among the
three absorbents, whereas it is the highest in Rectisol. The capture
process of Selexol is longer than the other two absorbents, whereas

Absorbent

Selexol

Rectisol

Water

Molar fraction of CO2

Operating pressure (atm)
Operating temperature (K)
Mean CO2 quasi-saturated
concentration (M)
Quasi-saturated time (s)
Absorption rate (M s1)

0.15
3060
303333
0.2500.830

240270
1.1904.442

303333
0.0650.266

0.2550.561
0.7421.951

0.1820.370
6.06612.946

0.0920.175
0.7071.521

water has the shortest absorption period. However, their absorption times are in a comparable state. After simultaneously considering the physical scales of cl;qss and tqss, the absorption rates of
water and Selexol are in the same order of magnitude, as shown
in Figs. 11c and 12c. In contrast, the absorption rate of Rectisol is
larger than the other two by an order of magnitude (Table 4). This
reects that using Rectisol gives the best performance of CO2 capture among the three absorbents. However, it should be mentioned
that the implementation of CO2 capture by Rectisol is based on low
temperature operation. This needs to refrigerate the solvent, thereby resulting in high capital and operating costs of the plant [10].
4. Conclusions
The capture process of carbon dioxide by a single droplet has
been analyzed through a theoretical approach where three different absorbents of Selexol (dimethylether polyethylene glycol), Rectisol (chilled methanol), and water have been regarded. In the
method, the CO2 diffusion in gas phase is solved through a similarity method, whereas the diffusion in the liquid phase is predicted
by use of the technique of separation of variable. The theoretical
difculty encountered at the interface is overcome using the nite
difference scheme. From the obtained results, it is found that
increasing temperature decreases both the CO2 capture amount
by a droplet and its absorption time, regardless of which absorbent
is employed. The inuence of varying temperature on the absorption time is beyond on the CO2 capture amount; this results in the
growth of the absorption rates of CO2 by the droplets when the
temperature increases. The variation of operating pressure almost
plays no part in determining the absorption time; this leads to a
pronounced growth in the absorption rate as the operating pressure is raised. When the absorption behavior of the three absorbents is compared with each other, more CO2 can be captured by
Rectisol than by the other two absorbents. Meanwhile, the absorption times of the three solvents are in a comparable state. As a consequence, the absorption rate of the Rectisol droplet is larger than
the other two by an order of magnitude. If the partial pressure of
CO2 in a ue gas is lifted, say, from oxyfuel combustion, the efciency of CO2 capture by a droplet can be further improved. The
present study has provided a fundamental insight into the application of sprays for CO2 capture using Selexol, Rectisol, and water as
solvents. If a droplet is in motion, the RanzMarshall correlation
can be employed to describe the inuence of convective ow on
the mass transfer. On the other hand, if the droplet is in a non-isothermal environment, the energy equations in the gas phase and
the liquid phase should be included in the governing equations,
and the ClausiusClapeyron equation has to be utilized to link
the vaporization or condensation process at the interface. This topic deserves further investigation in the future.
Acknowledgment
The authors gratefully acknowledge the nancial support of the
National Science Council, Taiwan, ROC, for this study.

W.-H. Chen et al. / Applied Energy 111 (2013) 731741

References
[1] Li Y, Liu Y, Zhang H, Liu W. Carbon dioxide capture technology. Energy Procedia
2011;11:250815.
[2] Gibbins J, Chalmers H. Carbon capture and storage. Energy Policy
2008;36:431722.
[3] Li H, Yan J, Yan J, Anheden M. Impurity impacts on the purication process in
oxy-fuel combustion based CO2 capture and storage system. Appl Energy
2009;86:20213.
[4] Li H, Ditaranto M, Yan J. Carbon capture with low energy penalty:
supplementary red natural gas combined cycles. Appl Energy 2012:1649.
[5] Hu Y, Li H, Yan J. Techno-economic evaluation of the evaporative gas turbine
cycle with different CO2 capture options. Appl Energy 2012;89:30314.
[6] Hu Y, Li X, Li H, Yan J. Peak and off-peak operations of the air separation unit in
oxy-coal combustion power generation systems. Appl Energy 2013. <http://
www.sciencedirect.com/science/article/pii/S0306261912008781>.
[7] Hedin N, Andersson L, Bergstrm L, Yan J. Adsorbents for the post-combustion
capture of CO2 using rapid temperature swing or vacuum swing adsorption.
Appl Energy 2013;104:41833.
[8] Cheung O, Bacsik Z, Liu Q, Mace A, Hedin N. Adsorption kinetics for CO2 on
highly selective zeolites NaKA and nano-NaKA. Appl Energy 2013. <http://
www.sciencedirect.com/science/article/pii/S0306261913000263>.
[9] Figueroa JD, Timothy F, Sean P, Howard M, Srivastava RD. Advances in CO2
capture technology The US Department of Energys Carbon Sequestration
Program. Int J Greenhouse Gas Control 2008;2:920.
[10] Olajire AA. CO2 capture and separation technologies for end-of-pipe
applications a review. Energy 2010;35:261028.
[11] Burr B, Lyddon L. A comparison of physical solvents for acid gas removal. Bryan
Research and Engineering Inc.; 2008.
[12] Chen WH, Lu JJ. Microphysics of atmospheric carbon dioxide uptake by a cloud
droplet
containing
a
solid
nucleus.
J
Geophys
Res-Atmos
2003;108(D15):44708.
[13] Lampert K, Ziebik A. Comparative analysis of energy requirements of CO2
removal from metallurgical fuel gases. Energy 2007;32:5217.
[14] Breckenridge W, Holiday A, Ong JOY, Sharp C. Use of Selexol process in coke
gasication to ammonia project. Laurance Reid Gas Conditioning Conference;
2000.
[15] Hackett GA, Gerdes K. Trace species partitioning as affected by cold gas
cleanup conditions: a thermodynamic analysis. Natl Energy Tech Lab
2011.
[16] Kaneco S, Katsumata H, Suzuki T, Ohta K. Electrochemical reduction of carbon
dioxide to ethylene at a copper electrode in methanol using potassium
hydroxide and rubidium hydroxide supporting electrolytes. Electrochimica
Acta 2006;51:331621.
[17] Zhou W, Zhu B, Chen D, Zhao F, Fei W. Technoeconomic assessment of Chinas
indirect coal liquefaction projects with different CO2 capture alternatives.
Energy 2011;36:655966.
[18] Kunze H, Spliethoff H. Assessment of oxy-fuel, pre- and post-combustionbased carbon capture for future IGCC plants. Appl Energy 2012;94:10916.
[19] Martelli E, Kreutz T, Carbo M, Consonni S, Jansen D. Shell coal IGCCS with
carbon capture: conventional gas quench vs. innovative congurations. Appl
Energy 2011;88:397889.
[20] Siefert NS, Litster S. Exergy and economic analyses of advanced IGCCCCS and
IGFCCCS power plants. Appl Energy 2013;107:31528.
[21] Strube R, Manfrida G. CO2 capture in coal-red power plants impact on plant
performance. Int J Greenhouse Gas Control 2011;5:71026.
[22] Chen C, Rubin ES. CO2 control technology effects on IGCC plant performance
and cost. Energy Policy 2009;37:91524.
[23] Li S, Robin S. Rectisol wash process simulation and analysis. J Cleaner Prod
2013;39:3218.

741

[24] Tippayawong N, Thanompongchart P. Biogas quality upgrade by simultaneous

removal of CO2 and H2S in a packed column reactor. Energy 2010;35:45315.
[25] Lu Y, Ye X, Zhang Z, Khodayari A, Djukadi T. Development of a carbonate
absorption-based process for post-combustion CO2 capture: the role of
biocatalyst to promote CO2 absorption rate. Energy Procedia 2011;4:128693.
[26] Li L, Zhao B. Numerical simulation of gas and liquid ow within a vortex spray
tower. Energy Procedia 2012;16:10727.
[27] Chen WH. Air pollutant absorption by single moving droplets with drag force
at moderate Reynolds numbers. Chem Eng Sci 2006;61:44958.
[28] Seinfeld JH, Pandis SN. Atmospheric chemistry and physics. New York: Wiley;
1998.
[29] Myers GE. Analytical methods in conduction heat transfer. 2nd ed. New
York: Genium Pub. Corp; 1987.
[30] Strauss WA. Partial differential equations: an introduction. 2nd ed. New
York: Wiley; 2008.
[31] Chen WH. An analysis of gas absorption by a liquid aerosol in a stationary
environment. Atmos Environ 2002;36:367183.
[32] Chen WH. Scavenging waves and inuence distances of gas absorption around
single liquid aerosols in clouds. Atmos Environ 2006;40:50011.
[33] Chen WH, Hou YL, Hung CI. A theoretical analysis of the capture of greenhouse
gases by single water droplet at atmospheric and elevated pressures. Appl
Energy 2011;88:512030.
[34] Poling BE, Prausnitz JM, OConnell JP. The properties of gases and liquids. 5th
ed. New York: McGraw-Hill; 2001.
[35] Li J, Mundhwa M, Henni A. Volumetric properties, viscosities, refractive
indices, and surface tensions for aqueous Genosorb 1753 solutions. J Chem Eng
Data 2007;52:9558.
[36] Xu Y, Schutte RP, Hepler LG. Solubilities of carbon dioxide, hydrogen sulde
and sulfur dioxide in physical solvents. Can J Chem Eng 1992;70:56973.
[37] Lunsford K, Mcintyre G. Decreasing contactor temperature could increase
performance. Bryan Research and Engineering Inc; 2006.
[38] Seinfeld JH. Atmospheric chemistry and physics of air pollution. New
York: Wiley; 1986.
[39] Bouillona BA, Hennes S, Mahieux C. ECO2: Post-combustion or oxyfuel a
comparison between coal power plants with integrated CO2 capture. Energy
Procedia 2009;1:401522.
[40] Sipcz N, Tobiesen FA, Assadi M. The use of articial neural network models
for CO2 capture plants. Appl Energy 2011;88:236876.
[41] Mores P, Scenna N, Mussati S. Post-combustion CO2 capture process:
equilibrium stage mathematical model of the chemical absorption of CO2
into monoethanolamine (MEA) aqueous solution. Chem Eng Res Des
2011;89:158799.
[42] Lawal A, Wang M, Stephenson P, Obi O. Demonstrating full-scale postcombustion CO2 capture for coal-red power plants through dynamic
modelling and simulation. Fuel 2012;101:11528.
[43] Chen WH, Chen SM, Hung CI. A theoretical approach of absorption processes of
air pollutants in sprays under dropletdroplet interaction. Sci Total Environ
2013;444:33646.
[44] Jordal K, Anheden M, Yan J, StrOmberg L. Oxyfuel combustion for coal-red
power generation with CO2 captureopportunities and challenges.
Greenhouse Gas Control Technol 2005;1:2019.
[45] Saida A, Eloneva S, Fogelholm CJ, Fagerlund J, Nduagu E, Zevenhoven R.
Integrated carbon capture and storage for an oxyfuel combustion process by
using carbonation of Mg(OH)2 produced from serpentinite rock. Energy
Procedia 2011;4:283946.
[46] Faber R, Yan J, Stark F, Priesnitz S. Flue gas desulphurization for hot recycle
oxyfuel combustion: experiences from the 30MWth oxyfuel pilot plant in
Schwarze Pumpe. Int J Greenhouse Gas Control 2011;5S:S21023.
[47] Hu Y, Yan J, Li H. Effects of ue gas recycle on oxy-coal power generation
systems. Appl Energy 2012;97:25563.