m
H
i,ref
k
gi
/D
i
Bi
H
Biot number for heat transfer, h
m
/
c dimensionless components concentration,
C/C
ref
c
g
i
dimensionless gas phase concentration,
C
g
i
C
g
i,ref
H
i,ref
c
L
i
dimensionless liquid phase concentration,
C
L
i
C
L
i,ref
C dimensional components concentration
C
i,ref
reference liquid phase reactant concentration
(liquid feed condition)
C
p
average mass heat capacity
C
g
i,ref
reference gas phase reactant concentration(gas
feed condition)
D
i
diffusivity coefcients in the liquid phase
f
g
dimensionless ow rate
h temperature dependency of solubility or
volatility
h
g
gas phase convective heat transfer coefcient
H solubility or vaporability
Ha
j
Hatta number for reaction j
H
ref
reference Henrys law constant
(gas feed condition)
(H
r
) heat of reaction
(H
s
) heat of solution
(H
vap
) heat of vaporization
k reaction rate constant
k
gi
gas side mass transfer coefcient based on
concentration driving force
k
L
liquid side mass transfer coefcient based on
concentration driving force
L
w
square of the lm thickness ratio
Le Lewis number
m
g
mass ow rate of gas phase
m
L
mass ow rate of liquid phase
M
j
the kinetic reaction rate parameter,
M
j
=
V
cell
(
L
a
m
)
Q
L
C
ref
R
ref
j
n
g
i
molar ow rate of component in bulk phase
N number of mixing cells
N
i
mass ux of component i
NR the number of reaction
NS the number of species
p partial pressure
q heat ux
Q volumetric ow rate
r dimensionless reaction rate of component,
R
j
/R
ref
j
R dimensional reaction rate of component
s
i
diffusivity ratio
S
g
heat transfer dimensionless termfor gas phase,
aV
cell
L
m
g
m
C
g
p
S
L
heat transfer dimensionless term for liquid
phase,
aV
cell
L
m
L
m
C
L
p
T temperature
u supercial velocity of phase
u
g
ref
reference supercial velocity of gas phase
being gas feed supercial velocity
u
L
ref
reference supercial velocity of liquid phase
being gas feed supercial velocity
V
cell
volume of tank or cell
Z direction of lm thickness
Greek letters
gL
Damkohler number for mass transfer,
aV
cell
k
L
u
L
ref
A
r
parameter of heat of reaction,
(H
r,j
)D
ref
C
ref
/
L
T
ref
s
parameter of heat of solution/vaporization at
interface, (H
Si
)D
i
C
i,ref
/
L
T
ref
Arrhenius number for reaction, E
a
/(RT
ref
)
Fi
the effective gas to liquid ow rate ratio,
u
L
ref
u
g
ref
H
i,ref
L
average heat transfer conductivity of the liquid
phase
s
Arrhenius number for solution/vaporization,
H
Si
/RT
ref
h
heat transfer lm thickness
m
mass transfer lm thickness
L
liquid phase holdup
dimensionless temperature, T/T
ref
dimensionless mass transfer lm thickness
stoichiometric parameter,
j
D
A
C
g,A
/D
B
C
b
B
ji
stoichiometric coefcient of species i in any
reaction j
i
ratio of C
i,ref
to C
ref
Subscripts
i component species
j reaction
g gas phase
A gas phase reactant
B liquid phase reactant
Superscripts
f liquid lm
g gas phase
L liquid phase
b phase bulk
A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473 2463
the rate constant but also the solubility of the gases partic
ipating in the reactions. In addition, the liquid phase reac
tants and/or products are volatile in some cases which adds
another degree of complexity to the problem. For modeling
a gasliquid reactor, the lm model appears as a submodel
and repeated solution of the lm model is needed for the
solution of the reactor model. The lm model equations are
a set of coupled nonlinear ordinary second order differen
tial equations with the nonlinear boundary conditions and
hence a general solution is a complicated task. A number of
papers have therefore examined the problemby either numer
ical method or approximate analytical methods (AlUbaidi &
Selim, 1996). These methods have been usually applied to a
simple reaction and a general case does not appear to have
been demonstrated. Additionally, the gas absorption accom
panied by exothermic reactions, was also investigated by
various authors (Bhattacharya, Gholap, & Chaudhari, 1988;
Rao, 1991; Vas Bhat, vanSwaaij, Benes, Kuipers, &Versteeg,
1997). These previous studies considered the temperature
effects in the lm model or penetration model in an approxi
mate manner to explain simultaneous heat and mass transfer
for certain simple reaction schemes. In addition, some papers
neglect gas lm resistance, while liquid components were
nonvolatile components. In view of these, a general model
and an efcient computational scheme are needed for the lm
model and this needs to be coupled to a mixing cell model
for the reactor itself. This paper is directed towards these
objectives and uses the boundary element method to solve
the lm model differential equations. The uxes at the inter
face and into the bulk are directly obtained as a part of this
novel solution method. These uxes are then directly used as
the link to the reactor model and used for solution of the reac
tor model. The boundary element method has been applied
to 1D boundary value problems in a number of contexts. The
details are available in the book by Ramachandran (1991).
Additional references as applied to 1D problems are avail
able in Ngoasuwan, Limtrakul and Ramachandran (2001),
Ramachandran (1994). The method has not been applied to
gas absorption with reaction which is a new feature of this
work. Two simple numerical test examples are shown for sim
ple isothermal and nonisothermal reactions. In addition, the
application to two industrially important case studies, chlo
rination of butanoic acid and oxidation of cyclohexane are
briey illustrated.
The paper is organized as follows: Section 2 provides a
detailed description of the mixing cell model for a general set
of nonisothermal reactions. It also outlines the relevant reac
tor scale dimensionless parameters and shows howthe reactor
model is linked to the lm model via interfacial uxes. Sec
tion 3 then provides a general description of the lm model.
Section 4 shows the model solution procedure. This section
indicates briey how the lm model can be solved by using
boundary integral methods. It then shows how the reactor
model can be often solved simply by modifying the bound
ary conditions of the lm model. Section 5 shows two simple
numerical test examples andSection6shows brieythe appli
cation to two industrially important case studies. Finally,
Section 7 provides a summary and the closing remarks.
2. Reactor model
2.1. Mixing cell model
The mixing cell model is useful to evaluate the perfor
mance of a gasliquid reactor, which has mixing character
istics, intermediate to the ideal situation of plug ow and
backmixed ow. A schematic representation of the mixing
cell model is shown in Fig. 1. The value of N would be 1
and for well mixed and plug ow reactors, respectively.
In each tank (cell) of the steady state gasliquid reactor, the
ow pattern is considered as well mixed.
The reactor model for each cell consists of species bal
ances for the bulk gas and the bulk liquid and the heat balance
for the gas phase and the liquid phase. The gas phase balances
need the mass and heat uxes at the gasliquid interphase.
The liquid phase balances need the heat and mass uxes at
the end of lm. These are then provided by the lm model
which is described in Section 3. The coupling of the gas phase
and liquid phase is via the uxes given by the lm model. A
schematic of this is shown in Fig. 2.
Fig. 1. Schematic of mixing cell representation of the reactor.
Fig. 2. Schematic of gasliquid reactor model for only tank or cell j.
2464 A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473
2.2. Mass and heat balances
The mass balance for a component in the gas bulk of each
tank (cell) is written as
aV
cell
N
f
i

Z=0
= (n
g
i
)
in
(n
g
i
)
out
(1)
where
N
f
i
= D
i
_
dC
f
i
dZ
_
z=0
and n
g
i
= Q
g
C
g
i
= A
r
u
g
C
g
i
(2)
where a is dened as interfacial area per volume of reactor;
V
cell
is dened as volume of tank or cell, N
f
i

Z=0
is dened
as interfacial molar ux, D
i
is dened as molar liquid phase
diffusivity, Zis denedas the distance coordinate onthe liquid
lm, Q
g
is dened as volumetric ow rate of gas phase, C
g
i
is dened as concentration of gas phase component, C
f
i
is
dened as concentration in the lm, A
r
is dened as cross
section area of reactor, u
g
is dened as supercial velocity of
gas phase and n
g
i
is dened as molar ow rate of component
in gas phase.
The heat balance for gas bulk is written as
aV
cell
q
f

Z=0
= m
g
C
g
p
(T
g
in
T
g
out
) (3)
The above equation is obtained by balancing the net rate of
heat of convection in the bulk gas to the interfacial ux to the
liquid given by Fouriers law as
q
f
=
L
_
dT
dZ
_
Z=0
.
Further, m
g
is dened as mass ow rate of gas phase, T is
dened as temperature,
C
g
p
is dened as average (mass based)
heat capacity of gas phase and
L
is dened as average ther
mal conductivity of the liquid.
The mass balance in liquid bulk for the dissolved gases,
liquid reactants, the liquid products and byproducts are given
by
V
cell
aN
f
i

Z=
m
= Q
L
C
L
i,in
Q
L
C
L
i,out
NR
j=1
V
cell
(
L
a
m
)
ji
R
b
j
= 0 (4)
where (N
f
i
)
Z=
m
is the mass ux at
m
again given by Ficks
law,
L
is a liquid phase hold up, Q
L
is dened as volumetric
ow rate of liquid phase,
ji
is stoichiometry of component
i in reaction j, C
L
i
is liquid bulk concentration of i and R
b
j
is
rate function for reaction j in the bulk liquid.
The heat balance in bulk of liquid involves a minor dif
culty because mass transfer liquid bulk and heat transfer
liquid bulk are not analogous. This is because of the fact
that the lm thickness for heat transfer is somewhat larger
than that for mass transfer. However it can be simplied by
assuming that this volume is innitesimal compared to the
total volume of bulk phase. Consequently, heat of reaction
evolved in this gap is small and is lumped into the bulk liquid
heat balance. Hence the heat ux at
m
is taken as equal to
heat ux at the end of the heat transfer lm. Eq. (5) below
then gives the heat balance by balancing the heat ux through
boundary liquid lm to the convective ow of heat and the
heat of reaction in bulk phase:
aV
cell
q
f
Z=
m
= m
L
C
L
p
[T
L
in
T
L
out
]
+
NR
j=1
V
cell
(
L
a
m
)R
b
j
(H
r,j
) (5)
where m
L
is dened as mass ow rate of liquid phase and
C
L
p
is dened as average (mass based) heat capacity of liquid
phase. Also q
f
Z=
m
is the heat ux at
m.
2.3. Dimensionless forms
The dimensionless representation of these equations is
now presented. The concentrations in the gas phase are nor
malized by a reference gas phase concentration in the feed,
C
g
i,ref
. This will usually be the concentration of the primary
gas phase reactant in the feed.
The dimensionless concentration of the species in the liq
uid lm as well as in the bulk liquid is obtained by dividing
the actual concentration by a reference concentration for each
species denoted as C
i,ref
. For gas species, C
g
i,ref
and C
i,ref
are
related by Henrys law. For nonvolatile liquid phase species,
some reference liquid concentration can be chosen, usually
the concentration of the main liquid phase reactant in the
feed. Note that C
i,ref
need not be different for each i and can
be same for some (or all) of the species. For example the prod
uct concentration in the incoming feed may be zero in which
case the reactant concentration is chosen for the normaliza
tion of the product concentration. Finally, the temperature
in the gas phase and liquid phase is normalized by the feed
temperature.
With these choices the following equations are obtained.
The gas phase mass balance given by Eq. (1) can be for
mulated into dimensionless form as follows:
(c
g
i
f
g
)
in
(c
g
i
f
g
)
out
+
gL
Fi
s
i
_
dc
f
i
d
_
=0
= 0 (6)
where c
g
i
is dimensionless of gas phase concentration dened
as
c
g
i
=
C
g
i
C
g
i,ref
and c
f
i
=
C
f
i
C
i,ref
(7)
where C
g
i,ref
is dened as reference gas phase reactant con
centration and C
i,ref
is the reference liquid concentration
(C
i,ref
= C
g
i,ref
/H
i,ref
). The dimensionless lm thickness is
dened that =
Z
m
and H
i,ref
is dened as reference Henrys
law constant for species i. The dimensionless ow rate is
dened as: f
g
=
Q
g
Q
g
ref
.
A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473 2465
The parameters appearing in Eq. (6) are dened as follows.
The Damkohler number (
gL
) for mass transfer is
gL
=
aV
cell
k
L
u
L
ref
A
r
(8)
The effective gas to liquid ow rate ratio (
Fi
)
Fi
=
u
L
ref
u
g
ref
H
i,ref
(9)
where u
g
ref
is dened as reference supercial velocity of gas
phase being gas feed supercial velocity and u
L
ref
is dened
as reference supercial velocity of liquid phase being liquid
feed supercial velocity.
The diffusivity ratio (s
i
)
s
i
=
D
i
D
ref
(10)
The mass transfer coefcient (k
L
) is derived from Ficks law:
k
L
=
D
ref
m
(11)
The dimensionless equation for gas phase heat balance can
be formulated as
(
g

in
g

out
) +S
g
_
_
d
f
d
=0
_
_
= 0 (12)
where
g
=
T
g
T
g
ref
and
L
=
T
L
T
g
ref
.
The heat transfer dimensionless term for gas phase, S
g
, is
obtained as
S
g
=
aV
cell
L
m
g
m
C
g
p
(13)
Liquid phase mass balance, Eq. (4) can be written in dimen
sionless form as
s
i
gL
_
dc
f
i
d
_
=1
= c
L
i

in
c
L
i

out
i
NR
j=1
ji
M
j
r
b
j
exp
_
j
_
1
1
L
__
= 0 (14)
where
gL
is the mass transfer Damkohler number dened
earlier by Eq. (8) and
i
=C
i,ref
/C
ref
.
The kinetic reaction rate parameter, M
j
, appearing in Eq.
(14) is dened as
M
j
=
V
cell
(
L
a
m
)
Q
L
C
ref
R
ref
j
and r
b
j
= R
b
j
/R
ref
j
is the dimensionless representation of the
rate function.
Arrhenius number (
j
) for liquid phase is written as
j
=
E
aj
RT
ref
(15)
The dimensionless liquid phase heat balance equation can be
written as
(
L

in
L

out
) S
L
_
d
L
d
=1
_
+
1
i
NR
j=1
B
j
ji
M
j
r
b
j
exp
_
_
1
1
L
__
= 0 (16)
The heat transfer dimensionless term for liquid phase, S
L
, is
formulated as follows:
S
L
=
aV
cell
L
m
L
m
C
L
p
=
gL
Le (17)
where Le is the Lewis number,
L
/
L
C
L
p
D
ref
.
The heat of reaction parameter, B
j
, is dened as
B
j
=
H
r,j
C
ref
L
C
L
p
T
ref
(18)
Eqs. (6), (12), (14) and (16) are then the dimensionless equa
tions needed in the model for each cell.
3. Film model for mass transfer with gasliquid
reaction
The mass transfer with chemical reaction in the steady
state lmcan be modeled by using the lmtheory. It is used in
order to balance the stagnant elements between bulk phases
and gasliquid interface. A schematic prole of gasliquid
contact according to lm model is shown in Fig. 3.
According to steady lm model accompanied by the reac
tions, for the gaseous species diffusing through the liquid
lm, the steady state mass balance and heat balance in the
liquid lm mass transfer are given as follows.
Fig. 3. Schematic proles of gasliquid contact according to the lmtheory.
2466 A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473
3.1. Mass transfer
D
i
d
2
C
f
i
dZ
2
=
NR
j=1
ji
R
j
(19)
Using the dimensionless variables earlier, the dimensionless
form of Eq. (19) is
d
2
c
f
i
d
2
=
1
s
i
i
NR
j=1
ji
Ha
2
j
r
j
(20)
where Ha
2
j
is the square of the Hatta number for the jth reac
tion; Ha
2
j
=
R
ref
j
2
m
D
ref
C
ref
.
Two boundary conditions are required to solve Eq. (20).
One is obtained by specifying the conditions at the interface
while the other is obtained by specifying the concentration
of the gaseous species in the liquid bulk. Thus
k
gi
(C
g
i
C
g
i,z=0
) = N
f
i,z=0
= D
i
dC
f
i,z=0
dZ
(21)
Appling the Henrys law for solubility of absorbed gas or
Antoines lawfor the vaporization, the interfacial partial pres
sure is transformed into equilibrium concentration as
C
g
i,z=0
= H
i
C
f
i,z=0
, where H
i
= H
i,ref
h
i
() (22)
where h() is the temperature dependency function for the
solubility or the vapor pressure. This is usually an exponential
function of temperature depending upon the heat of solution
or vaporization. The dimensionless equation corresponding
to Eq. (21) can be formulated as
Bi
mi
(c
g
i,out
h
i
(
f
=0
)c
f
i,=0
) =
_
dc
f
i
d
_
=0
(23)
where Biot number for gas phase mass transfer, Bi
mi
was
dened as
Bi
mi
=
m
H
i,ref
k
gi
D
i
(24)
On the other hand, in the case of nonvolatile components
Bi
mi
is zero. Thus the boundary condition at Z=0 is dened
as following. Also note that C
g
i
in Eq. (21) is taken as C
g
i,out
due to the assumption of complete mixing in each cell.
dc
f
i
d
=0
= 0 (25)
At the boundary between the liquid mass transfer lm and
liquid bulk (z =
m
), the concentration is the same. Thus:
c
f
i,=1
= c
b
i
= c
L
i,out
(26)
3.2. Heat transfer
The temperature prole in the lm T
f
is given by
L
_
d
2
T
f
dZ
2
_
NR
j=1
(H
r,j
)(R
j
) (27)
Substituting for the dimensionless temperature in Eq. (27),
the dimensionless formula for heat balance was obtained:
d
2
f
d
2
=
NR
j=1
H
2
aj
j
r
j
(28)
where
j
=
(H
r,j
)D
ref
C
ref
L
T
ref
=
B
j
Le
(29)
Boundary condition at z =0 for the temperature equation (27)
is described in Eq. (30). The summation of heat of convection,
heat of solution and heat of condensation equals the Fouriers
conductive heat ux.
L
_
dT
f
dZ
_
Z=0
= h
g
(T
g
T
f
z=0
)
+
NS
i=1
(H
Si
)
_
D
i
dC
f
i
dZ
_
z=0
(30)
where h
g
is denedas convective heat transfer coefcient, and
(H
Si
) is dened as heat of dissolution or vaporization.
Finally, the dimensionless term for boundary heat ux is
written as follows:
_
d
f
d
_
z=0
= Bi
H
(
g
f
=0
)
NS
i=1
Si
_
dc
f
i
d
_
=0
(31)
Biot number for gas phase heat transfer, Bi
H
, is dened as
Bi
H
=
h
g
L
(32)
and
Si
is dened as
Si
=
(H
Si
)D
i
C
i,ref
L
T
ref
(33)
The boundary condition at z =
m
is obtained from the fact
that the heat transfer lm thickness is larger that the mass
transfer lmthickness
_
h
< 1
_
. Therefore there is the tem
perature gradient at the distance of z =
m
to
h
. The heat ux
is equivalent to heat conduction or
q
f
Z=
h
=
L
T
L
T
f
Z=
m
m
(34)
The dimensionless form at z =
m
is formulated as
(L
1/2
w
1)
_
d
d
_
=1
=
f
=1
L
(35)
A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473 2467
Table 1
Summary of major dimensionless groups
Parameters Dimensionless group
Diffusivity ratios s
i
Effective gas to liquid ow ratios
Fi
Liquid phase mass transfer Damkohler number
gL
Gas heat transfer number S
g
Bulk reaction number M
j
Heat of reaction parameter B
j
Liquid heat transfer number S
L
Lewis number Le
Hatta number for each reaction Ha
j
Biot number for gas phase mass transfer Bi
mi
Biot number for gas lm heat transfer Bi
H
Heat of solution or vaporization parameter
s
where L
w
is the square of the lm thickness ratio dened as
_
m
_
2
= L
w
(36)
3.3. Summary of dimensionless parameters and the time
constants
Table 1 shows the summary of all the dimensionless
parameters dened in both the reactor and the lm model.
It may be noted that some of the parameters are interrelated
and not all of these can be chosen independently. Many of the
parameters can be expressed as the ratio of the time constants
for the various steps.
The time constants involved in the mass transfer processes
are rst identied and dened as follows:
1. Bulk liquid phase residence time
t
BL
=
V
cell
L
Q
L
(37)
2. Reaction time for jth reaction
t
R,j
=
C
ref
R
ref,j
(38)
3. Film diffusion time
t
D
=
2
m
D
ref
(39)
4. Mass transfer time for bulk liquid saturation
t
m
=
L
k
L
a
(40)
Some parameters appearing in the model are the ratios of
these time constants and can be identied as follows:
Ha
2
j
=
t
D
t
R,j
(41)
gL
=
t
BL
t
m
(42)
M
j
= Ha
2
j
t
BL
t
D
_
1 a
L
_
(43)
The gas phase residence time is dened as
t
g
= V
cell
g
Q
g
(44)
and appears in the parameter
Fi
.
Fi
=
t
g
t
L
g
1
H
i,ref
(45)
Note that the gas residence time is scaled by the Henrys law
constant here.
The heat transfer parameters needed are S
g
and S
L
(see
Eqs. (13) and (17) and these are related to
gL
as follows:
S
g
=
gL
u
L
u
g
Le
L
C
L
p
G
C
g
p
(46)
S
L
=
gL
Le (47)
Addition parameters needed are the Biot number for
gas phase mass and heat transfer and the heat of solu
tion/vaporization parameters.
4. Numerical solution methodology
The lm model was used solving BEM applied to subin
tervals over the main region of integration. The reactor model
can often be obtained directly fromthe lmmodel by modify
ing the boundary conditions. These procedures are explained
in the following sections.
4.1. Film model solution
The boundary element method as applied to a set of 1D
second order differential equations has been explained in
detail in Ramachandran (1994). Here we provide a discus
sion to the key aspect of the method without going into the
details.
The lm model equations are given by Eq. (20) for the
concentrations (N equations) and (28) for the temperature
f
.
These equations form a set of second order (coupled) differ
ential equations of the type:
d
2
c
i
d
2
= f
i
(c
1
, c
2
, . . . , c
NS
, c
NS+1
) (48)
where c
i
is to represent the set of lm variables including the
temperature
f
:
c
i
= f
i
(c
1
, c
2
, c
3
, . . . , c
NS
,
f
) (49)
and f
i
is the rate function (RHS) for the ith equation. NS is
the number of species and hence NS+1 is the total number
of equations.
The domain of integration is 01 for . However in viewof
the nonlinear form of the RHS of the differential equations,
the boundary element method is applied over subintervals in
this work and is closer to the nite element method.
2468 A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473
The weighted residual representation of Eq. (48) is used
as a starting point in the boundary element method. The rep
resentation is as follows:
_
b
a
G
d
2
c
i
d
2
d =
_
b
a
Gf
i
d (50)
The weighted residual formis integrated twice (in contrast to
nite elements where it is integrated only once) to provide an
integral formulation to the problem. By proper choice of the
weighting functions the second derivative can be eliminated.
The weighting functions are two independent solutions to the
adjoint differential equation:
d
2
G
d
2
= 0 (51)
The choice of G
1
=x a and G
2
=b x is used here.
For each element we then get two equations for each
species:
c
ai
+(b a)p
bi
c
bi
=
_
b
a
(x a)f
i
d (52)
and
(b a)p
ai
c
ai
+c
bi
=
_
b
a
(b x)f
i
d (53)
The variables used in the above equations are dened as fol
lows: c
ai
is the concentration of species i at x =a; p
ai
the
concentration gradient of species i at x =a; c
bi
the concen
tration of species i at x =b; p
bi
the concentration gradient of
species i at x =b.
Note that the gradients are also primary variables in this
methodinadditiontoconcentrations andare directlyobtained
as part of the solution. In fact the gradients obtained from the
lm model are the primary link to the reactor model and
the reactor model does not need information on the detailed
concentration/temperature distribution in the lm.
The variables are schematically illustrated in Fig. 4.
The system of equations is then augmented by the
boundary conditions. Note that the boundary conditions
are nonlinear (due to temperature effects on the solubility)
and iterative solution based on NewtonRaphson method
Fig. 4. Element level representation of the lm model denition of local
variables for any particular element.
is needed. These details will be provided in a forthcoming
paper and are not shown here.
4.2. Coupling with the reactor model
In this subsection we show that the reactor model can be
directly incorporated in the BEM solution by simply chang
ing the boundary conditions for many cases. We illustrate
this for the case of constant gas velocity (f
g
in
= f
g
out
). The
method is similar for varying gas velocity but is somewhat
more involved.
The key idea is that the gas phase mass balance (Eq. (6))
and the lm boundary conditions (23) can be combined to
obtain a modied boundary conditions for all the gas phase
species at =0. Using
_
dc
f
i
d
_
from Eq. (23) in Eq. (6) and
rearranging we obtain:
c
g
i,out
[1 +
gL
Fi
s
i
Bi
mi
]
= c
g
i,in
+
gL
Fi
s
i
Bi
mi
h
i
(
f
=0
)c
f
i,=0
(54)
Using this back in Eq. (6) we obtain
Bi
mi
(c
g
i,in
h
i
c
f
i,=0
) =
_
c
f
i
d
_
=0
(55)
where Bi
mi
is a modied Biot number dened as follows:
Bi
mi
=
Bi
mi
1 +
gL
Fi
s
i
Bi
mi
(56)
Note that Bi
mi
takes into account directly the concentration
change in the gas phase for each cell. The boundary con
dition (Eq. (55)) is directly in terms of the known inlet gas
concentration. Once the BEM lm model is solved with this
modication, C
g
i,out
can be directly calculated from Eq. (54)
above.
In a similar manner Eqs. (12) and (31) for gas phase heat
balance and the boundary condition for gas temperature can
be combined to give a composite boundary condition for the
lm temperature equation. The resulting equation is
_
d
f
d
_
=0
= Bi
H
(
g
f
=0
)
NS
i=1
Si
_
dc
f
i
d
_
=0
(57)
where
Bi
H
=
Bi
H
(1 +Bi
H
S
g
)
(58)
The boundary condition, at =1, needs no further algebraic
modications. They are directly in the form of a general
nonlinear Robin condition and can be incorporated into the
solution of the lm model by BEM. Note that these are non
linear coupled boundary conditions in view of the nonlinear
nature of the bulk reaction.
A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473 2469
5. Numerical tests
5.1. Test example 1: isothermal single reaction case
A simple single step reaction represented by
A +B Product
is considered as the rst test example with A being the gas
phase species and Bis being a nonvolatile liquid phase reac
tant. The kinetics is represented as rst order with respect to
Aand second order with respect to B. This kinetics scheme is
representative of oxidation of Fe
2+
EDTA complex which is
an important step in the regeneration of Fe
3+
complex formed
in the LoCat process for the removal of hydrogen sulde
used. The rate expression is selected
R
j
= k
2
C
A
C
2
B
The reference concentrations are chosen as
C
A,ref
=
C
g
A,in
H
A
, C
B,ref
= C
L
B,in
Also C
ref
=C
A,ref
for the kinetic time constants and kinetic
parameters.
The parameters needed in the lm model are then the tra
ditional Hatta number and parameter dened as follows:
Ha
2
A
= k
2
C
B,ref
2
D
A
(59)
=
2
D
A
D
B
C
g
A,in
/H
A
C
g
B,in
Additional parameter needed is Bi
mi
for external mass trans
fer. For isothermal conditions, heat transfer parameters are
not needed.
First we solve the lm model alone to check the nature
of solution. The chosen parameters were H
a
=25, =0.1,
Bi =250. Bulk A is taken as zero only for the purpose of
testing the lm model. The lm model solutions are shown
in Fig. 5. It is seen that there is considerable depletion of B
Fig. 5. Concentration proles for lm model alone for isothermal single
reaction rate, H
a
=25, =0.1, Bi =250.
Fig. 6. Concentration proles in the lm for isothermal single reaction rate,
gL
=10,
Fi
=0.03, M
j
=10
5
.
at the interface for these conditions. The predicted gradient
at the interface is in agreement with the earlier results.
Nowwe look at the reactor model for the following param
eters
gL
=10,
Fi
=0.03, M
j
=10
5
.
The modied Bi
mi
is obtained as
Bi
mi
=
250
1 +10 0.03 250
= 3.28
The lm model results are now shown in Fig. 6. The exit
concentration in the liquid is now 0.0515, the gas exit con
centration is 0.7287 and these are the reactor level results. It
may be useful to compare the uxes at =0 and 1 for the two
components. These are shown in the following inset:
Flux at =0 Flux at =1
C
A
0.9040 0.6156
C
B
0.0 0.02884
We nd that the signicant reaction is now taking place
in the bulk liquid as marked by the fact that ux at =1 is
comparable to ux at =0. This is because the bulk concen
tration of B is now very low due to low residence time of the
liquid.
The results for
gL
=1 are also shown for illustration. The
exit gas concentration is 0.866 while the liquid concentration
is 0.5565. The uxes are as follows:
Flux at =0 Flux at =1
C
A
4.435 2.11 10
2
C
B
0 0.4433
Most of the reaction is now in the lm since the bulk
liquid has now relatively high concentration of liquid phase
reactant.
5.2. Test example 2: nonisothermal effects
The parameters used here were as follows:
1
=22,
s
=7.5,
vap
=0, =0.005,
s
=0.001, Le =100,
g
in
=
L
in
= 1, Bi
Hg
=1.0. The results are shown in Fig. 7. The lm
2470 A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473
Fig. 7. Concentration proles in the lm for nonisothermal single reaction
rate,
i
=22,
s
=7.5,
vap
=0, =0.005,
s
=0.001, Le =100,
g
in
=
L
in
=
1, Bi
Hg
=1.0.
temperature has now increased to 1.0810 at the interface and
is 1.073 at =1. Thus there is no signicant gradient of the
temperature in the mass transfer lmbut the lmand the inter
facial temperatures are much higher than that in the bulk. The
effect of increased interfacial temperature is twofold: (i) it
reduces the gas solubility at the interface; (ii) it accelerates the
reaction causing the concentration of A to drop steeply near
=0 in contrast to the isothermal case. The computational
model shown here takes into account both these effects.
6. Case studies
This section shows the application of the model to two
industrially important case studies. Case study 1 deals with
the chlorination of butanoic acid while case study 2 deals
with oxidation of cyclohexane.
6.1. Chlorination of butanoic acid
The reaction scheme involves a series reaction for liquid
phase reactant butanoic acid and a parallel reaction for chlo
rine gas to form monochlorobutanoic acid and dichlorobu
tanoic acid and is represented as
C4
(l)
+Cl
2(g)
MC4
(l)
+HCl
(l)
, rate = R
1
,
C4
(l)
+2Cl
2(g)
DC4
(l)
+HCl
(l)
, rate = R
2
(60)
where C4 is the butanoic acid, MC4 is the monochlorinated
product and DC4 is the dichlorinated product.
Salmi, Paatero and Fagerstolt (1993) derived the kinetic
equations for this reaction scheme based on a proposed reac
tion mechanism resulting in the following form:
R
1
=
k
1
_
C
MC4,l
+k
2
1 +k
C
Cl
2
,l
(61)
R
2
= R
1
k
C
Cl
2
,l
(62)
where R
1
is the reaction rate of the main reaction, R
2
is the
reaction rate of side reaction, coefcient is proportional to
Table 2
Kinetic and Diffusion parameter for chlorination of C4 acid (Romanainen
and Salmi, 1992)
Kinetic parameter
k
1
= 0.1418 y
1/2
(mol/m
3
)
1/2
s
1
k
2
= 8.8013 y (mol/m
3
) s
1
k
=0.0013577 (m
3
/mol)
k
=0.01
y =0.037 (mole fraction of catalyst)
Component Diffusion coefcient, D
i
(m
2
/s)
C4 2.1 10
9
Cl
2
1 10
8
MC4 1 10
8
DC4 1 10
8
HCl 2.1 10
9
the active catalyst and the acid chloride concentration. is
given as follows:
=
[C
TOT
(1 +k
C
Cl
2
,l
)C
MC4,l
]
1/2
[C
TOT
(1 +k
C
Cl
2
,l
)C
MC4,l
]
1/2
+k
C
1/2
MC4,l
(63)
where C
TOT
is total concentration in the liquid phase. The cat
alyst concentration is included in the values of the parameter
k
1
and k
2
. The values of kinetic parameter such as k
1
, k
2
, k
and k
at 130
2
=
1
N
=
2
Pe
_
1
1
Pe
(1 e
Pe
)
_
(64)
Table 3 shows how the value of liquid phase Peclet number
(Pe) in the dispersion model is converted to the number of
mixing cell in the mixing cell model. The simulation results
obtainedfromthe dispersionmodel andthe mixingcell model
Fig. 10. Schematic diagram of the cyclohexane oxidation system.
Table 4
Industrial conditions of cyclohexane oxidation process
Reaction temperature (
C) 160
Reaction pressure (atm) 10
Volumetric reactor (m
3
) 254
Volumetric gas (air) ow rate (l/h) 5 10
4
Volumetric liquid (cyclohexane) ow rate (l/h) 520
Initial liquid phase concentration (kmol/m
3
) 7.52
Catalytic type Cobalt naphthenate
are illustrated in the yield proles of desired product (MC4)
as function of the liquid phase Peclet number (Pe) and the
number of mixing cells as shown in Fig. 8.
The dispersion model usually can be used well for the
system with ow that slightly deviates from plug ow. For
the behavior, which is not too large deviated from plug ow
behavior, both dispersion model and mixing cell model give
identical results. At low N and low Pe, the proles are never
identical due to the large deviation from the plug ow of the
system. The error fromthe dispersion model is usually higher
for these ranges of values of N.
6.2. Oxidation of cyclohexane
The liquidphase oxidation of cyclohexane is an indus
trially essential process for producing cyclohexanol and
cychohexanone. Both substances are extensively used to pro
duce caprolactam, adipic acid, polyamide bers, nylon 6 and
nylon 6,6. The cyclohexane oxidation is a reaction where
liquid cyclohexane is oxidized by bubbling air or oxygen
producing desired products under proper conditions. Salts of
cobalt, copper or manganese are usually used as homogenous
catalysts. However this reaction is relatively complicated
because major products are intermediates in a sequence of
reaction mechanism. Overoxidation generates various unus
able byproducts. In addition, the mechanisms of reactions
Fig. 9. Scheme of kinetics mechanism for cyclohexane oxidation according to Alagy et al. (1974).
2472 A. Kongto et al. / Computers and Chemical Engineering 29 (2005) 24612473
Table 5
Oxygen conversion, and Selectivity of CROH and CRO
Tank
th
%oxygen conversion %cyclohexane conversion Selectivity of cyclohexanol (CROH) Selectivity of cyclohexanone (CRO)
1 89.09 1.0 0.62 0.23
2 89.09 2.2 0.60 0.26
3 89.10 3.2 0.59 0.28
4 89.10 4.3 0.57 0.30
5 89.10 5.4 0.56 0.32
producing desired products proceed slowly and control the
rate of oxygen absorption. Therefore design of the reactor
requires investigation of both kinetic model and mass and
heat transfer.
The kinetic mechanism of cyclohexane oxidation is
proven to be a complex reaction of freeradical reactions that
proceed as multistage chain reactions. There are a number
of modied and simplied kinetic schemes, depending on
the type of catalysts. One of the important kinetics schemes
which is usually used is the model of Alagy, Trambouze and
van Landeghem (1974). The mechanism of this model is
indicated in Fig. 9 where CRHe, CROH, CRO and D are
dened as cyclohexane, cyclohexanol, cyclohexanone and
byproduct, respectively. The gasliquid reactor for industrial
oxidation of cyclohexane, multistage ow reactor, consists
of ve bubble tanks in series. Cyclohexane liquid is fed into
the tanks in series, while the air is injected into ve tanks in
parallel as shown in Fig. 10.
In each tank of the steady state gasliquid reactor, both gas
and liquid phase are considered as well mixed. Furthermore,
gas reactants fromgas bulk are transferred into the liquid lm
and liquid bulk where the reactions take place in liquid phase.
The industrial conditions are listed in Table 4.
In this case, kinetic model is based on Alagy et al. (1974).
The physical property data such as; Henrys law constant, H
and diffusivity, D were determined from Suresh, Sridharand
and Potter (1988). The hydrodynamics data such as k
L
and
a (interfacial area) were obtained using correlation of Akita
and Yoshida (1974). The diffusivities were taken from Reid,
Prausnitz and Poling (1987). Key results are shown below
and detailed modeling will be published elsewhere.
Table 5 shows the reactant conversion and product selec
tivity. The cyclohexane conversion is low in the range of
1.05.4% while the gas phase reactant conversion is almost
constant in each tank. This is due to feeding of oxygen in
parallel into each tank. The oxidation reaction is a slow
reaction and occurs mainly in the liquid bulk. Thus the con
version of cyclohexane is limited. Oxygen is consumed in
many steps of oxidation of various reactants as shown in the
kinetic mechanism. Therefore the conversion is relatively
high. Main products, cyclohexanol and cyclohexanone are
intermediate products. Selectivity of cyclohexanol decreases
with number of tanks while the selectivity of cyclohexanone
increases with number of tanks. This is due to overoxidation
of cyclohexanol to cycloxeanone as indicated in the kinetic
mechanism.
7. Conclusions
A comprehensive model was developed for gasliquid
reactors using the mixing cell approach. Heat and mass trans
fer effects were considered in the liquid lm. A boundary
element method was used to solve the lm model differen
tial equations. The uxes at the interface and into the bulk
were directly obtained as a part of the solution method.
These uxes were directly used as the link to the reac
tor model and used for solution of the reactor model. The
method was applied to gas absorption with reaction. Simple
isothermal and nonisothermal reactions were numerically
tested. In addition, the models were applied to two indus
trially important cases, chlorination of butanoic acid and
oxidation of cyclohexane. For the chlorination of butanoic
acid which is an autocatalytic reaction, the yield of desired
product, monochlorobutanoic acid, is favored by the high
degree of mixing in the liquid phase. Therefore, this reaction
should be carried out in a CSTR. In the case of cyclo
hexane oxidation, a series of ve bubble tanks with par
allel gas reactant feeding for cyclohexane oxidation was
applied. It was found that the cyclohexane conversion is
limited while the gas phase reactant conversion is almost
constant and relatively high in each tank. Due to the com
plex reaction, oxygen is consumed in many steps of oxida
tion and selectivity of main intermediate products depends
on the overoxidation in the seriesparallel oxidation kinetic
mechanism.
Acknowledgments
The nancial supports from the Kasetsart University
Research and Development Institute (KURDI), CHEADB
Graduate Engineering at Kasetsart University, and the Kaset
sart University graduated school, are acknowledged. P.A.
Ramachandran (Washington University) also wishes to
acknowledge partial support from NSF engineering centers
program EEC0310689.
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