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( | | c c c c
' ' + = +
( |
c c c c
( \ .
(1)
where
i
U and C are the time average velocity and
concentration respectively,
i
u c ' ' is the fluctuating
mass flux, which is an unknown variable to be solved.
The conventional way to solve
i
u c ' ' is by assum-
ing
t i
i
C
u c D
x
c
' ' =
c
, and the coefficient D
t
, commonly
called turbulent mass transfer diffusivity or dispersion
coefficient, can be found empirically. To avoid the use
of empirical method, a CMT
2
c
c c
'
' model was de-
veloped [13] to obtain the parameter D
t
. This model
has been successfully applied to simulating many
mass transfer processes, including distillation, chemi-
cal absorption, catalytic reaction and adsorption in
tray and packed columns [4].
In this study, another CMT method is proposed
by evaluating
i
u c ' ' directly in Eq. (1) instead of intro-
ducing the parameter D
t
. The model predictions on the
concentration profile and separation efficiency of a
commercial scale packed and a tray distillation col-
umns reported in the literature are given below and
compared with the experiment measurements.
2 THE PROPOSED FLUCTUATING MASS
FLUX MODEL
2.1 Model equations
The model assumptions are:
(1) The distillation operation is steady;
(2) Constant molar flow is applied for the gas and
liquid phases. This means that the heat of vaporization
and condensation of the separating component are
early equal, so that the energy equation can be omitted
in order to simplifying the simulation;
(3) Heat lost to the environment is neglected.
The proposed mathematical model, in pseudo
liquid phase form, is consisted of mass transfer equa-
tion set and the accompanied CFD set as follows:
(1) The mass transfer equation set:
Mass transfer equation,
( )
L L C i i
i i i
C
U C D u c S
x x x
o o
( | |
c c c
' ' = +
( |
c c c
( \ .
(2)
where
L
o is the fraction of liquid in the vapor-liquid
Received 2011-06-20, accepted 2011-09-05.
* Supported by the National Natural Science Foundation of China (20736005).
** To whom correspondence should be addressed. E-mail: ktyu@tju.edu.cn
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 718
mixture.
Transport equation for fluctuating mass flux
i
u c ' '
(see Appendix),
( )
( )
j i
j
i
i j ij i
j j j j
i i
i j j
j j j j j
U u c
x
u p c c
u u c Du c
x x x x
U u C c p c
u u u c D
x x x x x
o v
c
' ' =
c
| | | | ' ' ' ' c c c c
' ' ' ' ' + +
| |
|
c c c c
\ .
\ .
| | ' ' ' ' c c c c c
' ' ' ' + + + +
|
|
c c c c c
\ .
(3)
The foregoing equation should be modeled in
order that it can be used for computation. One of the
modeled form can be used as follows [5]:
2
1
2 3
i i i
j
j j j
i i
i j j i j
j j j
u c u c u c k
U c
t x x x
U U C
u u u c c u c c u c
x x k x
v
c
c
( | | ' ' ' ' ' ' c c c c
+ = +
( |
c c c c \ .
(
c c c | |
' ' ' ' ' ' ' ' + +
|
c c c
\ .
(4)
where the constants are:
1
c = 0.07,
2
c = 3.2,
3
c = 0.5.
In the foregoing equation, the variables k, c, v
and U
i
can be obtained by using k-c model of CFD
methodology, and the
i j
u u ' ' can be calculated from the
following Reynolds stress transport equation:
( )
2
i j i j
k
k
i j k jk i ik j
k
i j j
i
i k j k
k k k k
j
i i i
j i k k
u u u u
U
t x
u u u u p u p
x
u u U
U
u u u u
x x x x
u
u u u
p
x x x u
o o
c
c c
+ = +
c c c
(
c c
' ' + (
c c
(
(8)
where n represents the molecular viscosity of the liq-
uid phase, S
m
is the source term for the liquid flow,
i j
u u ' ' is calculated according to Boussinesqs hypothe-
sis as given in Eq. (6).
Equation of turbulent kinetic energy k:
( ) ( )
L L t
L
L t L
i
i j k i
j
i i
j i j
k kU k
t x x x
U
U U
x x x
o o
o
o
o o c
c c ( c c | |
+ = + +
( |
c c c c
\ .
| |
c
c c
| +
|
c c c
\ .
(9)
Equation of turbulent kinetic energy dissipation c:
( ) ( )
L L t
L
2
L 2 L
i
i i i
j
i i
t
j i i
U
t x x x
U
U U
C C
k x x x k
c
c c
o c o c c
o
o
c c
o o
1
c c ( c c | |
+ = + +
( |
c c c c
\ .
| |
c
c c
| +
|
c c c
\ .
(10)
where the constants are [6]: 0.09 C
= ,
1
1.44 C
c
= ,
2
1.92 C
c
= , 1.0
k
o = , 1.3
c
o = .
2.2 Boundary condition
2.2.1 Inlet conditions
For packed column [7],
in
U U = ,
in
C C = ,
2
in
0.003 k U = ,
1.5
in
in
H
0.09
k
d
c =
where d
H
is the hydraulic diameter of random packing,
which can be calculated by:
H
4
(1 )
d
a
There are no experimental measurements re-
ported or empirical correlations available from the
literature for determining the inlet condition of the
fluctuating mass flux
in i
u c ' ' . In the present study, by
considering the concept of turbulent intensity and the
analogy between momentum and mass transfer, it can
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 719
be estimated by:
2
in in in
TI
i
u c U C ' ' =
where TI is the turbulence intensity and can be calcu-
lated by the formula recommended by the FLUENT
Inc.:
( )
H
1/ 8
TI 0.16
d
Re
=
where
H
d
Re is the Reynolds number base on hydraulic
diameter of random packing.
For tray column [8],
in
U U = ,
in
C C = ,
2
in
0.003 k U = ,
1.5
in
in
0.09
0.03 / 2
k
W
c =
The inlet mass flux
in i
u c ' ' is the same as the
packed column.
2.2.2 Outlet conditions
The flow for both packed and tray columns at the
outlet is considered as fully developed, so that the zero
normal gradients are chosen for all variables except
pressure.
2.2.3 Wall conditions
The no-slip condition of flow is applied to the
wall for both packed and tray columns, and the zero
flux condition at the wall is adopted.
3 COMPARISON BETWEEN MODEL SIMU-
LATIONS AND EXPERIMENTAL MEASURE-
MENTS
The packed column The object of simulation is
an industrial scale packed column reported by Shariat
and Kunesh [9] which is 1.22 m in diameter and
packed randomly with 50.8 mm carbon Pall ring. The
mixture to be separated is cyclehexane (C
6
) and
n-heptane (n-C
7
). The operation is under total reflux
and at 165.5 kPa.
3.1 Evaluation of source terms
In numerical computation, the model equations
should be firstly discrete into a large number of small
finite elements. Thus the source terms are referred to
the conditions appeared in the individual element,
such as velocity, concentration and temperature ob-
tained in the course of numerical computation.
The source term S
C
in mass transfer Eq. (2), rep-
resented the mass of C
6
transferred from the liquid
phase to the gas phase, can be determined by solving
simultaneously the following rate equations:
( )
C L e I
S k a MB x x = (11)
( )
C G e I
S k a MB y y =
I
I
I
1 ( 1)
x
y
x
|
|
=
+
where k
L
and k
G
are respectively the film coefficients
of mass transfer of liquid phase and gas phase, a
e
is
the effective interfacial area, M is the molar mass of
C
6
, kgkmol
1
, B is the molar concentration in volume
basis of C
6
, kmolm
3
, x and y are the mole fraction of
C
6
in liquid and vapor phases respectively, the sub-
script I refers the interfacial condition where liquid
and vapor are in thermodynamic equilibrium, is the
relative volatility of the separating mixture.
The k
L
and k
G
can be calculated by using Wag-
ners formulas [10]:
0.5
L L
L
L
4 Du
k
|
o _
| |
=
|
t
\ .
( )
0.5
G G G
G
L
4 D u
k
|
o _
(
=
(
t
e L
1
a
a
o
where D
G
is the vapor molecular diffusion coefficient,
u
L
, u
G
are the liquid and vapor phase superficial ve-
locities,
L
| ,
G
| are the gas and liquid phases en-
hancement factors which are equal to unity at the op-
erating conditions concerned. The characteristic length
, for different type of packing can be expressed by:
2
pk
C Z _ =
where C
pk
is equal to 0.031 for 50.8 mm metal Pall
rings; and Z is the bed height.
The liquid volume fraction
L
o can be deter-
mined from the total liquid holdup H
t
and the porosity
y as follows:
t
L
H
o
=
t s op
H H H = +
where the equations used for calculation are: the static
holdup H
s
of metal Pall rings by [11], operating holdup
H
op
by [12] and porosity y of randomly packed bed by [13].
The source term S
m
in momentum transport Eq.
(8) can be calculated by:
( )
m LG L LS
S F F g o = + +
where F
LG
is the interface drag force between gas and
liquid phases, F
LS
is the flow resistance.
The F
LG
is related to the pressure drop caused by
interaction between the liquid and vapor phases. For
irrigated packing, the pressure drop
t
p A is equal to
the sum of dry bed
d
p A and the increased part of
pressure drop due liquid adhered to the packing
surface p
L
, thus
t d L
p p p A = A + A . The
d
p A ,
L
p A
can be calculated by [14]. Thus the F
LG
can be ex-
pressed by:
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 720
t
LG slip
slip
p
F U
U
A
=
where U
shp
is the slip velocity between gas phase and
liquid phase, which is defined as:
slip G
U U u =
where u is interstitial velocity.
The F
LS
created by the presence of random
packing can be treated as body force, which is calcu-
lated by [15]:
2
LS
2 2
e e
(1 ) (1 )
150 1.75 F u u
d d
(
= +
(
and
( )
e
6 1
d
a
=
The physical properties of the separating system
and the characteristics of metal Pall ring are given in
the published paper [9].
3.2 The simulated result and comparison
The commercial software FLUENT with finite
volume method was used for the numerical computation.
In order to obtain the axial concentration along the
column for the comparison with the reported measure-
ment, the simulated axial concentrations along radial
direction were averaged at different height of the column.
Figure 1 shows the comparison between the pro-
posed model predictions (solid lines) and the experi-
mental data (points) [9]. The agreement between them
is satisfactory. Besides, the simulations by Liu et al. [3]
using
2
c
c c
'
' model is also shown in Fig. 1. As seen
in the Fig. 1, the simulated results by
2
c
c c
'
' model
fit the experimental data better at the upper part of the
column and the proposed model fit the experimental
data better at the lower part of the column.
The simulated result of radial distribution of liq-
uid phase velocity is shown in Fig. 2. As seen in this
figure, for r/R from 0 to 0.8, no significant variation of
relative liquid velocity is found at z = 2.819 m and
F-factor = 1.52 ms
1
(kgm
3
)
0.5
. It can be explained
that the porosity is relatively uniform near the column
center. The obvious variation of relative velocity near
the wall region is mainly due to the non-homogenous
porosity. This phenomenon has been confirmed by
many investigators [16, 17].
Figure 3 shows the C
6
concentration profiles
along the column. The concentration near the column
center (r/R ranges from 00.7) is relative constant;
while in the near wall region (r/R ranges from
0.70.99), the concentration increased sharply with
fluctuation as shown in Fig. 4. This may be due to the
non-uniform porosity distribution and the uneven ve-
locity profile near the wall.
(a) F = 0.758 ms
1
(kgm
3
)
0.5
(b) F = 1.02 ms
1
(kgm
3
)
0.5
(c) F = 1.52 ms
1
(kgm
3
)
0.5
Figure 1 Comparisons of the concentration profiles in
liquid phase between model predictions and experimental
measurement
measured; predicted by proposed model; predicted
by Liu et al.
Figure 2 Relative velocity profile of liquid phase along the
radial direction at z = 2.819 m for F-factor = 1.52 ms
1
(kgm
3
)
0.5
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 721
Figure 4 Predicted profiles of C
6
concentration at differ-
ent packed height for F = 1.52 ms
1
(kgm
3
)
0.5
Figure 5 Comparisons of the predicted and experimental
HETP at different F-factor
measured; predicted by proposed model; predicted by
Liu et al.
The predicted and measured HETP value [9] for
different F-factor is shown in Fig. 5, where reasonable
agreement between them is seen. Compared with the
predictions obtained by
2
c
c c
'
' model [3], the predicted
HETP value obtained by proposed model fit the
experimental measurement better for F = 0.758
ms
1
(kgm
3
)
0.5
and F= 1.52 ms
1
(kgm
3
)
0.5
; however,
for F= 1.02 ms
1
(kgm
3
)
0.5
, the deviation is larger
than
2
c
c c
'
' model prediction.
4 THE TRAY COLUMN
A commercial scale sieve tray column for distil-
lation reported by Sakata and Yanagi [18] was simu-
lated by using the proposed model. The feed is a mix-
ture of cyclohexane/n-heptane (C
6
/n-C
7
) and the oper-
ating pressure is 165 kPa. Detailed data about the
column are available in the published literature. The
liquid in the downcomer is assumed to be completely
mixed and the computation followed a tray-by-tray
scheme to simulate the multi-tray column.
The mass transfer equation and the accompanied
CFD equations are similar to those giving in the above
section for packed column. The evaluation of the
relevant parameters should be reconsidered.
4.1 Evaluation of the source terms
The source term S
C
for mass transfer between
vapor and liquid phase can be calculated by following
equation:
( )
E
C OL e
S K a MB x x = (12)
where K
OL
is the overall liquid phase mass transfer
coefficient, x
E
is the liquid composition in mole frac-
tion and in equilibrium with the vapor passing through
the liquid layer on the tray.
The overall liquid phase mass transfer coefficient
(a) F = 0.758 ms
1
(kgm
3
)
0.5
(b) F = 1.02 ms
1
(kgm
3
)
0.5
(c) F = 1.52 ms
1
(kgm
3
)
0.5
Figure 3 C
6
concentration profiles in liquid phase predicted by proposed model at different F-factors
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 722
K
OL
can be expressed by the following relationship:
OL
L G
1
1/ 1/
K
k mk
=
+
where m is the coefficient of distribution between two
phases. The film coefficients of mass transfer k
L
and
k
G
are given by Zuiderweg [18] for sieve tray column
as follows:
L G
1
1
LPR
k mk
| |
=
|
\ .
G
2
G G
0.13 0.065
k
= (1.0<
G
<80)
where LPR is the liquid phase resistance which is 0.37,
and the average value of m covering the range of con-
centration under consideration was found to be 0.0055.
The effective vapor-liquid interfacial area a
e
was cal-
culated by Zuiderweg correlation [19].
The source term S
m
in momentum transport equa-
tion can be calculated by the following equation by
Zhang [20]:
G G
m
f
i
U
S U
h
=
where the liquid height h
f
is equal to
f w ow
h h h = + ,
and
ow
h is given by the following correlation [21]:
( )
3
ow h w
2.84 10 / h L l
=
The liquid volume fraction in tray column is obtained
by Bennett et al. [22] correlation:
( ) ( )
0.91
L G G L G
exp 12.55 U o
(
=
(
4.2 Comparison between simulation and experi-
mental measurement
For comparison with the reported measurement,
the simulated C
6
concentration should be averaged at
the outlet of each tray. As seen in Fig. 6, the agreement
between the simulation obtained by proposed model
and the experimental data [18] is satisfactory. The ob-
vious deviation at tray No. 4 may be due to the ex-
perimental error. For a distillation column separating a
binary mixture under total reflux, the curve connecting
the outlet concentration of each tray should be nearly
smooth. The experimental data at tray No. 4 is clear
outside of the smooth curve representing all other data.
Compared with the simulation obtained by Sun et al.
[2] using
2
c
c c
'
' model, the proposed model predic-
tions are somewhat higher.
Figures 7 and 8 show the concentration contours
of the x-y planes on trays No.6 and No.8. The concen-
tration patterns of the other six trays are similar to
those as shown in Figs. 7 and 8. The simulated con-
centration contour by using present model is also
compared with that by
2
c
c c
'
' model as reported by
Sun et al. [2] in Fig. 9. In this figure, the concentration
profiles simulated by both model is almost the same
except in the region near the wall where the present
model enables to give more detailed concentration
distribution than that by the
2
c
c c
'
' model.
Figure 7 Predicted concentration profiles of the x-y plane
on tray No. 8 at 20 mm (upper) and 70 mm (lower) above the
tray floor
The Murphree efficiencies for each tray were
calculated and compared with experimental data as
shown in Fig. 10. Except for trays No. 3 and No. 4,
Figure 6 Comparisons of the C
6
concentration at the
outlet of each tray between model simulation and experi-
mental measurement
experiments; predicted by proposed model; predicted
by Sun et al.
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 723
the predictions obtained by proposed model are in
agreement with the measurement except trays No. 3
and No. 4. The reason for the obvious deviation has
been given in previous section. Compared with the
predictions reported by Sun et al. [2], the proposed
model predictions are somewhat lower. This may be-
cause that the predicted concentration at the outlet of
each tray obtained by the proposed model is higher
than that by Sun et al [2].
5 CONCLUSIONS
A simplified fluctuating mass flux model (
i
u c ' '
model) derived from the turbulent mass flux transport
equation is proposed. The proposed model is charac-
terized by solving the parameter
i
u c ' ' directly in the
turbulent mass transfer equation instead of using the
empirical turbulent mass transfer diffusivity
t
D for
predicting the concentration profile and separation
efficiency of distillation column. The packed and
sieve tray distillation columns reported in the litera-
ture were simulated by the present model.
(1) For the simulated packed column, the con-
centration profile of the whole column, the average
axial concentration along column height and the
HETP of the separation were obtained. The simulated
results were in satisfactorily agreement with the re-
ported experimental measurements.
(2) For the sieve tray column, the concentration
profile on the tray, the average outlet concentration
Figure 8 Predicted concentration profiles of the x-y plane on tray No. 6 at 20 mm (left side) and 70 mm (right side) above the
tray floor
(a) Present model simulation (b)
2
c
c c
'
' model simulation
Figure 9 Comparison of simulated concentration profile on tray No. 8 at 20 mm above the tray floor by present model and
by
'
'
2
c
c
c model
Figure 10 Comparisons of Murphree efficiency for each
tray between the model predictions and the experimental
measurements
measurements; predicted by proposed model; predicted
by Sun et al.
Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011 724
and the Murphree tray efficiency of each tray were
obtained, which were confirmed by the reported ex-
perimental data.
(3) The simulated results by the proposed model
are very close to that by the
2
c
c c
'
' model.
ACKNOWLEDGEMENTS
The authors acknowledge financial support by
the National Natural Science Foundation of China
(Contract No. 20736005) and the assistance by the
staff in the State Key Laboratories for Chemical En-
gineering (Tianjin University).
NOMENCLATURE
a surface area per unit volume of packed column, m
1
a
e
effective area for mass transfer between the gas phase and
liquid phase, m
1
B molar concentration in volume basis, kmolm
3
C time average concentration, mass fraction
*
C time average equilibrium concentration, mass fraction
C
pk
characteristic constant of specific type packing
C
t
parameter in the expression of the mass turbulent diffusivity
C
1c
, C
2c
, C
3c
, C
n
model parameters in k-c model equations
c' fluctuating concentration, mass fraction
c
1
, c
2
, c
3
model parameters in transport equation for the turbulent
mass flux
D molecular diffusivity of C
6
in liquid phase, m
2
s
1
D
G
molecular diffusivity of C
6
in gas phase, m
2
s
1
D
t
turbulent mass turbulent diffusivity, m
2
s
1
d
e
equivalent diameter of random packing, m
d
H
hydraulic diameter of random packing, m
d
p
nominal diameter of the packed particle, m
F F factor, ms
1
(kgm
3
)
0.5
F
LG
interface drag force between gas phase and liquid phase,
kgm
2
s
2
F
LS
flow resistance created by the randomly packing, kgm
2
s
2
F
pd
dry packing factor, m
1
G
f
gas loading factor, kgm
2
s
1
g acceleration due to gravity, ms
2
H
op
operating holdup in packing column
H
s
static holdup in packing column
H
t
total liquid holdup in packing column
h
f
height of the liquid layer in tray column, m
h
w
weir height in tray column, m
K turbulent kinetic energy, m
2
s
2
K
OL
overall liquid phase mass transfer coefficient in tray column,
ms
1
k
G
gas phase mass transfer coefficient, ms
1
k
L
liquid phase mass transfer coefficient, ms
1
L liquid flow rate per unit cross-section area, kgm
2
s
1
L
f
liquid loading factor, kgm
2
s
1
L
h
liquid reflux rate, m
3
h
1
l
w
weir width, m
M mass per kilo-mole of C
6
, kgkmol
1
m distribution coefficient
p
d
period of oscillation normalized by the nominal particle size
p
t
total pressure of gas phase, kgm
1
s
2
p
d
dry-bed pressure drop per meter packing, kgm
1
s
2
p
L
wet-bed pressure drop per meter packing, kgm
1
s
2
p
t
total pressure drop per meter packing, kgm
1
s
2
R radius of the column, m
r position in radial direction, m
S
C
source term in concentration equation, kgm
3
s
1
S
m
source term in momentum transport equation, kgm
2
s
1
TI turbulence intensity
U
G
, U
L
vapor and liquid phase superficial velocities, respectively, ms
1
U
slip
slip velocity between gas and liquid phase, ms
1
u interstitial velocity vector of liquid, ms
1
i
u' fluctuating velocity, ms
1
W weir length, m
x C
6
mole fraction in liquid bulk
x
E
C
6
mole fraction in equilibrium with the vapor
x
I
C
6
mole fraction in liquid interface
y C
6
mole fraction in gas bulk
y
I
C
6
mole fraction in gas interface
Z packed bed height, m
z axial position, m
o
L
volume fraction of liquid phase
relative volatility
y porosity distribution of the random packing bed along the
radial direction
y
c c
' ' ' ' + =
c c
| | | | ' ' ' ' c c c c
' ' ' ' ' + +
| |
|
c c c c
\ .
\ .
| | ' ' ' ' c c c c c
' ' ' ' + + + +
|
|
c c c c c
\ .
(A5)