Journal of Colloid and Interface Science 296 (2006) 458–464

www.elsevier.com/locate/jcis

Fixed-bed adsorption of chlorinated hydrocarbons from multicomponent

aqueous solution onto activated carbon: Equilibrium column model
Robert Pełech ∗ , Eugeniusz Milchert, Marcin Bartkowiak
Department of Organic Technology, Szczecin University of Technology, Pułaskiego 10, PL 70-322 Szczecin, Poland
Received 20 July 2005; accepted 10 September 2005
Available online 10 October 2005

Abstract
The results of studies on the adsorption dynamics of light chlorinated hydrocarbons, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform,
carbon tetrachloride, 1,1-dichloroethene, perchloroethylene and 1,1,2-trichloroethene, from a seven-component solution on to activated carbon are
presented. The experimental results were described using the equilibrium model. The application of this model allows to determine the location
of the midpoint of the breakthrough profile.
© 2005 Elsevier Inc. All rights reserved.

Keywords: Activated carbon; Adsorption; Chlorinated hydrocarbons; Fixed bed; Wastewater

1. Introduction
Growing interest in the application of adsorption processes
for the treatment of industrial wastewater, as well for the recov-
ery of organic compounds from aqueous solution, has been ob-
served. These processes are used particularly in the case where
impurities did not undergo biological degradation and their con-
centration is very low. In general, the adsorption methods are
used as the final stage in industrial wastewater treatment [1–6].
The fundamental design solution of the adsorbers comprises
an apparatus with a fixed-bed adsorbent. The removal of or-
ganic compounds from wastewater is most often performed
using carbon adsorbents [7,8], in particular activated carbons.
The calculations of the adsorption process on a fixed bed are
restricted to the determination of the cause of the breakthrough
curve. Despite its apparent simplicity, the problem of opti-
mal design of such absorbers is extremely complicated [9].
The majority of existing adsorption models under the dynamic
conditions concern the removal of a single component from
a treated solution. The prediction of the course of the break-
through curves for multicomponent systems was solved in sev-
eral particular cases. However, a universal method has not yet
* Corresponding author. Fax: +48 91 449 43 65.
E-mail addresses: robert.pelech@ps.pl, gorzow@ps.pl (R. Pełech).
0021-9797/$ – see front matter © 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.09.020
been proposed; thus the problem is solved for the specific case
[10,11].
The physical phenomena occurring in adsorption columns
operating by elution chromatography under isothermal con-
ditions are typical examples of a nonstationary process. The
general mathematical model is impossible to solve by known
methods. For this reason, several simplifications are incorpo-
rated into modeling [12].
An approximate distribution of the concentration in an ad-
sorption column makes it possible to determine an equilibrium
model. Paderewski et al. [13] have determined the concentra-
tion distribution in a bed based on the equilibrium model dur-
ing the adsorption of a three-component mixture of acetone,
methanol, and benzene vapors. They calculated the adsorption
equilibrium for the particular components from the Markham–
Benton equation (extended Langmuir equation), whereas Crit-
tenden et al. [14] applied the equilibrium model to the determi-
nation of the concentration distribution in a bed in the case of
adsorption from a six-component aqueous solution. The adsorp-
tion equilibrium was calculated from the developed model IAS
(ideal adsorbed solution) in relation to the Freundlich equation
for the single-component solution.
In this work, the experimental results and a description of
multicomponent adsorption under dynamic conditions using the
equilibrium model are presented.
 R. Pełech et al. / Journal of Colloid and Interface Science 296 (2006) 458–464 459

2. Experimental: materials and methods

2.1. Materials

2.1.1. Sorbent
The adsorbent used in these studies was activated carbon of
the DTO type, supplied by GRYFSKAND SA (Poland). Ac-
cording to the manufacturer’s specifications, this adsorbent is Fig. 2. Schematic diagram of the experimental system: (1) glass adsorption col-
umn, (2) peristaltic pump, (3) solution reservoir, (4) damper, (5) sampling of
generally suitable for water treatment with activated carbon. eluate, (6) thermostat.
Adsorbent was sieved into several discrete particle size ranges.
The size range of activated carbon 0.4–0.63 mm was used in
2.2. Experimental methods
these studies. The sieved activated carbon was washed by dis-
tilled water to remove fines and then dried at 110 ◦ C in an oven
The studies were carried out under isothermal conditions
for 24 h. The carbon particles were assumed to be spheres hav-
at 30 ± 0.5 ◦ C. The experimental setup is shown in Fig. 2.
ing a diameter given by arithmetic mean value between respec-
An aqueous solution of chlorinated hydrocarbons was passed
tive mesh sizes (average particle diameter dz was 0.53 mm).
through a glass column with diameter 0.24 dm and height
Their properties are presented in Table 1. The surface area, pore
1.5 dm, which was packed with DTO activated carbon. The
size distribution, and pore diameter were measured with N2 (g)
composition of the feed solution was as follows: CCl4 , 12DCE,
adsorption (ASAP 2010 pore structure analyzer, Micromeritics,
S-TET, VDC, TRI, and PER with concentration 5 µmol/dm3
USA) at 77 K with liquid N2 ; the remaining values were taken
and CHCl3 with 15 µmol/dm3 . This composition corresponds
on the basis of data given by the manufacturer. The pore volume
to the average concentration of these compounds in wastewater
distribution is presented in Fig. 1 [1,4,6].
from a plant manufacturing vinyl chloride by the dichloroethane
method with the chlorine balance [15]. A seven-component so-
2.1.2. Sorbates
lution was supplied to the bottom of the column by a peristaltic
Seven chlorinated hydrocarbons, namely 1,2-dichloroethane
pump at a flow rate of 0.067 dm3 /min. Linear velocity recalcu-
(12DCE), 1,1,2,2-tetrachloroethane (S-TET), chloroform
lated on an empty adsorber amounted to 1.5 dm/min. For such
(CHCl3 ), carbon tetrachloride (CCl4 ), 1,1-dichloroethene (VDC),
established hydrodynamic conditions the Reynolds number was
perchloroethylene (PER) and 1,1,2-trichloroethene (TRI) (Fluka,
Re = 1.3. Samples of solution were collected at three heights
A.G.), were used in these studies.
of 0.4, 0.8, and 1.2 dm and were analyzed for chlorinated hy-
drocarbons content. During the process the inlet concentration
Table 1
Physical properties of DTO activated carbon
was also controlled. In order to maintain constant concentration
it was necessary to supplement the loss of a given chlorinated
Bulk density (g/dm3 ) 400
hydrocarbon due to its evaporation. For this purpose methanol
Apparent density (g/dm3 ) 860
Total surface (N2 BET method) (m2 /g) 943
solutions of the respective components with a concentration of
Pore volume (cm3 /g) 0.53 50 mmol/dm3 were used, which were added progressively as
Pore volume <1.5 nm (cm3 /g) 0.25 the concentration decreased, so that a required initial concen-
Porosity 0.45 tration Ci0 of a given component was maintained.
Average particle diameter (mm) 0.53
2.3. Analytical method

The determination of the chlorinated hydrocarbon concen-

trations was performed by gas chromatography. A detailed de-
scription of this method is provided in [4,6,16,17].

3. Theoretical background

In equilibrium adsorption theory it is assumed that the ad-

sorption equilibrium between the solid and mobile phases is
established instantly at each point of the bed. Thereby all the
mass transfer resistances are ignored. The principles that deter-
mine the equilibrium distribution of adsorbed substances in a
column were given by DeVault [18]. The equations used for the
description of this phenomenon are derived based on the fol-
lowing assumptions:

Fig. 1. Pore size distribution for DTO activated carbon. • process proceeds isothermally,
460 R. Pełech et al. / Journal of Colloid and Interface Science 296 (2006) 458–464

• axial diffusion and radial mass transfer are negligible, All the n components occur in band 1, whereas in each subse-
• pressure drop in a bed is insignificant. quent band there will be n − k components, where k denotes the
band number. In accordance with the assumption of the equilib-
The mass balance equations have the form rium model and designation of the components in the sequence
∂Ci ∂Ci ρa ∂ai of decreasing adsorption affinity, for the component i, i adsorp-
+ + = 0, (1) tion bands will be formed.
∂x ∂t ε ∂t
The component i = 1 is located in one band k = 1, i = 2
ai = fi (C1 , C2 , . . . , Cn ), (2) in two bands k = 1 and k = 2, for which the mass balance is
expressed by the equations
with the initial and boundary conditions  
a2,1 = f C20 Θ2,1 , (14)
Ci (0, x) = ai (0, x) = 0, Ci (t, 0) = Ci0 , i = 1,2, . . . . (3)
It is assumed that the substances have different sorption affini- a20 x2 − a2,1 x1
ties with respect to a given adsorbent and they form the adsorp- a2,2 = Θ2,2 . (15)
x 2 − x1
tion series
Since the remaining components do not influence the adsorp-
A1 > A2 > · · · > Ai , (4) tion of component 2 in band 2, the concentration in this band
can be directly calculated from the adsorption isotherm equa-
where A is adsorption affinity [10,12–14].
tion in the single-component system.
The equilibrium model was solved, describing the adsorp-
The component i = 3 is located in the three bands k =
tion in the multicomponent system by the equation
1, 2, 3, thus its mass balance can be presented as
ai = f (Ce,i )Θi , (5)  
a3,1 = f C30 Θ3,1 , (16)
where
  
amax − i−11 ai a30 x3 − a3,1 x1
Θi = . (6) a3,2 = Θ3,2 , (17)
amax x 3 − x1
A function f (Cei ) corresponds to the adsorption isotherm in the
single-component system. The adsorption equilibrium in such C3,2 = f (a2,2 , a3,2 , . . . , an,2 ), (18)
a system was described by the Langmuir equation [16,19]
where the first character of the index denotes the component
bCe,i number and the second one the band number.
f (Ce,i ) = am . (7)
1 + bCe,i The adsorption of component 3 in band 2 is affected by
component 2; hence the concentration in this band should be
The total adsorption of component i in the band with width xi
calculated taking into consideration the parameter Θ. After the
can be expressed by
rearrangement of the Langmuir equation, the concentration is
qtCi0 calculated from the equation
ai0 = , (8)
xi ρ b F a3,2
C3,2 = , (19)
where b3 (am Θ3,2 − a3 )

xi = Ui dt (9) a30 x3 − a3,1 x1 − a3,2 (x2 − x1 )
a3,3 = Θ3,3 . (20)
and x 3 − x2
q The concentration of component 3 in band 3 is calculated in
= w. (10)
F the same manner as component 2 in band 2. The adsorption of
Than Eq. (8) takes the form component i in band k can be written by the recurrent balance
equation
wtCi0
ai0 = . (11) ai0 xi −ai,1 (x1 −x0 )−ai,2 (x2 −x1 )−···−ai,k−1 (xi−1 −xi−2 )
xi ρ b ai,k = xi −xk Θi,k (21)
The adsorption magnitude of component i in any band k is and the concentration of component i in band k as
equal to
ai,k
Ci,k = . (22)
ai,k = f (C1,k , C2,k , . . . , Ci,k , . . . , Cn,k ), (12) bi (am Θi,k − ai,k )
whereas the adsorption magnitude of any component in band 1 According to the statement that components with lower sorp-
amounts tion affinity do not influence on adsorption of components with
  higher affinity [16], the velocity of the concentration wave front
ai,1 = f C10 , C20 , . . . , Ci0 , . . . , Cn0 . (13) of component i will be determined by the adsorption isotherms
 R. Pełech et al. / Journal of Colloid and Interface Science 296 (2006) 458–464 461

Table 2
The velocities of the concentration wavefronts of particular components
Compound PER S-TET TRI CCl4 VDC CHCl3 12DCE
U (dm/min·103 ) 0.11 0.27 0.49 0.66 0.82 1.05 2.51

in a single-component system. The velocities of the concentra-

tion wave fronts are determined from the relationship [20,21]
w
Ui = . (23)
1 + ρb (dai /dCi )
To calculate the velocity of the concentration wave front of
band k, the knowledge of the component concentrations at the
front of this band is required. The concentrations at the sorption
fronts undergo constant changes from a value Ci0 at the column
inlet to a value Ci (x). However, the analytical solution of this
problem is impossible because the concentration is a function
of velocity.
A method of successive approximations was utilized for the
calculation of velocity of the concentration wave front. In the
first step, the value of the velocity for the conditions existing at
the column inlet was calculated from the equation [13,22]
w height of 12 cm by 12DCE. The calculated profiles of these
Ui = . (24)
1 + (ai0 ρb )/Ci0
The obtained value was substituted into Eq. (21), and after the
substitution,
xi = Ui t,
this equation takes the form
ai0 Ui −ai,1 (U1 −U0 )−ai,2 (U2 −U1 )−···−ai,k−1 (Ui−1 −Ui−2 )
ai,k = Ui −Uk
(26)
The calculated value Ci from Eq. (22) allows the calculation
of a new value Ui from Eq. (23). Subsequently, after the deter-
mination of the average value of velocity of the concentration
p−1 p
wave front between the iterated values Ui and Ui ,
p−1 p and VDC with concentrations 1.024, 1.055, and 1.069C 0 ; and
Ui + Ui
Ui = , (27)
2 at 1.020, 1.045, 1.056, and 1.063C 0 ; x3 = 1.06 cm, 12DCE,
the consecutive iteration step was calculated.
The average difference between the values in the first itera-
tion step and the twentieth step was found to amount to 0.08%.
This allows the assumption of practically constant velocity of
concentration wave front along the column in relation to the ini-
tial values, which is equal to the value obtained from Eq. (23).
This results from the fact that the adsorption isotherms in the
studied concentration range possess a shape close to linear. This
allows assuming da/dC = const and as a consequence, constant
velocity of the concentration wave front. Their values are com-
piled in Table 2.
4. Results and discussion
The calculated distribution of concentration (Eqs. (22)–(25))
in the bed during the process of chlorinated hydrocarbon ad-
sorption from seven-component aqueous solution is shown in
Fig. 3. Distribution of adsorptive components concentration calculated from
equilibrium column model.
Fig. 3, whereas the distribution of adsorptive components along
the bed depth is presented in Fig. 4. Figs. 3 and 4 correspond
to the moment of equilibrium breakthrough of a bed layer with
concentrations at the bed outlet as a function of time are pre-
sented in Fig. 5. To show more distinctly the eluent concentra-
tion, the concentration profiles in Figs. 3–5 are presented in the
range of relative concentrations Ci /Ci0 = 0.95–1.07. The ob-
(25) tained model indicates that the concentration profile of 12DCE
considerably overtakes the profiles of the remaining compo-
nents. At the moment of the equilibrium breakthrough of the
bed by 12DCE, the CHCl3 profile will be located at a height of
Θi,k .
5.0 cm, whereas VDC, CCl4 , TRI, S-TET, and PER are at the
heights 3.9, 3.2, 2.4, 1.3, and 0.5 cm, respectively. In the zone
x7 = 6.96 cm there is only 12DCE, the concentration of which
in the liquid phase amounted to 1.031C 0 . In the zone x6 =
1.12 cm there are 12DCE and CHCl3 with the concentrations
1.027 and 1.06C 0 ; in x5 = 0.75 cm there are 12DCE, CHCl3
successively, x4 = 0.82 cm, 12DCE, CHCl3 , VDC and CCl4
CHCl3 , VDC, CCl4 , and TRI at 1.014, 1.014, 1.036, 1.042,
and 1.051C 0 ; x2 = 0.75 cm, 12DCE, CHCl3 , VDC, CCl4 , TRI,
and S-TET at 1.007, 1.016, 1.020, 1.023, 1.029, and 1.050C 0 .
For the zone x1 = 0.54 cm there are all the components sup-
plied to the bed with concentrations equal to the inlet ones. The
presence of 12DCE considerably decreases the effectiveness of
column performance. If the working time the bed will be lim-
ited to the moment of the appearance of this component at the
outlet, then more than 50% of the adsorption zone will be not
available for remaining adsorbates. Obviously such a distrib-
ution will be possible only in the case of lack of any kinetic
effects of the adsorption process. However, this allows the de-
termination of the sequence of appearance and the degrees of
overshoot concentrations of the particular components at the
outlet of the adsorption column.
The course of the breakthrough curves obtained experimen-
tally (points) and calculated from the equilibrium model (bro-
462 R. Pełech et al. / Journal of Colloid and Interface Science 296 (2006) 458–464

Fig. 5. Breakthrough curves calculated from equilibrium column model.

Fig. 6. Experimental breakthrough curves and curves calculated from equilib-

rium column model, bed depth 1.2 dm.

ken line) as a function of time at the bed depth of 1.2 dm is

Fig. 4. Distribution of adsorptive components concentration calculated from
equilibrium column model along a bed.
shown in Fig. 6. Exemplary courses of the breakthrough curves
of component as a function of the relative volume of treated
solution V /Vads are shown in Fig. 7. The changes
 of the total
concentration of chlorinated hydrocarbons Ci / Ci0 (sum)
at the column outlet are also shown in Fig. 7. The breakthrough
curves calculated from the equilibrium model determine the
surroundings of the central point (∼0.5Cmax /C 0 ) for the indi-
vidual experimental curves. The breakthrough curve calculated
in
 relation
 to the sum of concentrations of the column outlet
Ci / Ci0 = f (V /Vads ) precisely reflects the experimental
data.
The experimental breakthrough curves for each component
were constricted with increased bed depth. The difference de-
creases as
V (t0.1 − t0.95 )q
 = , (28)
Vads Vads
where tbi = t0.1 and t0.95 denotes the moment of reaching the
concentration 0.1Ci0 and 0.95Ci0 at the column outlet.
 R. Pełech et al. / Journal of Colloid and Interface Science 296 (2006) 458–464
Fig. 7. Breakthrough curves, experimental and calculated from equilibrium column model.
This indicates that for H → ∞ the experimental break-
through curve will approach a shape obtained from the equi-
librium model. This also results from an increase of the relative
volume of the treated solution with increasing height of bed for
the particular components. The relative amount of treated solu-
tion was defined as
qtbi wF tbi tbi
Ψi = = = . (29)
Vads FH tc
The dependence of relative volume of solution as a function
of the bed depth was shown in Fig. 8. Extrapolation of the
courses beyond the measurement range was performed with the
assumption that at H → ∞ this value is equal to that calcu-
lated from the equilibrium model. For a bed depth of about
10 dm, the volume of treated solution per unit of adsorbent
volume—Ψ —increases distinctly. Above this height the incre-
ment volume dΨ/dH is already insignificant. An increase of
bed depth above 10 dm should not cause a pronounced chanse
of the effective utilization of the adsorbent. However, it only
allows prolonging the time of the adsorption cycle. This opera-
tion, however, may unfavorably influence the process due to an
increase of the flow resistance. The application of too high an
463
adsorption bed causes a large part of it not to participate in the
process of mass transfer. A dead layer of adsorbent is formed,
which only causes flow resistances.
5. Conclusion
The presented solution of the equilibrium model allows de-
termining the midpoint of the breakthrough curve of adsorption
of chlorinated hydrocarbons from multicomponent aqueous so-
lutions and the degree of overshoot concentrations of the partic-
ular components at the column outlet. The changes of velocity
of the equilibrium profile moving along the bed are negligible.
They can be omitted in practical calculations and the constant
value of front migration resulting from Eq. (24) and the inlet
conditions can be assumed. It was found that a profile of the
experimental curve approaches the equilibrium shape with in-
creasing bed depth.
Appendix A. Nomenclature
A adsorption affinity
464 R. Pełech et al. / Journal of Colloid and Interface Science 296 (2006) 458–464

Fig. 8. Relative volume of treated solution as a function of bed depth.

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