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Received 12 April 2006; received in revised form 1 February 2007; accepted 2 February 2007
Available online 20 February 2007
Abstract
The work focuses on a hybrid process for treating air charged with a hydrophobic volatile organic compound (VOC), coupling an absorption
process with membrane pervaporation in order to reuse the absorbent. Toluene was chosen as the target VOC. Four topics were investigated:
choice of the absorbent, hydrodynamics and mass transfer in a packed column, regeneration by pervaporation and nally analysis of the coupling
of the two processes. In a previous study, 7 absorbents were compared with regard to experimental data (gasliquid equilibrium constants,
viscosity) and data from the literature. Di(2-ethylhexyl) adipate (DEHA) was shown to be the most suitable absorbent. In the rst part of this
work, experiments in a packed column showed that the viscosity of DEHA led to an increase in pressure drop, which nevertheless remained at
a reasonable level. Mass transfer experiments were performed and kinetic constants (KL a) calculated. It was proven than washing with DEHA
is highly efcient for toluene absorption. The most innovative part of the work is the regeneration of used absorbent by pervaporation. PDMS
was chosen as the active membrane layer. Pervaporation ow rates of toluene were measured for the DEHAtoluene solutions corresponding
to column foot concentrations. Transfer resistance is mainly controlled by the liquid boundary layer close to the membrane. The system was
modelled and several interesting conclusions deduced. Solving the equations by means of a numerical method enabled calculation of the column
height and membrane surface area required to treat a 10 000 m3 h1 gas ow charged with 5 g m3 of toluene.
2006 Elsevier Ltd. All rights reserved.
Keywords: Absorption; Chemical processes; Environment; Mass transfer; Membranes; Packed bed
1. Introduction
Atmospheric volatile organic compounds (VOCs) are involved in photochemical reactions creating ground-level
ozone (urban smog) and entail environmental threats such
as global warming, acid rain and air toxins. Although VOCs
are emitted naturally, human sources are predominant in urban/industrialized areas. In order to reduce anthropic emissions, legislation such as the Clean Air Act Amendments
(EPA, 1998) and EEC Directives (EEC, 1999, 2001) specify
maximum concentration levels for VOC emissions into the
atmosphere. When no upstream process improvement can lead
Corresponding author. Tel.: +33 4 42 90 85 01; fax: +33 4 42 90 85 15.
2577
(1)
ln H = 26.925
CG
H MDEHA
CL = H CL .
RT DEHA
(4)
This dimensionless Henrys constant H related to concentrations will be used in modelling. Absorption of gaseous toluene
2578
Table 1
Selection of physicochemical properties of the system
Pure component properties
Binary properties
Pure DEHA
Molar weight
(g mol1 )
Density (25 C)
(kg m3 )
Fusion
temperature ( C)
350.8
Vaporization
temperature ( C)
Viscosity (25 C)
(mPa s)
Vapor pressure
(20 C) (Pa)
Pure toluene
TolueneDEHA
Activity coefcient
(25 C)
Henrys law constant H
(25 C) (kPa)
Diffusion coefcient DL
(25 C) (m2 s1 )
92.14
910
864
76
95
210
110
1.93
8.65 1010
ToluenePDMS
11.2
7.48 106
0.52
Partition coefcient S
(25 C)
Diffusion coefcient DM
(25 C) (m2 s1 )
3804
1018
1.10 1010
Fig. 3. Pressure drops and liquid retention in the packed column in function of gas velocity and liquid ow rate.
591
T
2
.
(5)
The equilibrium between liquid and gas phases can be deduced from the previous data by considering a pseudogas phase.
The equilibrium is represented by the equation
CM S
H MDEHA
CL .
RT DEHA
(6)
2579
Table 2
Experimental results of mass transfer in the packed column
Experiment [Toluene] L
G
KL a
number
(mg m3 ) (kg m2 s1 ) (kg m2 s1 ) (s1 )
1
2
3
4
5
6
7
4990
1205
1193
5038
520
1005
1005
13.16
13.16
9.87
6.58
6.58
6.58
6.58
0.51
0.51
0.51
0.51
1.16
1.21
1.81
KG a
(s1 )
2580
packing used in this study. As expected, simply using the correlations of Onda et al. (1968) gives values very far from the
experimental results. Billets more recent correlation does give
predictions closer to reality, but still very far from experimental values (overestimating KL by a factor of 1050), which are
therefore invalid for an industrial utilization.
Neither correlation from the literature is therefore satisfactory for modelling our system. There is currently a lack of
knowledge concerning mass transfer in a packed column with
viscous uids. We shall therefore propose a correlation enabling
the prediction of our results with a view to the industrial scaleup of an absorption column. In the framework of this study,
we propose an empirical correlation. The form followed by our
experimental results is
ShL =
KL
a
C
=
A ScL ReB
G ReL .
aD L
awet
(7)
Table 3
Toluene ow measured during pervaporation of pure toluene (T = 48 C)
Toluene concentration in feed
(g L1 )
Liquid
(m s1 )
4.6
4.6
4.6
6.3
6.3
6.3
10.7
10.7
10.7
0.34
0.60
0.95
0.34
0.60
0.95
0.34
0.60
1.30
velocity
Average pervaporation ow
rate (kg m2 h1 )
3.8
5.1
6.2
5.0
6.8
8.6
8.4
11.1
16.9
PDMS membrane (PERVAP 1060) was used in order to characterize the pervaporation of toluene from DEHA mixtures.
A previous study (Heymes et al., 2006c) aimed to examine
the feasibility to regenerate the used DEHA by pervaporation
with a PDMS membrane (PERVAP 1060). Toluene concentrations into liquid were chosen in accordance of a real absorbent solution concentration at the bottom of the absorption
column. Theoretically, the absorption tower treating an exhaust
gas (25 C) charged with toluene at 5 g m3 will provide a maximum concentration of 17 g L1 (DEHA). Since the thermodynamic equilibrium will never be reached in an absorption tower,
the liquid concentration range was chosen as [110 g L1 ] for
the experimental investigations.
The points of interest are the selectivity of the separation
and the toluene ow rate extracted from the liquid mixture.
Table 3 gives experimental toluene ow rates recovered in cold
traps at different concentrations and liquid velocities. All experiments were performed at 48 C. Results show that toluene
can be extracted from the tolueneDEHA mixtures even at low
concentrations. Infrared spectrometry of the permeates revealed
no DEHA in the liquid samples.
However, ow rates were very low (< 20 g m2 h1 ) and
will require a large membrane area to regenerate sufciently the
absorbent. This negative conclusion is an evident weakness of
the hybrid process and it was necessary to identify the reason
of that low level of ow rate. Experiments led with different
membrane thicknesses, different support layer and different liquid velocities proved that the main resistance to mass transfer
is located in the liquid boundary layer at the membrane surface
(Heymes et al., 2006c). Hydrodynamics of the liquid upstream
of the membrane is the determining parameter of the separation.
The experiments of this piece of work were performed in a
small laboratory device (S = 55 cm2 ), designed to test different
membranes but not to characterize hydrodynamics in a general
manner. Therefore, an empirical correlation based on the results
of this piece of work would not be valid to design an industrial
pervaporation unit. Correlations from literature will be used in
the modelling part.
3. Discussion
In this part, the experimental results and conclusions will
be used in order to study the hybrid process. The classical
2581
Fig. 5. Evolution of toluene concentration into the liquid during the rst three loops.
(8)
(9)
where
ML
CL,abs
=
(11)
ML
= QL (CL+ CL ) = KL SCL,perv
,
(12)
RT DEHA
CG,E
H MDEHA
and
CL = 0.
However, the concentration CL+ is lower than this equilibrium value and CL is not zero. The values of this concentration depend on the efciency and scaling of the apparatus used.
Solving previous equations independently and successively allows drawing the concentration into the liquid loop (Fig. 5).
where
ML
CL,perv
=
CL+ CL
.
ln(CL+ /CL )
(13)
2582
10
20
30
40
50
60
Reynolds number
217 334 484 667 880 1118
118 231 431 772 1334 2231
Henrys constant H (106 )
Air-membrane solubility constant S 2500 1352 777 470 298 197
all cases promote one side and harm the other side. A best
temperature, ideal for the overall process, should be determined.
Fig. 6 cannot be used to calculate that ideal temperature since
both processes are coupled. In the previous considerations, the
liquid was considered as pure at the inlet of the absorber and enriched with 10 g L1 at the inlet of the membrane device. This
would not be the case in the coupled process and complicates
the understanding of the unit. Fig. 6 shows that increasing the
temperature will decrease the absorption efciency, and consequently the liquid enrichment at the bottom of the absorber.
For example, raising the temperature from 20 to 60 C will
lower the bottom concentration from 1.4 to 0.22 g L1 . Consequently, the regeneration will be harder, and nally increasing
the temperature will also reduce the pervaporation efciency.
3.1.3. Inuence of liquid ow rate
The liquid ow rate has a strong effect on mass transfer due to
boundary layers effects and diffusion resistances. Moreover, in
the packed column, the liquid ow rate has to be high enough to
absorb sufciently the toluene. This point can be checked by the
absorption rate dened as R=L/GH . The higher the R will be,
the better the absorption will be. But the ow rates cannot vary
widely in a packed column since the hydrodynamics has to be
located in the loading zone conditions. It is always desirable to
be situated in a domain close to 60% of ooding, since this zone
corresponds to the best contact of gas and liquid (maximum interface area). Decreasing the liquid ow rate will lead below the
loading zone with poor mass transfer efciency, rising up the
liquid ow rate can lead to ooding. In pervaporation, increasing the liquid ow rate will promote turbulence and increase
mass transfer. Two equations were used to check this point:
Mass transfer in the packed column (Eq. (7)):
Sh =
KLabs
a
0.048
= 1.67 108
ScL Re1.7
.
G ReL
aD L
awet
2583
K
G G,in CG,out )
L
.
QL (CL+ CL ) = QG (CG,in CG,out )
ln CL+ = KL S
CL
QL
(16)
= QG 1
Q
CG,out
CG,out H CL
L H CL+
.
=
Q
1
H
CG,in
CG,in CG,out
CG,in
MS
K
H
C
/C
C
L+
G,in
G,in
L
ln
=
H CL /CG,out CG,out
QL
(17)
2584
H CL+
CG,in
and
X =
H CL
.
CG,out
The problem can thus be reduced to the resolution of this system of three independent equations with four dimensionless
parameters. A and P can be rewritten as
a
KLabs aV (CL,eq
CL )
KLabs aV C G
=
H QG C G
Q G CG
with CL = 0 (pure absorbent),
A=
X+ and X represent the ratio of the hypothetic gas concentration in equilibrium with the liquid with the real gas conperv
perv
perv
KL S(CL CL,eq )
K SC L
centration. In all cases X+ and X would be as 0 < X+ < 1
=
P= L
QL CL
Q L CL
and 0 < X < 1. The case X+ = X = 1corresponds to an inperv
with CL,eq = 0 (membrane resistance negligible).
nite absorption column achieving thermodynamic equilibriums.
Feeding the absorption column with pure liquid would lead to
X = 0. We obtain the following system:
abs
KL aV (1 X+ ) (CG,out /CG,in )(1 X )
CG,out
= QG 1
H ln((CG,in /CG,out
CG,in
)(1 X
+ )/(1 X))
Q
CG,out
CG,out
L
.
(18)
X
=
Q
1
X
+
H
CG,in
CG,in
ln CG,in X+ = KL S
CG,out SX
QL
Four ratios appear:
KLabs aV
which characterizes the absorption column,
H QG
perv
K S
P= L
which characterizes the pervaporation device,
QL
CG,out
E=
which characterizes the overall efciency,
CG,in
QL
R=
which characterizes theow rates in the system.
H QG
A=
A
=
(1
E)
ln((1 X+ )/E(1 X ))
EX
)
=
(1
E)
R(X
.
+
X
+
ln
=P
EX
(19)
1 X+
E(1
X
)
ln
=
(1
X
+
E(1
X
)
(1 E)
.
X+ EX =
R
ln X+ = P
EX
(20)
The smallest form of the system is
1 X+
R1
ln
=
A
E(1
X
)
R
(1 E)
.
X+ EX =
R
ln X+ = P
EX
(21)
2585
RSK R + 1 S
=
X
RS(K 1)
RS exp(K) R + K(1 S)
X+ =
.
(22)
R(K 1)
[K 1](1 S)
ln(P ) = 1 +
R(SK 1) + 1 S
The above points have shown that the coupling values can
have opposite inuences on the efciency of either operation
To determine X , X+ and A, the resolution of the system gives
in the process. It may therefore be interesting to uncouple
the following equalities:
(1 S)
X
=
RS[exp(P ) 1]
(1 S) exp(P )
X+ =
.
(23)
R[exp(P ) 1]
R1
A =
2586
Fig. 11. Diagram of the principle of the process using a buffer container.
the buffer volume would be both lower than that at the foot of
the column and higher than that of the liquid regenerated by
the pervaporation module:
dV CM
Q1 CL+ + Q3 CL = Q3 CM + Q2 CM +
dt
.
dV
Q1 + Q3 = Q2 + Q3 +
dt
(24)
In the case of a permanent regime, we obtain
Q1
Q3
CM =
CL+ +
CL
,
Q2 + Q 3
Q2 + Q 3
Q1 = Q 2
(25)
and thus,
CM =
Q2
Q3
CL +
CL .
Q 2 + Q 3 + Q2 + Q 3
(26)
2587
the simplest version of the process is chosen. (iii) The absorption column is a packed column lled with Hiow rings. (iv)
The pervaporation process is carried out in a 1 mbar vacuum.
Based on the results of this work, it was decided to use a planar
pervaporation module tted with PDMS membranes. This is a
distinctly optimistic hypothesis, since industrial plants operate
at downstream pressures of 100 mbar. Nonetheless, this downstream pressure of 1 mbar will be retained so as to be able to
use the results of this study.
The quantity of toluene to be recovered per hour is
48 800 g h1 . In order to determine the diameter of the column,
we choose an arbitrary liquid ow rate R = 5, which is a median value. For 60% ooding, the calculated column diameter
is 130 cm. The empty column gas speed would therefore be
2.09 m s1 , and the surface liquid ow from 3.03103 m s1 .
With these values, the KL a in the column is 7.6 103 s1 .
The value of the parameter S is xed at 0.0024 (CG,in =
5 g m3 and CG,out = 0.12 g m3 ). R is chosen as parameter, A
is the variable and X , X+ and P are the solutions determined
using the equations given above. The results are presented in
Fig. 12. A good deal of information can be concluded from that
gure:
2588
Fig. 12. Relation between column height and membrane surface area.
maintained at 100 C for 30 days showed that the refraction index and viscosity of the DEHA were unchanged. Nonetheless,
further studies at higher temperature or lower pressure are indispensable in order to decide whether distillation should be
used for the regeneration process. The comparison between distillation and pervaporation requires a technical-economic analysis which is beyond the scope of this paper for reason similar
to those mentioned above. Nonetheless, an essential point in
the comparison is the operating mode of the plant for reasons
of thermal inertia; distillation is more cost-effective in continuous operation, whereas pervaporation is potentially suited to
continuous or sequential regimes.
4. Conclusion
VOCs are chemical species involved in the problems of atmospheric pollution. They are currently the target of regulation
intended to reduce their emission levels. This measure must
therefore be accompanied by the development of processes
able to satisfy the new requirement in terms of emissions. This
study falls within the scope of that general context. The aim of
this research was to develop a treatment process for air loaded
with hydrophobic compounds by coupling absorption and in
situ membrane-based regeneration. The approach can be split
into several steps. The rst consisted in nding an absorbent
likely to be suitable for an industrial application: DEHA. The
second concerned the characterization and validation of the hydrophobic absorption by means of a pilot-scale apparatus. The
next was devoted to studying tolueneabsorbent separation using a dense membrane. Finally, the work was completed with
a study of the coupling of the absorption step and regeneration
by pervaporation.
DEHA was used in a pilot-scale packed absorption column.
High efciencies were observed when the column was fed with
pure liquid. These efciencies fell sharply when the absorbent
2589
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