Chemical Engineering Science 61 (2006) 65116529

www.elsevier.com/locate/ces
Simulations of chemical absorption in pilot-scale and industrial-scale packed
columns by computational mass transfer
G.B. Liu
a
, K.T. Yu
a
, X.G. Yuan
a,
, C.J. Liu
a
, Q.C. Guo
b
a
State Key Laboratory for Chemical Engineering (Tianjin University), Chemical Engineering Research Center and School of Chemical Engineering and
Technology, Tianjin University, Tianjin, 300072, China
b
Institute of photoelectronics thin lm devices and technique, Nankai University, Tianjin, 300071, China
Received 28 December 2005; received in revised form 22 May 2006; accepted 22 May 2006
Available online 3 June 2006
Abstract
A complex computational mass transfer model (CMT) is proposed for modeling the chemical absorption process with heat effect in packed
columns. The feature of the proposed model is able to predict the concentration and temperature as well as the velocity distributions at once
along the column without assuming the turbulent Schmidt number, or using the experimentally measured turbulent mass transfer diffusivity.
The present model consists of the differential mass transfer equation with its auxiliary closing equations and the accompanied formulations of
computational uid dynamics (CFD) and computational heat transfer (CHT). In the mathematical expression for the accompanied CFD and
CHT, the conventional methods of k.c and t
2
.c
t
are used for closing the momentum and heat transfer equations. While for the mass transfer
equation, the recently developed concentration variance c
2
and its dissipation rate c
c
equations (Liu, 2003) are adopted for its closure. To test the
validity of the present model, simulations were made for a pilot-scale randomly packed chemical absorption column of 0.1 m ID and 7 m high,
packed with 1/2

ceramic Berl saddles for CO

2
removal from gas mixture by aqueous monoethanolamine (MEA) solutions (Tontiwachwuthikul
et al., 1992 ) and an industrial-scale randomly packed chemical absorption column of 1.9 m ID and 26.6 m high, packed with 2

stainless
steel Pall rings for CO
2
removal from natural gas by aqueous MEA solutions (Pintola et al., 1993). The simulated results were compared
with the published experimental data and satisfactory agreement was found between them in both concentration and temperature distributions.
Furthermore, the result of computation also reveals that the turbulent mass transfer diffusivity D
t
varies along axial and radial directions. Thus
the common viewpoint of assuming constant D
t
throughout the whole column is questionable, even for the small size packed column. Finally,
the analogy between mass transfer and heat transfer in chemical absorption is demonstrated by the similarity of their diffusivity proles.
2006 Elsevier Ltd. All rights reserved.
Keywords: Computational mass transfer (CMT); Turbulent mass transfer diffusivity; Simulation; Packed bed; Chemical absorption; Mathematical modeling
1. Introduction
In the chemical industry, packed columns have been widely
used in separation and purication processes involving gas and
liquid contact such as distillation and absorption due to its high
efciency, high capacity and lowpressure drop. Despite the suc-
cess of applying structured packing in the recent years (Gualito
et al., 1997; Spiegel and Meier, 2003), the randomly packed
columns are still commonly used in the separation processes.
The mass transfer process undertaking in a packed column,

Corresponding author. Tel.: +86 22 27404732; fax: +86 22 27404496.

E-mail address: yuanxg@tju.edu.cn (X.G. Yuan).
0009-2509/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2006.05.035
especially the diffusion of species in the liquid phase, is strongly
coupled with the extent of turbulent ow as well as the heat
effect if involved. As the process is complicated, the behavior
and prediction of the mass transfer in packed column have been
an active research area for decades in both experimental work
and mathematical modeling. It is known that, in most case,
the conventional plug-ow assumption is not applicable due
to the presence of non-uniform packing and the creating tur-
bulence, especially in the case of column-to-particle diameter
ratios ( =aspect ratios) lower than about 10 (Wen et al., 2001;
Giese et al., 1998; Ziolkowska and Ziolkowski, 1988; Lerou
and Froment, 1977; Bey and Eigenberger, 1997; Zhang, 1986;
Zhang and Yu, 1988; Yuan et al., 1989). Thus the investigation
6512 G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529
on the non-uniform distributions of velocity and temperature
in the packed column have been received much attention in the
past. The notable advance is coming from the use of compu-
tational uid dynamics (CFD) and computational heat transfer
(CHT) to help the solution of this problem, as the velocity and
temperature proles in the packed column can be predicted by
such methodology (Yin et al., 2000, 2002; Hjertager et al., 2002;
Liu, 2001, Jiang et al., 2002a,b). However, for the prediction of
concentration prole, it is necessary to use the empirical turbu-
lent Schmidt numbers or the experimentally determined disper-
sion coefcients obtained by tracer technique as an approximate
substitution to the unknown turbulent mass transfer diffusivity
(Yin et al., 2000; de Lemos and Mesquita, 2003). Obviously,
the use of such empirical method for nding the concentration
distribution is not dependable, especially for the cases where
the empirical relationship or the experimental coefcients for
the investigated system are unavailable. The best way of over-
coming this difculty is to eliminate the turbulent mass transfer
diffusivity from the differential mass transfer equation in the
model computation. The recently developed c
2
.c
c
model pro-
posed by Liu (2003) is suitable for this purpose. With the idea
of using such model, Sun et al. (2005) successfully obtained the
concentration proles on the sieve trays of a commercial-scale
distillation column without relying on the empirical correlation
of turbulent mass transfer diffusivity and showed satisfactory
agreement with the published experimental measurement.
The chemical absorption has been extensively used in gas
purication as well as in many chemical processes. For in-
stance, the absorption of CO
2
in randomly packed columns by
alkaline solutions such as NaOH, monoethanolamine (MEA),
diethanolamine (DEA) and methyldiethanolamine (MDEA)
aqueous solutions is commonly adopted in acid gas treatments.
Among them, the use of aqueous MEA solutions as absorbent
takes more share in the industrial process of CO
2
removal, and
the research concerned have been reported (Danckwerts, 1979;
Hikita et al., 1979; Tontiwachwuthikul et al., 1992; Astarita
et al., 1964; Aboudheir et al., 2003). However, the investiga-
tions were mostly based on overall mass balances and plug
ow, without considering the non-ideal behaviors of ow, heat
and mass transfer in the randomly packed bed. The problem
of close modeling is remained to be solved.
With the increasing power of computer and rapid devel-
opment of numerical computational method, it is possible to
solve the problem by establishing a complex model to describe
in-depth the transport phenomena of the chemical absorption
process with a set of differential equations. Thus, a complex
computational mass transfer model (CMT) is proposed in this
paper for modeling the chemical absorption process with heat
effect. The present model consists of the differential mass trans-
fer equation, closing with the c
2
.c
c
equations, and the accom-
panied formulations of CFD and CHT. In the mathematical
formulation of the accompanied CFD and CHT, the conven-
tional methods of k.c and t
2
.c
t
are used for closing the mo-
mentum and heat transfer equations. To testify the validity of
the proposed model, simulation was made to a pilot-scale and
an industrial-scale randomly packed columns undertaking the
chemical absorption of CO
2
by aqueous MEA solution. The
simulated results on the distributions of temperature and con-
centration along the axial and radial directions were compared
with the published experimental data.
2. The reaction mechanism of CO
2
absorption by aqueous
MEA solution
When CO
2
is being absorbed and reacts with aqueous MEA
solutions, the following three overall reactions are taken place
at the condition of carbonation ratio (or CO
2
loading) less than
0.5 mol of CO
2
per mole of MEA. (Danckwerts, 1979; Astarita
et al., 1964):
CO
2,g
CO
2,L
+H
A
, (1)
CO
2,L
+2BNH
2
k
2
BNHCOO

+BNH
+
3
+H
R
, (2)
CO
2,L
+BNHCOO

+2H
2
O BNH
+
3
+2HCO

3
, (3)
where letter B denotes the group HOCH
2
CH
2
, step (1) repre-
sents the physical absorption of CO
2
by water, H
A
is the accom-
panied heat of solution. At very short times of the liquidgas
encountered in industrial absorbers, the reaction (3) can be ne-
glected, and only reaction (2) affects the absorption rate of CO
2
(Sada et al., 1976). Reaction (2) takes place in two steps:
CO
2,L
+BNH

2
BNHCOO

+H
+
, (4)
BNH
2
+H
+
BNH
+
3
. (5)
Reaction (4) could be considered as second order, and is the
rate controlling step, because reaction (5) is a proton transfer
reaction and virtually instantaneous. Therefore, the absorption
of CO
2
in MEA solutions can be regarded as gas absorption
accompanied by an irreversible second-order reaction with a
stoichiometric coefcient of 2, and the overall reaction is rep-
resented by reaction (2). The reaction rate Rc can be expressed
by the following equation:
Rc =k
2
[CO
2
][MEA]. (6)
3. The experimental data available
The validity of the proposed model for the chemical absorp-
tion of CO
2
by MEA solution can be testied by the compar-
ison between the model prediction and the experimental data.
There are two sets of data available:
(1) The experimental data of a pilot-scale column were re-
ported by Tontiwachwuthikul et al. (1992). They conducted the
experiment for the absorption of CO
2
from air by using aque-
ous MEA solution at total pressure of 103.15 kPa in a column
of 0.1 m ID and packed with 1/2

( 1.27 cm) ceramic Berl

saddles with a total packing height of 6.55 m. The column con-
sisted of six equal-height sections, and the samples were taken
at the inlet and outlet of each section for analyzing the concen-
tration.
(2) The operating data of an industrial column were reported
by Pintola et al. (1993). The column was used for reducing the
CO
2
content in the natural gas from approximately 2% to less
G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529 6513
than 100 ppm by the aqueous MEA solution absorption. The
column was 1.9 min diameter and packed with 2

stainless steel
Pall rings in three sections with total packing height of 14.1 m.
The operating pressure was ranging from 5.39 to 7.60 atm. All
their experimental data were given only at the top and the
bottom of column.
4. The computational mass transfer (CMT) model for the
chemical absorption concerned
4.1. Assumptions
The following assumptions are made for the present CMT
model for simulating the chemical absorption of CO
2
by aque-
ous MEA solution in randomly packed columns:
1. The pseudo-single-liquid model is used and the liquid
phase is assumed to be pseudo-continuous, and the gas phase
is considered to be uniform along the radial direction. The ow
is axis-symmetric.
2. The gas absorption operation is steady, and the liquid is
incompressible, which means the liquid density does not vary
with the liquid temperature and concentration. This assumption
is reasonable for the current cases where the changes of liquid
temperature and liquid concentration are not large enough to
make substantial variation of the liquid density.
3. Only the CO
2
component in the gas phase is absorbed
by the aqueous MEA solutions, and the solvent water does not
transfer to the gas phase.
4. The heat of solution and reaction generated is all absorbed
instantaneously by the liquid phase, and the effect of packing
on the heat transfer is neglected. There is not heat transfer
between gas and liquid phases.
5. The gas absorption process is adiabatic, which means that
there is no heat exchange between the column and environment.
This is reasonable and justied by Pandya (1983).
4.2. Model equations
The CMT model consists of the differential mass transfer
equation with its auxiliary closing equations and the accompa-
nied formulations of CFD and CHT.
4.2.1. The mass transfer equation and its auxiliary closing
equations
(1) The equation for time average MEA mass fraction

C in
liquid phase:
(jhu

C) = (hjD
eff

C) +MC, (7)
where MC is the MEA sink term which comes from the chem-
ical reaction between absorbed CO
2
and MEA aqueous solu-
tions, D
eff
is the effective diffusivity of MEA, which is dened
by
D
eff
=D +D
t
, (8)
where D is the molecular diffusivity of MEAin the liquid phase,
and D
t
is the turbulent diffusivity for mass transfer, which can
be solved by using the c
2
.c
c
model (Liu, 2003) as follows.
According to the c
2
.c
c
model, the D
t
can be expressed by
D
t
=C
c0
k
_
k
c
c
2
c
c
_
1/2
, (9)
where the concentration variance c
2
and its dissipation rate c
c
are dened by
c
2
cc, (10)
c
c
D
_
jc
jx
j
jc
jx
j
_
. (11)
The detailed derivation of c
2
.c
c
model was given by Liu
(2003) and Sun et al. (2005). The model equations used in this
paper are given below.
(2) The concentration variance c
2
equation:
(jhuc
2
)
_
jh
_
D +
D
t
o
c
_
c
2
_
=2jhD
t

C

C 2jhc
c
(12)
(3) The dissipation rate c
c
equation:
(jhuc
c
)
_
jh
_
D +
D
t
o
c
c
_
c
c
_
=C
c1
jhD
t

C

C
c
c
c
2
C
c2
jh
c
2
c
c
2
C
c3
jh
cc
c
k
. (13)
The constants in Eqs. (9)(13) are given as follows (Zhang,
2002):
C
c0
=0.11, C
c1
=1.8, C
c2
=2.2, C
c3
=0.8,
o
c
=1.0 and o
c
c
=1.0.
4.2.2. The accompanied CFD equations
(1) The continuity equation:
(jhu) =M, (14)
where j is the liquid density, h is the volume fraction of liquid
phase based on pore space, u is the interstitial velocity vector,
M is the source term of the continuity equation due to the
chemical absorption of CO
2
from gas phase, which is equal to
the quantity of CO
2
absorbed by the aqueous solutions per unit
volume and unit time.
(2) The momentum equation:
(jhuu) (hj
eff
(u +(u)
T

2
3
uI))
=hp +F
LG
+h(F
LS
+jg), (15)
j
eff
=j +j
t
, (16)
j
t
=jC
j
k
2
c
, (17)
6514 G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529
where j, j
t
and j
eff
represent the molecular, turbulent and
effective viscosities of the liquid, respectively. The turbulent
viscosity j
t
is unknown and can be solved simultaneously by
the standard k-c model equations given below, and I is the unit
tensor. F
LG
is the interface drag force between gas phase and
liquid phase, F
LS
is the ow resistance created by the random
packing, which is considered to be the body force.
(3) The turbulent kinetic energy k equation:
(jhuk)
_
h
_
j +
j
t
o
k
_
k
_
=hj
eff
u ((u +(u)
T
)
2
3
uI) jhc. (18)
(4) The turbulent dissipation rate c equation:
(jhuc)
_
h
_
j +
j
t
o
c
_
c
_
=c
1
hj
eff
u ((u +(u)
T
)
2
3
uI)
c
k
c
2
jh
c
2
k
(19)
the parameters which appear in k.c model Eqs. (17)(19) are
customarily chosen to be
C
j
=0.09, o
k
=1.0, o
c
=1.3,
c
1
=1.44 and c
2
=1.92.
4.2.3. The accompanied CHT equations
(1) The time averaged liquid temperature T equation:
(c
p
jhuT ) = (c
p
jh:
eff
T ) +Q, (20)
where c
p
is the liquid phase specic heat and taken as a con-
stant; :
eff
is the effective thermal diffusivity of liquid phase,
dened as :
eff
=:+:
t
, in which : and :
t
are the molecular and
turbulent thermal diffusivities, respectively, and :
t
can be cal-
culated by the t
2
.c
t
closing equation set given below; Q is the
thermal source term including the heat of solution and reaction
and other thermal effects.
(2) The temperature variance t
2
equation: The model equa-
tions of temperature variance t
2
and its dissipation rate c
t
pro-
posed by Nagano and Kim (1988) were used. However, in this
paper, some terms of the t
2
and c
t
equations were neglected
due to their unimportance as compared with other terms. The
simplied model equations were given as follows:
(jhut
2
)
_
jh
_
: +
:
t
o
t
_
t
2
_
=2jh:
t

T

T 2jhc
t
. (21)
(3) The dissipation rate c
t
equation:
(jhuc
t
)
_
jh
_
: +
:
t
:
c
t
_
c
t
_
=C
t 1
jh:
t

T

T
c
t
t
2
C
t 2
jh
c
2
t
t
2
C
t 3
jh
cc
t
k
, (22)
the model constants in t
2
.c
t
equations are (Nagano and Kim,
1988):
C
t 0
=0.11, C
t 1
=1.8, C
t 2
=2.2, C
t 3
=0.8,
o
t
=1.0 and o
c
t
=1.0.
The concentration and the temperature as well as the velocity
distributions in the absorption column can be obtained by the si-
multaneous solution of the foregoing model Eqs. (7), (12)(15),
(18)(22) without assuming the empirical Schmidt number or
knowing the experimental mass transfer diffusivity. However,
before the computation of foregoing equation system, the terms
of h, M, F
LG
, F
LS
, MC, Q appearing in the equations must
be determined. In this paper, most of these terms are obtained
from existing correlations as shown in the following sections.
4.3. Evaluation of various terms in the model
4.3.1. The volume fraction of liquid phase
The volume fraction of liquid phase h based on pore space
can be determined from the total liquid holdup H
t
and the
porosity under the operating condition of the gasliquid two
phases ow:
h =H
t
/. (23)
The total liquid holdup can be obtained as follows:
H
t
=H
s
+H
op
. (24)
Shulman et al. (1955) reported the value of static holdup H
s
to be 0.0317 for 1/2-in ceramic Berl saddles. The static holdup
H
s
for stainless steel Pall rings could be determined from the
correlation by Engel et al. (1997):
H
s
=0.033 exp
_
0.22
gj
oa
2
_
. (25)
Otake and Okada obtained a correlation for the operating
holdup H
op
, as reported by Sater and Levenspiel (1966):
H
op
=1.295(Re)
0.676
L
(Ga)
0.44
L
(ad
p
), (26)
where (Re)
L
=d
p
L/j is the Reynolds number of liquid phase;
(Ga)
L
= d
3
p
gj
2
/j
2
is the Gallileo number of liquid phase; a
is the surface area per unit volume of packed bed; d
p
is the
nominal diameter of the packed particle.
The porosity of randomly packed bed is changed from a
constant around the center to a maximum in the neighborhood
of the wall region, which were observed by many experimental
investigations (Giese et al., 1998; de Klerk, 2003; Roblee et al.,
1958). Thus the uneven porosity distribution should be consid-
ered and calculated by the following correlation given by Liu
(2001):
=

+
(1

)
2
Er
_
(1 0.3p
d
)
cos
_
2
c

+1.6Er
2
R r
p
d
d
p
_
+0.3p
d
_
, (27)
G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529 6515
where

is the porosity of an unbounded packing, R is the

radius of the column, r is the position in radial direction, Er is
the exponential decaying function, which is given by
Er =exp
_
1.2p
d
_
R r
d
p
_
3/4
_
, (28)
where p
d
is the period of oscillation normalized by the nominal
particle size and p
d
=0.94 for Berl saddles, p
d
=0.94 (2 +
1.414)/3 for Pall rings; c

is a constant depending on the ratio

of the particle size to column size:
c

=
2R
n

p
d
d
p
1.6 exp
_
2.4p
d
_
R
d
p
_
3/4
_
, (29)
where
n

=int
_
2
1 +1.6 exp[2.4p
d
(R/d
p
)
3/4
]
R
p
d
d
p
_
. (30)
4.3.2. The source term M in continuity equation
The source termM, the rate of mass transfer per unit volume,
can be determined from the following equation based on the
well-known two-lm model:
M =K
G
a
eff
M
CO
2
(p
CO
2
p
e,CO
2
), (31)
where the overall coefcient of gas phase K
G
is related to the
individual lm coefcients as follows:
1
K
G
=
1
k
G
+
1
k
L
EHe
. (32)
In the foregoing equations, k
L
, k
G
are the lm coefcients
of mass transfer of liquid phase and gas phase respectively; :
eff
is the effective area for mass transfer between the gas phase
and liquid phase; M
CO
2
is the molecular weight of CO
2
; p
CO
2
is the partial pressure of CO
2
in main body of gas; p
e,CO
2
is
partial pressure of CO
2
in equilibrium with the solution; E
is the enhancement factor for the mass transfer process with
chemical reaction; He is the Henrys constant.
The liquid phase and gas phase mass transfer coefcients k
L
,
k
G
are determined from the correlations by Onda et al. (1968):
k
L
=0.0051
_
jg
j
_
1/3
_
L
a
w
j
_
2/3
_
j
jD
CO
2
,L
_
1/2
(ad
p
)
0.4
,
(33)
k
G
=5.23
_
G
aj
G
_
0.7
_
j
G
j
G
D
G
_
1/3
(ad
p
)
2
_
R
G
T
aD
G
_
1
, (34)
where the wetted surface area a
w
is obtained from the following
correlation by Onda et al. (1968):
a
w
a
=1exp
_
1.45
_
o
ct
o
_
0.75
_
L
aj
_
0.1
_
L
2
a
j
2
g
_
0.05
_
L
2
jao
_
0.2
_
.
(35)
According to the research result by Onda et al. (1968),
the :
w
in Eq. (35) is considered to be equal to :
eff
, and the
ow rate of liquid is related to the local liquid velocity by
L =jh|u|.
The viscosity j of aqueous MEA solutions can be calcu-
lated from the correlation developed from experimental data by
Weiland et al. (1998):
j
j
H
2
O
=exp
_
100

C(2373 +2118.6

C)[r
c
(2.2589 +0.0093 T +1.015

C) +1.0]
T
2
_
, (36)
where r
c
is the carbonation ratio of aqueous MEA solutions.
The surface tension o of aqueous MEA solutions is deter-
mined by following equation (Vazquez et al., 1997):
o =o
H
2
O
(o
H
2
O
o
MEA
)

_
1+
(0.630361.3 10
5
(T 273.15))x
H
2
O
1(0.9472 10
5
(T 273.15))x
H
2
O
_
x
MEA
.
(37)
The pure liquid surface tensions of water and MEA are obtained
as follows:
o
H
2
O
=76.0852 0.1609(T 273.15), (38)
o
MEA
=53.082 0.1648(T 273.15), (39)
where x
H
2
O
and x
MEA
denote the molar fractions of water and
MEA in aqueous MEA solutions, respectively.
The enhancement factor E, which is dened as the ratio of the
mass transfer coefcient k
R,L
for the absorption with chemical
reaction to the mass transfer coefcient k
L
for the physical
absorption (Danckwerts, 1970), varies along the column height.
For the irreversible second-order reaction such as CO
2
MEA
reaction, Wellek et al. (1978) derived the following explicit
correlation for the calculation of enhancement factor E with
deviation less than 3%:
E =1 +((E
i
1)
1.35
+(E
1
1)
1.35
)
1/1.35
, (40)
where
E
i
=1 +
DX
MEA
2D
CO
2
,L
X
i,CO
2
, (41)
E
1
=

Ha
tanh

Ha
, (42)
Ha =
D
CO
2
,L
k
2
X
MEA
(k
L
)
2
. (43)
Here X
MEA
denotes the molar concentration of MEA in liquid
phase; D
CO
2
,L
represents the molecular diffusivity of CO
2
in
6516 G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529
aqueous MEA solutions; and k
2
is the second-order reaction
rate constant for CO
2
MEA reaction.
Due to the chemical reaction of CO
2
with MEA, the molec-
ular diffusivity of CO
2
in the MEA aqueous solution D
CO
2
,L
can be determined by the use of N
2
O analogy as follows:
D
CO
2
,L
=D
N
2
O,L
(D
CO
2
/D
N
2
O
)
w
. (44)
The diffusivities of CO
2
and N
2
O in the pure water are deter-
mined from the correlations by Versteeg and Vanswaaij (1988):
(D
CO
2
)
w
=2.35 10
6
exp(2119/T ), (45)
(D
N
2
O
)
w
=5.07 10
6
exp(2371/T ). (46)
The diffusivity of N
2
O in aqueous MEA solutions is deter-
mined by the correlation reported by Ko et al. (2001):
D
N
2
O,L
=(5.07 +0.865X
MEA
+0.278X
2
MEA
)
exp
_
2371.0 93.4X
MEA
T
_
10
6
. (47)
The diffusivity of MEA molecule in aqueous MEA solutions
is calculated by using the correlation given by Snijder et al.
(1993):
D =exp(13.275 2198.3/T 0.078142X
MEA
). (48)
The second-order reaction rate constant k
2
for CO
2
MEA
reaction is obtained from the correlation by Hikita et al. (1979):
log k
2
=10.99 2152/T . (49)
According to Pohorecki and Moniuk (1988), the molar con-
centration of CO
2
at interface X
i,CO
2
can be expressed in terms
of Henrys law:
X
i,CO
2
=Hep
t
y
CO
2
, (50)
where He is the Henrys constant for CO
2
in MEA solutions; p
t
is the total pressure of gas phase; y
CO
2
is the volume fraction
of CO
2
in gas phase. Similar to the calculation of D
CO
2
,L
, He
is also determined by the use of N
2
O analogy in the following
form:
He =He
N
2
O
(He
CO
2
/He
N
2
O
)
w
. (51)
The Henrys constant for CO
2
and N
2
O in water can be ob-
tained from the following correlations proposed by Versteeg
and Vanswaaij (1988):
(He
CO
2
)
w
=(2.82 10
6
exp(2044/T ))
1
, (52)
(He
N
2
O
)
w
=(8.552 10
6
exp(2284/T ))
1
. (53)
The Henrys constant for N
2
O in aqueous MEA solutions is
calculated from the semi-empirical model developed by Wang
et al. (1992):
ln He
N
2
O
=v
MEA
ln(He
N
2
O
)
MEA
+v
H
2
O
ln(He
H
2
O
)
w
+
MEA,H
2
O
, (54)
where the excess Henrys quantity
MEA,H
2
O
for the present
system can be determined by the correlation of Tsai et al.
(2000):

MEA,H
2
O
= v
MEA
v
H
2
O
(4.793 7.446 10
3
T
2.201v
H
2
O
), (55)
where v
MEA
and v
H
2
O
denote the volume fractions of MEA
and water in aqueous MEA solutions respectively; the Henrys
constant (He
N
2
O
)
MEA
for N
2
O in pure MEA liquid is obtained
from the correlation developed from the experimental data by
Wang et al. (1992):
(He
N
2
O
)
MEA
=(1.207 10
5
exp(1136.5/T ))
1
. (56)
In order to calculate the gas phase lm coefcient k
G
, some
physical properties of gas phase, such as molecular diffusiv-
ity D
G
of CO
2
in gas phase, viscosity j
G
and density j
G
of
gas phase, should be known. In this paper, D
G
in the gas mix-
ture is obtained from the Blancs law and the binary molecular
diffusivity was calculated by empirical correlation reported by
Poling et al. (2001). The gas mixture viscosity j
G
is calcu-
lated by Bromley and Wilke correlation reported by Perry and
Green (2001). The viscosity of air and pure CO
2
is obtained
from Geankoplis (2003), and the vapor viscosity of pure hy-
drocarbons at low pressure is predicted by the method of Stiel
and Thodos reported by Perry and Green (2001). The density
of gas mixture and pure components can be obtained according
to the method of Lee and Kesler, which was reported by Perry
and Green (2001).
4.3.3. Interface drag force F
LG
For irrigated packing, the pressure drop is greater than the
dry bed pressure drop p
d
because of the presence of liquid
adhered to the packing surface. The part of increased pressure
drop, p
L
, represents the interfacial drag force between gas
and liquid phases. Robbins (1991) correlated the total pressure
drop including p
d
and p
L
for irrigated packing as follows:
p
t
=p
d
+p
L
, (57)
p
d
=p
1
G
2
f
10
p
2
L
f
, (58)
p
L
=0.774
_
L
f
20000
_
0.1
(p
1
G
2
f
10
p
2
L
f
)
4
, (59)
where p
1
=0.04002, p
2
=0.0199, G
f
is the gas loading fac-
tor, and L
f
is the liquid loading factor. G
f
and L
f
can be
determined by the following correlations:
G
f
=G
_
1.2
j
G
_
0.5
_
F
pd
65.62
_
0.5
for p
t
1.0 atm, (60)
G
f
=G
_
1.2
j
G
_
0.5
_
F
pd
65.62
_
0.5
10
0.0187j
G
for p
t
>1.0 atm,
(61)
L
f
=L
_
1000
j
__
F
pd
65.62
_
0.5
j
0.2
for F
pd
15, (62)
L
f
=L
_
1000
j
__
65.62
F
pd
_
0.5
j
0.1
for F
pd
<15. (63)
G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529 6517
The term F
pd
is a dry packing factor, specied for a given
packing type and size. For 1/2

( 1.27 cm) ceramic Berl sad-

dles, F
pd
= 900 m
1
, and for 2

stainless steel Pall rings,

F
pd
= 79 m
1
. Since the total operating pressure of chemical
absorption in this study is more than 1.0 atm, Eqs. (61) and (62)
are chosen to evaluate L
f
and G
f
.
Finally, the interface drag force F
LG
can be calculated by
F
LG
=
p
L
|u
slip
|
u
slip
, (64)
where u
slip
is the slip velocity between gas and liquid phases,
which is dened by
u
slip
=u
G
u. (65)
As the quasi-single-liquid-phase CFD method is applied in the
present work, thus the average u
G
in axial direction is deter-
mined from gas phase ow rate G, and the u
G
in radial direc-
tion is set to be zero.
4.3.4. Body force F
LS
The resistance of liquid ow due to the presence of random
packing is considered as body force, which can be calculated
by Ergun (1952) equation with replacing the mean porosity

by the porosity distribution function .

F
LS
=
_
150j
(1 )
2

2
d
2
e
+1.75j
(1 )
d
e
|u|
_
u, (66)
where d
e
is the equivalent diameter of random packing, which
is dened by
d
e
=
6(1

)
a
. (67)
4.3.5. The sink term MC in

C equation
The rate of MEA consumed per unit volume for absorbing
CO
2
from the gas phase, MC, can be calculated according to
the chemical reaction (2) as follows:
MC =
M
44
61 2. (68)
4.3.6. The heat effect Q
The temperature of liquid phase will be increased due to the
heat of absorption and reaction, and as a result, the parameters
such as He, k
2
and D
CO
2
,L
as well as the absorption rate of
CO
2
will be changed. Therefore, the increase of temperature in
liquid must be properly evaluated. The total heat effect Q can
be calculated as follows:
Q=
M
M
CO
2
(H
A
+H
R
), (69)
where H
A
is the heat of physical absorption, H
A
= 1.9924
10
7
J kmol
1
CO
2
absorbed (Danckwerts, 1970), and H
R
de-
notes the heat of chemical reaction, H
R
=8.444310
7
J kmol
1
CO
2
(Kohl and Riesenfeld, 1985).
Fig. 1. The simulation domain and boundary conditions arrangement.
4.4. The boundary conditions
The computational domain and boundaries are shown in
Fig. 1. The boundary conditions for the above equation set are
specied as follows:
(1) Inlet: At the top of the column, the boundary condition
for the liquid phase is set to be u =u
inlet
, v
inlet
=0, T =T
inlet
,

C = C
inlet
, k
inlet
= 0.003u
2
inlet
, c
inlet
= 0.09(k
1.5
inlet
/d
H
) (Khalil
et al., 1975). The term d
H
denotes the hydraulic diameter of
random packing (Bird et al., 2002), which can be calculated by
d
H
=4

/a(1

).
The boundary condition for temperature variance t
2
is
taken from the work of Tavoularis and Corrsin (1981a,b) and
Ferchichi and Tavoularis (2002). After averaging their results,
we get the following equation:
t
2
inlet
=(0.082T )
2
. (70)
As the change of temperature due to the chemical absorption
at the inlet is innitesimal or very small, the T is set to be
0.1 K for the convenience of computation.
There are no existing experimental measurements or empir-
ical correlations for the inlet condition of the concentration
variance c
2
. However, by the analogy between heat and mass
transfer, we may assume that
c
2
inlet
=(0.082C
inlet
)
2
. (71)
The inlet condition for c
c
is a complicated problem and could
be obtained by using the basic relationship of turbulent mass
transfer diffusivity D
t
and the time scale ratio R
t
:
R
t

k/c
c
2
/c
c
. (72)
Combining Eqs. (10) and (56), we get
R
t
=
_
C
c0
k
2
c
1
D
t
_
2
. (73)
6518 G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529
Different values of the ratio R
t
were reported in the literatures.
According to the viewpoint of Launder (1976), it may not be
a universal constant and may strongly depend on the nature
of the ow eld. As an approximation, we may let R
t
to be
a xed value only at the inlet boundary, and such value can
be determined from the experimental dispersion coefcient ob-
tained by using inert tracer technique, which is applicable to
the end conditions of

C=0. The diffusivity D
t
at

C=0 for a
column randomly packed with 1/2

( 1.27 cm) ceramic Berl

saddles was measured by using the inert tracer technique by
Sater and Levenspiel (1966), and correlated the coefcient of
dispersion of liquid phase , i.e. equivalent to the D
t
, by the
following equation:
_
Ud
p
D
t
_
=7.58 10
3
_
d
p
L
j
_
0.7030.238
, (74)
where U is the liquid supercial velocity. Later, Michell and
Furzer (1972) correlated the dispersion coefcient according to
their own and some published data in the following form:
|u|d
p
D
t
=1.00
_
u
inter
d
p
j
j
_
0.7
_
d
3
p
gj
2
j
2
_
0.32
. (75)
According to Eqs. (74) and (75), the order of magnitude for
D
t
is about 10
3
. By taking their average value of D
t
, and
substituting into Eq. (73), the value of R
t
was found to be about
0.4. Therefore, the boundary condition at the inlet for c
c
can
be given as follows:
c
c,inlet
=0.4
_
c
inlet
k
inlet
_
c
2
inlet
. (76)
By the analogy between heat and mass transfer, the boundary
condition for dissipation rate c
t
of temperature variance is set
to be
c
t,inlet
=0.4
_
c
inlet
k
inlet
_
t
2
inlet
. (77)
The specic values calculated from the foregoing relation-
ships for the inlet boundary condition of the present simulation
are listed in Appendix A.
(2) Outow: The liquid ow at the bottom exit of the column
is considered to be close to the fully developed condition, so
the outow boundary condition of zero normal gradient for
all ow variables except pressure is chosen under the platform
of the software FLUENT 6.1.
(3) Axis: Under the assumption that all variables 1are axially
symmetrical, we have j1/jr =0 at r =0.
(4) Wall: The no-slip condition is applied to the wall, and
the ow behavior in the near wall region is approximated by
using the standard wall functions. The zero ux condition is
applied for other variables.
4.5. Numerical procedure
The model equations were solved numerically by using the
commercial software FLUENT 6.1 with nite volume method.
The simulation was done under the condition of steady two-
dimensional owof axial and radial symmetry. The well-known
SIMPLEC algorithm is used to solve the pressurevelocity cou-
pling problem in the momentum equations.
The grid arrangement for the simulation of pilot-scale col-
umn of 6.55 m height and 0.05 m radius is as follows: there
are 1310 nodes uniformly distributed along the column height
and 80 nodes non-uniformly distributed along the radial direc-
tion with high grid resolution at the near wall region, so the
total numbers are about 104 800 quadrilateral cells. While the
grid arrangement for simulating the commercial-scale column
of 14.1 m height and 0.95 m radius, there are 1000 nodes uni-
formly distributed along the column height and 75 nodes non-
uniformly distributed along the radial direction with higher grid
resolution at the near wall region, so the total numbers are
about 75000 quadrilateral cells. The one-order upwind spatial
discretization scheme was used for all differential equations.
5. Comparison between simulated results and
experimental data
5.1. Comparison between simulated and experimental results
for pilot-scale column
Twelve sets of experimental data for chemical absorption of
CO
2
from mixture of CO
2
and air by aqueous MEA solutions in
a pilot-scale column were reported by Tontiwachwuthikul et al.
(1992), including the variation of radial averaged carbonation
ration ( =CO
2
loading), the temperature in the liquid phase and
the radial averaged CO
2
concentration in the gas phase along
the column height. In this paper, only the simulated results on
experiments T13, T14, T17, and T22 are used as examples for
comparison.
In Figs. 25, the square and circle symbols represent the
experimental data, and the solid lines indicate the simulated
results which are obtained after radial average. As seen from
the gures, the simulated and experimental results on the CO
2
loading in liquid phase and the CO
2
volume percentage in gas
phase are in satisfactory agreement.
It is interesting to compare the simulated results between
using the present model without knowing the coefcient of dis-
persion and using the conventional model with published ex-
perimental coefcient. The conventional simulated model used
is one-dimensional with axial mixing, and the axial dispersion
coefcient is calculated by Eq. (74). Take run T17 as an ex-
ample, the simulated results by the conventional model on gas
CO
2
concentration and liquid CO
2
loading proles are shown
in Fig. 4(a) by the dash dot lines along the axial direction. It
should be pointed out that the column is taller than it is needed
for the separation concerned as seen on the axial concentration
prole, in which the change of liquid phase concentration is
becoming very small in the upper part of the column. It means
that the separation is approaching to the equilibrium state at
some distance from the column bottom and thus results almost
the same concentration regardless what model is being used
for the simulation. However, the difference is clearly seen at
the lower part of the column, as the simulation by using the
G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529 6519
Fig. 2. Predicted (solid lines) and experimental (points) results for Run
T13: (a) gas CO
2
concentration and liquid CO
2
loading proles; (b) liquid
temperature and enhancement factor.
present model give better prediction than the conventional. In
order to display clearly the difference of the simulated results,
a table for comparison is given in Appendix B, in which the ex-
perimental measurements, the predictions by the present model
and the conventional one for run T17 are listed. It is seen that
the present model give better prediction.
As shown in Figs. 2(b)5(b), the predicted temperature pro-
les along the column show somewhat higher than the exper-
imental measurement, especially at the column bottom. The
discrepancy may be due to the following reasons: rstly, the
present modeling neglects the heat transfer between gas and
liquid phases, that is the cooling of descending liquid by the
entering gas; secondly, the evaporation of solvent water in liq-
uid phase is also neglected, so that the liquid temperature is
overestimated; thirdly, the assumptions of adiabatic operation
and neglecting the heat transfer between the solid packing and
the uid are also the causes of producing error.
5.2. Comparison between simulated and measured results for
industrial-scale column
Fifteen sets of data for chemical absorption of CO
2
from
natural gas mixture by aqueous MEA solutions in an industrial-
Fig. 3. Predicted (solid lines) and experimental (points) results for Run
T14: (a) gas CO
2
concentration and liquid CO
2
loading proles; (b) liquid
temperature and enhancement factor.
scale column were reported by Pintola et al. (1993), including
the CO
2
volume percentage in the gas phase and the CO
2
load-
ing with temperature in the liquid phase. In this paper, only the
simulated results on experimental Run 115 was presented as an
example for comparison.
As shown in Fig. 6, the simulated top and bottom concentra-
tions by using the proposed model are closely checked by the
reported measurement. Furthermore, our simulation is better
than that given by Pintola et al. (1993), as shown inAppendix C.
For Run 115, the typical CO
2
volume percentage in gas
phase, the CO
2
loading, the temperature of liquid phase and
the enhancement factor along the column are shown in Fig. 6.
It is seen from the gure that 99% of the CO
2
was absorbed
by aqueous MEA solutions in the bottom two sections of the
column, and only little CO
2
was removed in the top section.
Figs. 710 show the radial variation of the CO
2
concentration
in gas phase, the CO
2
loading, the liquid temperature and the
free MEA concentration of liquid phase at different height of
the column.
As seen from Figs. 79, the CO
2
concentration in gas phase,
the CO
2
loading and the temperature of liquid phase are de-
creased from column center to column wall at different height
of the column. It could be explained that the ow of liquid
6520 G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529
Fig. 4. Comparisons between the predicted values by present model (solid
lines) and by one-dimensional with axial mixing model (dash dot lines) with
experimental (points) results for Run T17: (a) gas CO
2
concentration and
liquid CO
2
loading proles; (b) liquid temperature and enhancement factor.
phase is slow down near the wall in the randomly packed
column, resulting in worse contact with the gas phase, and
consequently less CO
2
to be absorbed, producing less exother-
mic heat of solution and reaction. It may be also noted from
Fig. 10 that, at a xed axial position, the radial difference of
free MEA concentration in the liquid phase is larger at the bot-
tom of the column than at the top.
Fig. 11 shows the axial distribution of the CO
2
concentration
in the gas phase, the CO
2
loading, the free MEA molar con-
centration and the liquid temperature. It can be seen that most
absorptions are taken place at the bottom part of the column,
and the top part has a little effect on the CO
2
removal.
5.3. Liquid velocity prole
Due to the non-uniform packing structure and higher poros-
ity near the wall region, the uid ow deviates from the plug
ow. As seen from Fig. 12, in both the pilot-scale and the
industrial-scale columns, the wall ow effect is clearly seen,
and the ow behaves relatively uniform only about 2d
p
apart
from the wall. This phenomenon has been conrmed by many
investigators (Liu, 2001; Giese et al., 1998).
Fig. 5. Predicted (solid lines) and experimental (points) results for Run
T22: (a) gas CO
2
concentration and liquid CO
2
loading proles; (b) liquid
temperature and enhancement factor.
5.4. Turbulent mass transfer diffusivity D
t
The turbulent mass transfer diffusivity or dispersion coef-
cient D
t
is often neglected or assumed to be constant in the
packed column design. However, according to the calculated
D
t
by using the proposed model, it varies from top to bottom
and from center to wall of the columns as shown in Figs. 13(a),
14 (a) and 15 (a). Furthermore, the calculated D
t
for the in-
dustrial column are very closer to the reported experimental
measurements. From Fig. 14(a), the turbulent diffusivity D
t
ob-
tained by the present model is ranging from 6.010
4
m
2
/s to
1.5 10
3
m
2
/s, while the values calculated from the empiri-
cal correlations obtained by using inert tracer technique with no
mass transfer by Sater and Levenspiel (1966) and by Michell
and Furzer (1972) are 0.001011 and 0.00116 m
2
/s, respectively.
Although they are practically in the same order of magnitude,
the difference in values between them demonstrates that the D
t
is changed somewhat due to the process effect of mass transfer.
The variations of D
t
with radius at different axial positions
are presented in Figs. 13(a) and 14(a). Generally speaking, D
t
is found to be substantially constant around the center region of
the packed bed, and increased to a maximum near the column
wall, and then decreased sharply to the wall surface for both the
pilot-scale column and the industrial-scale column. Such phe-
G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529 6521
Fig. 6. Predicted (solid lines) and experimental (points) results for Run
115: (a) gas CO
2
concentration and liquid CO
2
loading proles; (b) liquid
temperature and enhancement factor.
Fig. 7. Gas CO
2
concentration proles along the radial direction at different
height.
nomenon is consistent with the experimental results by Fahien
and Smith (1955) and Dorweiler and Fahien (1959) on using
gas phase tracer technique. The uneven D
t
distribution is re-
lated to the mal-distributed elds of ow and concentration as
shown in Figs. 11(c) and 12.
Fig. 8. The CO
2
loading proles along the radial direction at different height.
Fig. 9. The temperature proles of liquid along the radial direction at different
height.
Fig. 10. The free MEA concentration proles along the radial direction at
different height.
6522 G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529
Fig. 11. Axial distributions of: (a) CO
2
concentration; (b) CO
2
loading; (c) free MEA concentration; and (d) liquid temperature for Run 115.
The predicted D
t
along the column height varies little for the
pilot-scale column as shown in Fig. 13(a), which results from
the lower liquid Reynolds number and higher volume fraction
of CO
2
in gas phase. While for the industrial column, the D
t
is
gradually decreased as approaching to the bottom of the column
as shown in Fig. 14(a), which is probably due to the higher
liquid Reynolds number and lower volume fraction of CO
2
in
gas phase. The axial distribution of D
t
for the industrial column
is shown in Fig. 15(a).
5.5. Analogy between turbulent mass transfer and heat transfer
In applying the present model, both turbulent mass trans-
fer diffusivity D
t
and turbulent heat transfer diffusivity :
t
can
G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529 6523
Fig. 12. Relative axial velocity prole of the liquid along the radial direction for Run T22 and Run 115.
be solved and show in Figs. 1315. From these gures, It
can be clearly seen the similarity between them in spite of
having a little difference. For example, the volume average
values of D
t
and :
t
calculated for Run 115 of the industrial
column are 0.001049 and 0.001107 m
2
/s, respectively, while
those in the Run T22 of the pilot-scale column are 0.001144 and
0.001169 m
2
/s; the approximate equality of D
t
and :
t
demon-
strates the analogy between turbulent mass transfer and heat
transfer.
5.6. Distribution of radial average enhancement factor E
along the column
The enhancement factor E is an important parameter for
chemical absorption, and its accurate estimation is essential for
proper modeling the mass transfer process. The enhancement
factor is inuenced by many aspects, such as the physical prop-
erties of liquid and gas, the MEA concentration in liquid phase,
the CO
2
concentration in gas phase, the ow eld, the reaction
rate and the others; therefore it is a varying parameter along
the column as shown in Figs. 2 (b)6 (b).
5.7. Study on the inuence of grid number on the accuracy of
numerical simulation
Generally, the number of grid to be used in simulation has
considerable effect on the numerical result. Regarding this as-
pect, it is necessary to test whether the use of 75 grid points in
radial simulation is sufcient for the industrial scale absorption
column with 1.9 m in diameter. Taking Run 115 of the large
column concerned, it was simulated with 75 and 225 points
separately in the radial direction, and using the second order
upwind discretisation scheme for the differential equations in-
stead of rst order upwind scheme. The simulated radial gas
CO
2
concentration proles with 75 and 225 radial grid points
are given in Fig. 16.
It can be seen from Fig. 16 that the difference of the simu-
lated results is small. It could be understood that, the numerical
accuracy of the present simulation with 75 radial grid points is
sufcient in practical sense, and it has very weak improvement
on the increasing number of grids beyond 75.
However, there is no doubt that the numerical accuracy could
be further improved by precise simulation with very large num-
ber of grid points.
6524 G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529
Fig. 13. Turbulent diffusivity proles along radial direction for Run T22: (a) turbulent mass transfer diffusivity proles; and (b) turbulent heat transfer diffusivity
proles.
Fig. 14. Turbulent diffusivity along radial direction for Run 115: (a) turbulent mass transfer diffusivity proles; and (b) turbulent heat transfer diffusivity proles.
Fig. 15. Distribution of turbulent diffusivity for Run 115: (a) turbulent mass transfer diffusivity; and (b) turbulent heat transfer diffusivity.
G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529 6525
Fig. 16. The simulated gas CO
2
concentration proles with 75 and 225 grid
points in the radial direction at x =13.0 m.
6. Conclusions
The following conclusions can be drawn from the present
work:
(1) A complex model of computational mass transfer is pro-
posed for simulating the concentration, temperature and
velocity distributions for a chemical absorption process
with heat effect. The proposed model is applied to a pilot-
scale packed column undertaking the chemical absorption
of CO
2
from air by MEA aqueous solutions, and to an
industrial-scale packed column for the chemical absorption
of CO
2
from natural gas mixture by aqueous MEA solu-
tion. The simulated results are in satisfactory agreement
with the experimental data reported by Tontiwachwuthikul
et al. (1992) and by Pintola et al. (1993).
(2) The proposed model is able to predict the turbulent mass
transfer diffusivity D
t
, which shows varying along the axial
and radial directions.
(3) The computed proles of D
t
for mass transfer and :
t
for
heat transfer are found to be very similar, and the calculated
volume average values of D
t
and :
t
are nearly equal, which
demonstrates the analogy between turbulent mass and heat
transfer.
(4) The enhancement factor of chemical absorption predicted
from the proposed model varies signicantly along the
column.
(5) The proposed model is useful for simulating chemical ab-
sorption and relevant process with heat effect without re-
lying on the experimental measurement of turbulent mass
transfer and heat transfer diffusivities, especially for cases
where the empirical turbulent Schmidt number or the dis-
persion coefcients is not available.
Notation
a surface area per unit volume of packed
bed, 1/m
a
eff
effective area for mass transfer between
the gas phase and liquid phase, 1/m
a
w
wetted surface area, 1/m
c
2
concentration variance, dimensionless
c
p
liquid phase specic heat, J/kg/K
c

a constant depending on the ratio of the

particle size to column size, dimension-
less

C average concentration of mass fraction,

dimensionless
C
j
, c
1
, c
2
model parameters in kc model equa-
tions, dimensionless
C
c0
, C
c1
, C
c2
, C
c3
model parameters in c
2
.c
c
model equa-
tions, dimensionless
C
t 0
, C
t 1
, C
t 2
, C
t 3
model parameters in t
2
.c
t
equations,
dimensionless
[CO
2
], [MEA] molar concentration of CO
2
and MEA
in solution, respectively, kmol/m
3
d
e
equivalent diameter of random pack-
ing, m
d
H
hydraulic diameter of random pack-
ing, m
d
p
nominal diameter of the packed parti-
cle, m
D molecular diffusivity of MEA molecu-
lar in aqueous MEA solutions, m
2
/s
D
CO
2
,L
molecular diffusivity of CO
2
in aque-
ous MEA solutions,m
2
/s
(D
CO
2
)
w
, (D
N
2
O
)
w
diffusivity of CO
2
and N
2
O in the pure
water, respectively, m
2
/s
D
eff
effective diffusivity of MEA, m
2
/s
D
G
molecular diffusivity of CO
2
in gas
phase, m
2
/s
D
N
2
O,L
diffusivity of N
2
O in aqueous MEA so-
lution, m
2
/s
D
t
turbulent diffusivity for mass transfer,
m
2
/s
E enhancement factor, dimensionless
F
LG
interface drag force between gas phase
and liquid phase, N/m
3
F
LS
owresistance created by the randomly
packing, N/m
3
F
pd
dry packing factor, 1/m
g acceleration due to gravity, m/s
2
G gas phase ow rate per unit cross-
section area, kg/m
2
/s
G
f
gas loading factor, kg/m
2
/s
(Ga)
L
Gallileo number of the liquid phase, di-
mensionless
h volume fraction of liquid phase based
on pore space, dimensionless
H
A
physical absorption heat of mol CO
2
absorbed, J/kmol
H
op
operating holdup, dimensionless
H
R
chemical reaction heat of mol CO
2
ab-
sorbed, J/kmol
6526 G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529
H
s
static holdup, dimensionless
H
t
total liquid holdup, dimensionless
He Henrys constant for CO
2
in MEA so-
lutions, kmol/m
3
/kPa
(He
CO
2
)
w
,(He
N
2
O
)
w
, Henrys constant for CO
2
and N
2
O in
water, respectively, kmol/m
3
/kPa
He
N
2
O
Henrys constant for N
2
O in aqueous
MEA solutions, kmol/m
3
/kPa
(He
N
2
O
)
MEA
Henrys constant for N
2
O in pure MEA
liquid, kmol/m
3
/kPa
k
2
second-order reaction rate constant,
m
3
/kmol/s
k
G
gas phase mass transfer coefcient,
kmol/m/s/kPa
k
L
liquid phase mass transfer coefcient
without chemical reaction, m/s
k
R,L
liquid phase mass transfer coefcient
with chemical reaction, m/s
K turbulent kinetic energy, m
2
/s
2
K
G
overall coefcient of gas phase,
kmol/m
2
/s
1
/kPa
L liquid ow rate per unit cross-section
area, kg/m
2
/s
L
f
liquid loading factor, kg/m
2
/s
M CO
2
quantity absorbed by the aqueous
solution per unit volume and unit time,
kg/m
3
/s
M
CO
2
molecular weight of CO
2
, kg/kmol
MC sink term of MEA conservation equa-
tion, kg/m
3
/s
p
1
, p
2
constants, dimensionless
p
d
period of oscillation normalized by the
nominal particle size, dimensionless
p
e,CO
2
partial pressure of CO
2
in equilibrium
with solutions, kPa
p
t
total pressure of gas phase, kPa
p
d
dry-bed pressure drop per meter pack-
ing, N/m
3
p
L
wet-bed pressure drop per meter pack-
ing, N/m
3
p
t
total pressure drop per meter packing,
N/m
3
P
CO
2
partial pressure of CO
2
in main body
of gas, kPa
Q thermal source term of temperature
equation, J/m
3
/s
r
c
carbonation ratio (CO
2
loading) of the
aqueous MEA solutions, mol CO
2
/ mol
MEA
R position in radial direction, m
R radius of the column, m
R
G
gas universal constant, kJ/kmol/K
(Re)
L
Reynolds number of liquid phase, di-
mensionless
Rc the rate of reaction, kmol/m
3
/s
Rt velocity to concentration time scale ra-
tio, dimensionless
t
2
temperature variance , dimensionless
T liquid temperature, K
u interstitial velocity vector of liquid, m/s
u
G
gas velocity vector, m/s
u
slip
slip velocity vector between gas phase
and liquid phase, m/s
U liquid supercial velocity, m/s
v
MEA
, v
H
2
O
volume fraction of water and MEA in
aqueous MEA solutions, respectively,
dimensionless
x
H
2
O
, x
MEA
molar fraction of water and MEA in
aqueous MEA solutions, respectively,
dimensionless
X
CO
2
molar concentration of CO
2
in the liq-
uid bulk, kmol/m
3
X
i,CO
2
molar concentration of CO
2
at inter-
face, kmol/m
3
X
MEA
molar concentration of MEA in liquid
phase, kmol/m
3
y
CO
2
volume fraction of CO
2
in gas
phase,dimensionless
Greek letters
:, :
eff
, :
t
molecular, turbulent and effective ther-
mal diffusivities, respectively, m
2
/s
porosity distribution of the random
packing bed along the radial direction,
dimensionless

porosity in an unbounded packing, di-

mensionless
c turbulent dissipation rate, m
2
s
3
c
c
turbulent dissipation rate of concentra-
tion uctuation, 1/s
c
t
turbulent dissipation rate of tempera-
ture uctuation, 1/s
j, j
t
, j
eff
, liquid molecular, turbulent and effec-
tive viscosity, respectively, kg/m/s
j
G
gas phase viscosity, kg/m/s
j liquid density, kg/m
3
j
G
gas phase density, kg/m
3
o surface tension of aqueous MEA solu-
tions, dynes/cm, or N/m
o
ct
critical surface tension of the pack-
ing material, N/m, for ceramic, o
ct
=
0.061 N/m, for stainless steel, o
ct
=
0.071 N/m
o
c
, o
c
c
model parameters in c
2
.c
c
model equa-
tions, dimensionless
o
H
2
O
pure water surface tension, dynes/cm
o
k
,o
c
model parameters in kc model equa-
tions, dimensionless
o
MEA
pure MEA surface tension, dynes/cm
o
t
, o
c
t
model parameters in t
2
.c
t
model equa-
tions, dimensionless

MEA,H
2
O
excess Henrys quantity, kmol/m
3
/kPa
1 variable, dimensionless
G.B. Liu et al. / Chemical Engineering Science 61 (2006) 65116529 6527
Table 1
The specic values for the inlet boundary condition of the present simulation
u (m/s) v (m/s) h C T (K) k (m/s)
2
(m
2
/s
3
) c
2

c
(s
1
) t
2
(K
2
) (s
1
)
T13 0.0387 0 0.1563 0.121878 292.15 4.492E 6 6.106E 8 9.988E 5 4.073E 7 6.724E 5 2.742E 7
T14 0.0387 0 0.1563 0.093115 292.15 4.492E 6 6.106E 8 5.830E 5 2.377E 7 6.724E 5 2.742E 7
T17 0.0387 0 0.1563 0.121805 293.15 4.492E 6 6.106E 8 9.976E 5 4.068E 7 6.724E 5 2.742E 7
T22 0.0304 0 0.1399 0.182817 292.15 2.777E 6 2.967E 8 2.247E 4 7.204E 7 6.724E 5 2.742E 7
Run 115 0.1372 0 0.0319 0.219380 312.95 5.651E 5 4.351E 7 3.236E 4 9.967E 7 6.724E 5 2.071E 7
Table 2
Comparison between experimental, two and one dimensional simulation results for Run T17
T17 CO
2
concentration in gas phase (%) CO
2
loading in liquid phase
Exp. Two dim. One dim. Exp. Two dim. One dim.
x =0.0 m 0.0 0.0265 0.0389 0.237 0.237 0.237
x =1.05 m 0.0 0.1045 0.1101 (0.237) 0.238 0.238
x =2.15 m 0.8 0.4596 0.3288 0.243 0.241 0.240
x =3.25 m 2.0 1.4343 0.9797 0.256 0.252 0.247
x =4.35 m 5.3 4.1456 2.8740 0.296 0.282 0.267
x =5.45 m 10.2 9.7249 7.7675 0.350 0.347 0.324
x =6.55 m 15.6 15.60 15.60 0.428 0.427 0.427
Table 3
Comparison of CO
2
concentration in gas phase exit between the results of
experimental, by the proposed model and by Pintola et al. (1993)
Run
No.
Exp. CO
2
(ppm)
Simu. CO
2
(proposed)
(ppm)
Simu. CO
2
(Pintola et al.
1993) (ppm)
101 8.0 9.1 65.2
102 11.5 2.4 17.5
103 14.5 27.5 13.0
104 8.7 10.0 30.6
105 9.7 4.7 19.1
106 12.0 2.1 13.1
107 6.5 8.1 39.1
108 15.0 7.4 45.3
109 8.7 5.0 45.4
110 16.0 8.0 55.5
111 13.0 4.8 37.4
112 5.3 9.1 54.7
113 28.0 9.3 60.4
114 74.0 2.2 41.5
115 4.8 8.5 41.5
Subscripts
eff effective, dimensionless
G gas, dimensionless
I interface, dimensionless
L liquid, dimensionless
R reaction, dimensionless
slip slip, dimensionless
S solid, dimensionless
t time scale, dimensionless
Acknowledgments
The authors acknowledge the nancial support by the Na-
tional Natural Science Foundation of China (Contract no.
20136010) and the assistance from the staff in the State Key
Laboratories for Chemical Engineering (Tianjin University).
Appendix A
The specic values for the inlet boundary condition of the
present simulation are given in Table 1.
Appendix B
Comparison between experimental, two and one dimen-
sional simulation results for Run T17 are given in Table 2.
Appendix C
Comparison of CO
2
concentration in gas phase exit be-
tween the results of experimental, by the proposed model and
by Pintola et al. (1993) are given in Table 3.
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