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Dispersion in activated carbon packed beds:

adsorbent double porosity media.

G.Drazer, R.Chertcoff, L.Bruno, M.Rosen


Grupo de Medios Porosos - Universidad de Buenos Aires
Paseo Colon 850 Buenos Aires 1063 (Argentina)
Tel. : 54 1 342 9184 - Fax : 54 1 331 0129
Abstract
We present experimental axial dispersion curves of a radioactive tracer flowing along activated
carbon packed beds. Since the grains have pores that are small compared with their size, these beds
have a bimodal pore size distribution which affects dispersion. We show that basic dispersion
mechanisms, such as trapping effects due to adsorption inside the grains, and structural properties of
these beds, can be quantified from dispersion curves.
Resume
Nous prsentons les rsultats exprimentaux des curves de dispersion axiale dun traceur radioactif
qui se dplace tout au long dun milieu poreux de charbon actif. Devant la taille des graines, les pores
sont petits. Alors, le milieu a une distribution bimodel de pores qui modifie la dispersion. Nous
dmontrons que les mcanismes basiques de la dispersion: les effets de pigeage ds ladsorption
lintrieur des grains et les proprirs structurelles du lit peuvent tre quantifis en utilisant des curves
de dispersion avec un modle macroscopique de 4 paramtres.

1. Introduction
In a great variety of adsorption processes the fluid phase flows through an adsorbent
packed bed. Axial dispersion is inherent to these processes due to the disordered networks of
pores. Although minimization of axial mixing could be a design objective, axial dispersion
curves are very useful since they allow the characterization of the porous medium and the
physicochemical interactions between the fluid and the solid matrix.
In the present work we study tracer dispersion in double porosity media (porous media
with bimodal pore size distribution): packed beds of activated carbon grains. There are two
main mechanisms which account for axial dispersion in these systems. Trapping effects due to
adsorption inside the grains and hydrodynamic dispersion arising from the spatial fluctuation
of the flow velocity around the adsorbent particles. The contribution of molecular diffusion to
axial dispersion is negligible at high Peclet numbers (Pe).
The high permeability contrast between the near-atomic size pores inside the carbon
grains, and the large pores consisting of interstices between the carbon grains in the packing
column (mobile zones where convective transport is dominant: voidage), makes diffusive
transport the only exchange mechanism between them. Due to this fact, time spent diffusing
inside the grains can also be seen as a trapping mechanism and contributes to axial dispersion
in a similar way adsorption does.
We study these basic dispersion mechanisms and their relation with parameters used in
macroscopic models, such as dispersion coefficient DL, mobile fluid fraction f, characteristic

exchange time , between immobile regions (pore space inside the grains where convective
transport is negligible) and mobile regions, and asymptotic mean tracer velocity U.

2. Experimental
We use a cylinder packed with activated carbon grains obtained from apricot pit. Table
I summarizes our measured carbon grains characteristics: mean radius (Rp), internal porosity
(P), self-diffusion coefficient (DS) and adsorption isotherm parameters (k and n), as well as
packed bed ones: voidage (), total packed bed porosity (T) and mobile fluid fraction (f).
Carbon
grains
Packed
beds

P
0.45 0.05

0.45 0.02

Rp
0.65 mm

DS
( 1.5 0.1)10-6cm2/s
T
0.7 0.06

k
1.0 0.4
f
0.65 0.08

n
0.63 0.13

Table I. Measured characteristics of activated carbon grains and packed bed.

A plastic filter is placed at both ends of the medium preventing the outflow of the
carbon grains. Three layers of glass beads (with a 0.4 cm mean diameter) are placed at the
inlet to insure an uniform fluid injection distribution over the full cross section of the medium
[1].
In all experiments we use 0.1 M NaI solutions, tagged with I131 radioisotope, or
untagged. The porous medium is initially filled with the untagged solution. At the inlet
section of the medium, a tagged solution is injected at constant flow rate and concentration, in
the initial time (t=0) and thereafter (stepwise tracer concentration variation). By means of a
scintillation detector placed outside and along the medium, the radioactive tracer allows us to
measure the transit time distribution of the tracer particles at different locations along the
porous medium.
An electronic scales collecting the effluent allows us to measure the injection rate.
We performed these experiments at five different injection rates, with Peclet numbers
ranging between 10 and 100. In figure 1 we show the experimental results obtained for two
different injection rates.
Let us note that although we induce stepwise variation of the tracer concentration, the
total salt concentration remains constant during displacements tests.
b)
1.0

1.0

0.8

0.8

C(t) / C

C(t) / C

a)

0.6

0.6

0.4

0.4

0.2

0.2

0.0
0

10000

20000

30000

40000

Time [s]

50000

0.0
0

2000

4000

6000

8000

10000

Time [s]

Figure 1. Tracer concentration variations inside the packed bed for a) Pe = 15 and b) Pe = 100
at 2,8,14,20 and 26 cm from the inlet. Solid line represents the best fit with a 4 parameters
model (Coats-Smith model [2,3,4]).

3. Macroscopic Equations
We use a four parameters model (Coats-Smith model [2,3,4]) to study the tracer
dispersion curves. This model accounts for the mass balance equations for an element of the
adsorption column and for an adsorbent particle. The concentration inside the grains is

approximated as uniform and the exchange between the mobile and immobile zones is
described by a linear rate expression:
f

cm
c q
+ (1 f ) i + = D 2cm vcm
t
t t

c i q c m c i
+
=
t
t 0

(1)

(2)

The characteristic exchange time 0 is related to the self-diffusivity inside the grains
by:

0 =

R 2p
15D s

(3)

The self-diffusion coefficient was previously obtained from independent


measurements of activated carbon uptake rate in batch systems [5] (see Table I ). Therefore
we can estimate 0 = (190 40) s.
As already mentioned, the total solute concentration remains constant. Therefore the
total adsorbed concentration also remains constant and can be obtained through the
equilibrium isotherm. We experimentally obtained a Freundlich equilibrium isotherm; the
parameters summarized in Table I.
Using the fact that the proportion of tagged adsorbed particles in equilibrium q*/qT is
equal to that in solution ci/cT, the linear equilibrium isotherm for the adsorbed tagged particles
concentration becomes apparent [5,6,7]:
q* =

qT
kc n
c i = T ci = (kc Tn 1 )c i = R(cT )c i
cT
cT

(4)

Assuming local equilibrium between the adsorbed phase and the fluid phase within the
porous grain at any axial position ( q(x,t)=q*(x,t) ), Eqs. (1) and (2) can be rewritten as:
fe

c m
c
+ (1 f e ) i = D L 2 c m Uc m
t
t

c i c m c i
=

(5)

(6)

where the definitions and estimated values of the parameters will be given below.
U is the asymptotic mean tracer velocity: U = (fe / f) (Q / A ).
= (1+R) 0 = (600400)s, and fe = f / [ f + (1+R) (1-f)] = 0.40.2 can be estimated
using Eqs. (3) and (4). A more precise estimated value of will be obtained below from the
measured (through dispersion curves) R value.
Finally the longitudinal dispersion coefficient is expected to have a linear dependence
with the asymptotic mean velocity :

D L U

(7)

where the dispersivity is the Lagrangian correlation length of the fluid velocity. For packed
beds ~ RP [3,4]. Therefore we can estimate ~ 0.65 mm.

4. Experimental results
The experimental tracer dispersion curves can be accurately fitted with solutions of
Eqs. (5) and (6). Figure 1 shows the fitted solutions of the theoretical model, where we use a
unique set of parameters ( DL, fe, U, ) for all curves obtained at different distances from the
inlet.
In figure 2 we display the parameters fitted values, obtained at five different Peclet
number.
Let us note first that fe is constant with Peclet number (figure 2a). The obtained value
fe = 0.440.01 is in agreement with our previous estimation.
The linear relation between the asymptotic mean tracer velocity U and injection rate Q
(figure 2b) implies that also f is independent on the injection rate. We obtain f = 0.65 0.02
from the constant ratio U/Q, using previously computed fe value from dispersion curves.
a)

b)
1.0

6
0.8

U [cm/s] x 103

fe

0.6

0.4

0.2
2

fe = 0.44 0.01

U = (0.193 0.003)[1/cm ] Q

0.0
0

20

40

60

80

100

120

10

15

20

25

30

35

Q x 103 [cm3/s]

Pe
c)

d)
1000

Dh/Dm

800

[s]

600

10

400

200

= (360 30) [s]

Dh = (5.3 5)10-5 cm 2/s + (0.12 0.06) cm U


1

0
0

20

40

60

Pe

80

100

120

10

100

Pe

Fig.2 Experimental values obtained from dispersion curves.

Now, taking fe and f values equal to the mean values determined experimentally, we
can improve the accuracy in our estimation, leading to = (440 190) s. This estimation
agrees with the mean value obtained from dispersion curves (figure 2c) = (360 30) s. In
figure 2c the independence on flow velocity can be observed.
Finally in the log-log plot of figure 2d, we display the variation of the normalized
dispersion coefficient with the Peclet number. From the slope of the linear fit we obtain =
(1.2 0.6) mm. In spite of the high experimental uncertainty, the value is consistent with the
expected one.

In table II we summarized the estimated (obtained from our characterization


measurements) and experimental (obtained from the dispersion curves) values for the
parameters used in the macroscopic description.

Estimated
Experimental

F
0.65 0.08
0.65 0.02

fe
0.40.2
0.440.01

(440 190) s
(360 30) s

~ 0.65 mm
(1.2 .6) mm

Table II. Summary of parameters estimated and experimental values.

5. Conclusions
We have presented experimental axial dispersion curves in double porosity activated
carbon packed beds. The used radioactive tagging technique has allowed us to work in an
adsorption linear regime. We have analyzed the experimental data with a four parameters
model (Coats-Smith [2,3,4]). We fitted the simultaneous recordings of tracer activity at
different cross sections along the porous medium using a unique set of macroscopic
parameters. Thanks to this procedure we have obtained reliable and precise parameters value.
The constant value of the flowing fluid fraction f independent on the flow velocity
confirms that convection inside the carbon grains is negligible in the Peclet numbers range we
have worked. The constancy of the effective mobile fraction fe implies that the equilibrium
adsorbed tracer concentration is also velocity independent. The fitted values agree with the
estimated ones based in characterization measurements (table II).
The observed independence of the characteristic exchange time on the flow velocity
confirms diffusive transport as the single exchange mechanism between the adsorbent
particles and the surrounding fluid. The agreement between the mean value obtained from
dispersion curves and the estimated value using the self-diffusion coefficient also confirms
diffusion as the dominant transport mechanism inside the grains.
As already mentioned, in spite of the large experimental uncertainty, the longitudinal
dispersion coefficient displays a roughly linear dependence on velocity. The dispersivity is
as expected, of the order of the grain radius.
Our experimental results demonstrate therefore that dispersion curves performed at
different cross sections of a packed bed are a very sensitive probe of its detailed structure and
physicochemical properties. Similar results can be obtained studying the velocity dependence
of the asymptotic longitudinal dispersion coefficient, where the effects of all mechanisms
which contribute to axial dispersion are lumped into a single coefficient [6].
As the injection rate is increased the uniform concentration approximation used in
eq.(2) becomes inaccurate. When the mean tracer transit time is small compared to ,
concentration variations take place also in characteristic times smaller than . In such cases the
complete diffusion equation inside the grains should be used [3,4,6].

Acknowledgments
The authors would like to thank J.P. Hulin for useful discussions. G.D. has been partially
supported by a CONICET Argentina fellowship.

Nomenclature
A
ci
cm
cT
D
DL
Dm

packed bed cross section


tagged solute concentration in solution in the interior of the carbon grains.
tagged solute concentration in solution outside the grains
total solute concentration in solution.
dispersion coefficient
longitudinal dispersion coefficient
= 1.52 10-5 cm2 / s, molecular diffusion coefficient

DS
self diffusion coefficient inside the carbon grains.
f
mobile fluid fraction
fe
= f / (f + (1+R)(1-f)), effective mobile fluid fraction
k,n
Freundlich isotherm constants
Pe
= U RP / Dm, Peclet number
q
adsorbed solute concentration
qT
total concentration of adsorbed solute in equilibrium
*
q
concentration of tagged adsorbed solute in equilibrium
R(cT) proportionality factor in adsorption linear regime (see eq.(4))
RP
carbon grain mean radius
U
= (fe / f)(Q/A ), asymptotic mean tracer velocity.
v
average mobile fluid velocity
Greek symbols

P
T

packing structure porosity (voidage)


carbon grains internal porosity
= + (1-) P total packed bed porosity
Lagrangian correlation length
characteristic exchange time
= 0 (1 + R), effective characteristic exchange time

References
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