Journal of Food Engineering 84 (2008) 8291

www.elsevier.com/locate/jfoodeng

Recovery of the main pear aroma compound by adsorption/desorption

onto commercial granular activated carbon: Equilibrium and kinetics
Nazely Diban, Gema Ruiz, Ane Urtiaga, Inmaculada Ortiz *
Department of Chemical Engineering, University of Cantabria, Avda. de los Castros s/n, 39005 Santander, Spain

Received 4 December 2006; received in revised form 12 April 2007; accepted 19 April 2007
Available online 3 May 2007

Abstract

Adsorption and posterior desorption of ethyl 2,4-decadienoate from model aqueous solutions on granular activated carbon (GAC)
were investigated as ecient technologies in the recovery and concentration of this valuable aroma component, one of the compounds
responsible of the typical avour impact of pears. The equilibrium and kinetics of the separation processes were analyzed at dierent
temperatures. The thermodynamic parameters were obtained from the equilibrium data, being (DH) = 38.35 kJ mol1, indicating
the exothermic and physical nature of the adsorption process. A kinetic model that considers the inuence of external mass transfer
and intraparticle diusion was developed and permitted the estimation of the eective pore diusivity, Dp , ranging between
0.47  109 and 6.14  109 m2 s1 when the operation temperatures changed from 283 to 322 K. In the desorption step aroma concen-
trations could reach values up to 40 times higher than the initial ethyl 2,4-decadienoate solution for the simulations presented in this
work thus showing the viability of the concentration process.
2007 Elsevier Ltd. All rights reserved.

Keywords: Adsorption; Desorption; Aroma compounds; Granular activated carbon; Equilibrium; Kinetic modeling

1. Introduction work (Diban, Ruiz, Urtiaga, & Ortiz, 2007) a viability

Fruit juices are usually concentrated during industrial
processing, that is, water is removed in order to improve
the microbiological stability and to reduce storage and
transport costs. During the concentration by means of
evaporation loss of the aroma compounds occur that usu-
ally lower the quality of the product (Bomben, Briun, Thi-
jssen, & Merson, 1973). The aroma recovery is currently
performed by rectication, which is also a thermal treat-
ment with the consequently energy consumption and phys-
ical aroma losses.
Although the application of adsorption to aroma recov-
ery is not very common, it is considered by certain authors
(Edris, Girgis, & Fadel, 2003; Karlsson & Tragardh, 1997)
as an alternative to those thermal treatments. In a previous
*
Corresponding author. Tel.: +34 942 20 15 85; fax: +34 942 20 15 91.
E-mail address: ortizi@unican.es (I. Ortiz).
study of an adsorption process for the recovery of the main
pear aroma compound was reported.
Flavours are key compounds for food industry. After
separation of the aroma from the aqueous waste stream,
its recovery and concentration into an organic phase
becomes necessary in order to obtain a high quality extract.
Several techniques of desorption are available in the litera-
ture, such as the classical thermal regeneration desorption
(Chu, Baharin, Che Man, & Quek, 2004), high pressure
and temperature regeneration (Salvador & Sanchez Jime-
nez, 1999), by means of a stripping phase (Gupta, Mittal,
& Gajbe, 2005), and more recent techniques such as ultra-
sonic desorption (Juang, Lin, & Cheng, 2006).
In this work, the separation and concentration of the
main pear aroma compound, ethyl 2,4-decadienoate, from
aqueous solutions, was analysed by means of adsorption
on granular activated carbon (GAC) using a combination
of thermal and stripping regeneration as the desorption

0260-8774/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2007.04.024
 N. Diban et al. / Journal of Food Engineering 84 (2008) 8291 83

Nomenclature

ap supercial area of the granular activated carbon r radial coordinate (m)

particle Rg universal gas constant (J mol1 K1)
c liquid-phase concentration of the solute inside Rp radius of the granular activated carbon particle
the particle (mol m3) (m)
C concentration of the solute in the interstitial DS entropy change of adsorption (J mol1 K1)
uid (mol m3) t time (s)
Dm liquid-phase molecular diusivity (m2 s1) T absolute temperature (K)
Dp eective diusion coecient (m2 s1) u0 interstitial uid velocity (m s1)
Ds solid-phase surface diusivity (m2 s1) V volume of ethanol (m3)
E axial dispersion coecient (m2 s1) W mass of granular activated carbon (kg)
F ow rate (m3 s1) z axial coordinate (m)
DG free energy of adsorption (kJ mol1)
DH enthalpy change of adsorption (kJ mol1) Greek letters
KF Freundlich equilibrium constant ee bed porosity
(mol kg1)(mol m3)1/n ep particle porosity
KL Langmuir equilibrium constant (mol kg1) qp particle density (kg m3)
(mol m3) s average particle tortuosity
Km external mass transfer coecient (m s1)
L length of the xed bed of granular activated car- Subscripts
bon (m) d desorption
1/n Freundlich equilibrium parameter e equilibrium
OLS ordinary least squares coecient exp experimental
q solid-phase concentration of the solute sim simulated
(mol kg1) t stirred tank
qmax Langmuir maximum capacity of adsorption 0 feed
(mol kg1)

technique. Thermal desorption was selected by its wide use
and simplicity using ethanol as the solvent in order to
recover the aroma. The equilibrium and kinetics of the sys-
tem were studied at dierent temperatures. The thermody-
namic parameters were obtained from the equilibrium
data. The kinetic model proposed previously for the
adsorption operation (Diban et al., 2007), including
liquid-lm mass transport resistance and intraparticle diu-
sion, was studied in a wider range of temperatures, from
283 to 322 K, tting adequately the adsorption and desorp-
tion data obtained in a granular activated carbon xed-bed
column. The detailed description of the system allows fore-
casting the behaviour of the separation process for aroma
recovery employing adsorption onto activated carbon
and determining the best operation conditions.
2. Materials and methods
2.1. Activated carbon
The adsorbent used in this study was the commercial
Aquasorb 2000 granular activated carbon (GAC) supplied
by Jacobi Carbons. Activation procedure and physical
properties determination and characteristic values were
reported previously (Diban et al., 2007).
2.2. Analytical method
The concentration of ethyl 2,4-decadienoate in aqueous/
ethanol samples was measured by means of GC (Thermo
Quest, model 8000 TOP) with a ame ionization detector
(FID) and equipped with a DB-Wax chromatographic col-
umn (30 m  0.25 mm ID). The details of the chromato-
graphic method can be found in a previous work (Diban
et al., 2007).
2.3. Adsorption and desorption set-up
Model solutions (0.11 mol m3) of ethyl 2,4-decadieno-
ate (SigmaAldrich) diluted in a mixture of 30/70 v/v% eth-
anol absolute (Panreac Qumica) and Milli-Q water
(Millipore Corporation) were used in the adsorption exper-
iments. Desorption experiments were performed using
2.5  104 m3/5.0  104 m3 of ethanol absolute. A xed
bed conguration was used in the adsorption/desorption
experiments. Adsorption experiments were performed
working in a once-through mode, while a batch system
was used during desorption runs. The experimental set-up
employed was described in detail in a previous work
(Diban et al., 2007).
In the present work, the glass column, with an internal
diameter of 6  103 m, was provided with a jacket for
84 N. Diban et al. / Journal of Food Engineering 84 (2008) 8291

Table 1 that the equilibrium had been reached between the

Experimental conditions adsorbed solute and the solute in the liquid phase, with
T F C0 Fixed-bed a concentration Ce (mol m3) of the same value than the
(K) (m3 s1) (mol m3) length (m) inlet concentration. The values of the equilibrium concen-
Adsorption (once- 283 6  108 0.18 0.037 tration of the solute adsorbed onto the GAC sorbent, qe
through mode) 0.24 0.037 (mol kg1), were obtained by integration of the area above
ethanol/water % 0.56 0.039
v/v = 30/70 298 5.4  108 0.11 0.041
the adsorption kinetic curves represented in Figs. 1ac.
0.20a 0.030 This area represents the amount of solute removed from
0.22a 0.035 the feed stream. In a previous work (Diban et al., 2007),
0.28a 0.055 several experiments were carried out working at room
0.39a 0.060 temperature, data given in Fig. 1b. These results have been
0.62 0.038
310 6  108 0.11 0.039
included in the analysis of the inuence of the temperature
0.17 0.036 on the adsorption equilibrium, and new data at 0.11 and
0.23 0.037 0.62 mol m3 were added to that set of experiments in
0.42 0.039 order to generalise the former isotherm for a wider range
1.07 0.039 of concentrations.
q0 Fixed-bed Several desorption experiments were performed at
(mol kg1) length (m) 322 K, temperature below the maximum temperature rec-
Desorption (batch 322 1.8  107 0.137 0.039 ommended to preserve the quality of the aroma com-
mode) ethanol/ 0.142 0.036 pounds, 338 K (Belitz & Grosch, 1987), in order to
water % v/ 0.148 0.038
recover and concentrate the valuable aroma in an organic
v = 100/0 0.159 0.037
0.266 0.039 liquid phase. A previously loaded GAC bed with ethyl
0.323 0.036 2,4-decadienoate was employed to perform one set of
0.333 0.038 desorption runs, until almost complete regeneration of
0.357 0.037 the GAC was reached. After each set of desorption runs,
0.733 0.039
the xed-bed was replenished with fresh GAC and the
0.856 0.038
1.014 0.037 whole adsorption/desorption procedure was repeated.
1.632 0.038 The loading step was made at 310 K varying the feed solu-
2.744 0.039 tion concentration (C0). As a result, in the desorption runs,
a
Experiments published in Diban et al. (2007). the initial amount of adsorbed ethyl 2,4-decadienoate onto
the GAC xed-bed (q0) varied in the range
0.137 < q0 < 2.744 mol kg1 and the rest of the parameters
the circulation of the thermostating uid which permitted were kept constant. Volumes of 2.5  104 and
the study of the inuence of the temperature on the adsorp- 5.0  104 m3 of ethanol were employed as solvent to
tion/desorption process. The column was lled with a xed recover the aroma from the granular activated carbon
bed GAC supported on washed glass wool QP (Panreac working in recycling mode. Fig. 1d shows the evolution
Qumica). The bed length was kept constant at approxi- with time of the concentration of ethyl 2,4-decadienoate
mately 3.9 0.2  102 m in all the experiments performed inside the stirred tank obtained in the desorption runs.
in the present work. The desorption experiments were led to proceed until
The detailed experimental conditions for both adsorp- the solute concentration in the recycling tank, Ct
tion and desorption experiments are shown in Table 1. (mol m3), shown in Fig. 1d, remained constant for a per-
iod of time longer than 1 h. In that moment equilibrium
3. Results and discussion was considered to be reached and Ct = Cd = Ce. The equi-
librium values qe (mol kg1) were determined from mass
3.1. Equilibrium analysis balance as given in the following equation:
VC e
Several adsorption experiments were performed in a qe 1
W
once-through mode working in the temperature range of
283310 K. Feed concentration (C0) was varied from where V is the volume of ethanol employed to carry out the
approximately 0.1 to 1 mol m3, keeping constant the rest desorption run.
of parameters (W, amount of GAC; F, feed ow rate and In this study, the well-known Langmuir and Freundlich
composition of the solvent, ethanol/water ratio). The models, Eqs. (2) and (3), representative of favourable iso-
obtained adsorption kinetic curves of adsorption of ethyl therms of adsorption, were used to correlate the experi-
2,4-decadienoate on GAC are plotted in Figs. 1ac. mental results. This kind of isotherms has been widely
Experiments were led to proceed until the solute con- employed by other authors (Gimeno, Plucinski, Kolacz-
centration in the outlet stream was equal to the inlet or kowski, Rivas, & Alvarez, 2003; Gonzalez-Serrano, Cor-
feed concentration (C0), at this moment it was considered dero, Rodriguez-Mirasol, Cotoruelo, & Rodriguez, 2004;
 N. Diban et al. / Journal of Food Engineering 84 (2008) 8291 85

a 283 K 310 K
0.6 c 1.2

0.5 1
C (mol m-3)

0.4

C (mol m-3)
0.8

0.3 0.6

0.2 0.4

0.1 0.2

0 0
0 20 40 60 80 100 120 140 0 10 20 30 40 50
time (h) time (h)
C0=0.18 mol m-3 C0=0.25 mol m-3 C0=0.56 mol m-3 C0=0.11 mol m -3 C0=0.17 mol m -3 C0=0.23 mol m -3 C0=0.42 mol m -3
+ C0=1.05 mol m -3

298 K 322 K
b d 3.5
0.6
3
0.5

C (mol m-3)
2.5
C (mol m-3)

0.4
2
0.3 1.5
t

0.2 1

0.1 0.5

0 0
0 20 40 60 0 0.5 1 1.5 2 2.5 3

time (h) time (h)

-3 -3 (*) -3 (*)
q0=0.137 mol kg-1 q0=0.142 mol kg-1 q0=0.148 mol kg-1 x q0=0.159 mol kg-1
C0=0.12 mol m C0=0.20 mol m C0=0.22 mol m
q0=0.266 mol kg-1 q0=0.323 mol kg-1 + q0=0.333 mol kg-1 - q0=0.357 mol kg-1
C0=0.28 mol m -3 (*) + C0=0.39 mol m -3 (*) C0=0.62 mol m -3
q0=0.733 mol kg-1 q0=0.856 mol kg-1 q0=1.014 mol kg-1 q0=1.632 mol kg-1
q0=2.744 mol kg-1

Fig. 1. Experimental and simulated data of once-through mode adsorption at (a) 283 K, at (b) 298 K, at (c) 310 K and (d) batch desorption experimental
curves at 322 K. Solid lines () represent the simulated curves. *Curves published in Diban et al. (2007).

Souchon, Rojas, Voilley, & Grevillot, 1996) in order to it is an empirical equation. Langmuir isotherm gives infor-
describe the equilibrium behaviour of similar systems. mation of the total capacity of the adsorbent (GAC) for the
qmax K L C e solute ethyl 2,4-decadienoate, by means of the value of the
qe 2 parameter qmax. The equilibrium parameter KL, is related
1 K LCe
to the thermodynamic parameters DG, (DH) and DS (free
qe K F C e1=n 3 energy, enthalpy change and entropy change of adsorp-
The comparison between the experimental and simu- tion), as given by Eq. (4) and the vant Ho equation
lated equilibrium data is shown in Fig. 2. This plot shows (Eq. (5)), indicating the anity for the binding of the
an increase in the adsorption capacity when temperature adsorbate onto the adsorbent of the system
decreases. The calculated values of the parameters for both DG Rg T ln K L 4
isotherms, Langmuir and Freundlich are shown in Table 2. DS DH 1
In a previous work (Diban et al., 2007) the equilibrium ln K L 5
Rg Rg T
data obtained at 298 K were tted to the Freundlich and
Langmuir isotherms and the characteristic parameters cal- where Rg and T are the universal gas constant
culated. New experimental data were added to the data (8.314 J mol1 K1) and temperature in Kelvin units,
already published at 298 K, obtaining new expressions of respectively.
the isotherms. The values of the thermodynamic parameters (DH)
Freundlich and Langmuir isotherms are based on the and DS have been obtained from the slope and the inter-
theory of a monolayer adsorption, onto a heterogeneous cept of the plot ln KL versus 1/T, Fig. 3. The standard
and homogeneous surface bound, respectively (Ruthven, Gibbs free energy was calculated at each of the analysed
1984). Although the Freundlich isotherm is widely used, values of temperature, Table 2.
86 N. Diban et al. / Journal of Food Engineering 84 (2008) 8291

3.5 2.5

3
2
qe (mol Kg-1)

2.5
1.5

ln KL
2

1.5 1

1
0.5
0.5
0
0
3 3.1 3.2 3.3 3.4 3.5 3.6
0 1 2 3
-3 -1
Ce (mol m-3) 1/T x 10 (K )

Fig. 3. ln KL versus 1/T  103. Linear regression coecient r2 = 0.97.

Fig. 2. Comparison between experimental and simulated (- - - - -) Lang-
muir and () Freundlich isotherms of adsorption of ethyl 2,4-
decadienoate onto GAC at () 283, (h) 298, (N) 310 and () 322 K
(desorption).
In Table 3, a comparison of the thermodynamic param-
eters obtained in this work with other values reported in
the literature corresponding to the adsorption of organic
compounds on granular activated carbons is given. The
negative values for DG, in the range 1.07 to
5.33 kJ mol1, conrm the feasibility of the process and
spontaneous nature of the adsorption of ethyl 2,4-decadie-
noate. The values of (DH) and DS were 38.35 kJ mol1
and 120 J mol1 K1 respectively, conrming the exo-
thermic nature of the process and the decreasing of ran-
domness at the solid-solution interface during adsorption.
Being the calculated value of (DH) < 40 kJ mol1, it can
be concluded that the adsorption of ethyl 2,4-decadienoate
on granular activated carbon is governed by physical inter-
actions (Lucas, Cocero, Zetzl, & Brunner, 2004; Karlsson
& Tragardh, 1997).
The value of qmax, the maximum capacity of adsorption
of ethyl 2,4-decadienoate onto GAC Aquasorb shown in
Table 2, was 3.42 0.25 mol kg1 for the adsorption
experiments performed at 283, 298 and 310 K, showing a
constant value of qmax according to Langmuir theory.
However, data obtained during desorption at 322 K, led
to values of qmax of 0.48 mol kg1 that were considerably
lower than the values obtained in the adsorption runs.
The observed dierence could be attributed to the inuence
of the liquid solvent on the adsorption capacity as it has
been pointed out by other authors (Jarvie, Hand, Bhu-
vendralingam, Crittenden, & Hokanson, 2005; Komiyama
& Smith, 1974; Matsui, Fukuda, Inoue, & Matsushita,
2003). These works agree with the idea that the maximum
capacity of adsorption decreases with the increase of the
presence of an organic compound in the solvent, reducing
the water content, due to a mechanism of adsorption site
competence between the organic adsorbate and the organic
solvent, together with a greater attraction of the ethanol to
the adsorbate in comparison with water. The adsorption
runs were performed using 70%/30% v/v water/ethanol
solutions as solvent, while the desorption runs employed
100% ethanol, so that the shift in the value of the maximum
adsorption capacity, qmax, can be attributed to the inu-
ence of the solvent used in the experiments.
3.2. Kinetic analysis
Kinetic analysis becomes a key point in the knowledge
of the behaviour of a system. In a previous work (Diban
et al., 2007), a mathematical kinetic model was developed
to t the kinetic data of adsorption of ethyl 2,4-decadieno-
ate onto granular activated carbon working in a xed-bed
at room temperature. In this work, the kinetic model has
been used to t the adsorption and desorption results
obtained at dierent temperatures 283322 K, working in
the range of concentrations (0.101.00 mol m3) for
adsorption and (0.1372.744 mol kg1) for desorption,
obtaining the dependence of the kinetic parameters with
temperature. The kinetic model that describes the continu-
ous adsorption of ethyl 2,4-decadienoate in a xed bed of
granular activated carbon is aimed at the prediction of
the evolution with time of the concentration of the adsor-
bate in the uid leaving the GAC column, as a function
of the operation conditions (Rivero, Ibanez, & Ortiz,
2002; Rivero, Primo, & Ortiz, 2004), whereas in the desorp-

Table 2
Freundlich, Langmuir and thermodynamic parameters
T (K) Freundlich parameters Langmuir parameters Thermodynamic parameters
KF (mol kg1) (mol m3)1/n 1/n r2 qmax (mol kg1) KL (m3 mol1) r2 DG (kJ mol1) DH (kJ mol1) DS (kJ mol1 K1)
283 3.2 0.26 0.98 3.20 9.64 0.95 5.33 38.35 0.12
298 3.0 0.30 0.95 3.38 5.02 0.94 4.00
310 2.8 0.65 0.99 3.69 1.98 0.96 1.75
322 0.3 0.69 0.97 0.48 1.49 0.93 1.07
 N. Diban et al. / Journal of Food Engineering 84 (2008) 8291 87

Table 3
Literature comparison of thermodynamic parameters for adsorption of organic compounds onto granular activated carbon
Chern and Chien (2002) Enthalpy change of adsorption, Entropy change of adsorption,
(DH) (kJ mol1) (DS) (J mol1 K1)
p-Nitrophenol Commercial 14.5 29.1
activated carbon
Gimeno et al. (2003) Free Energy of adsorption, (DG)
(kJ mol1)
4-Chloro-2- Aquacarb 207C 30.8334.93
methylphenoxyacetic Aquacarb 208A 29.5831.22
acid Aquacarb 208EA 27.6431.41
Otero et al. (2005) Enthalpy change of adsorption, (DH) (kJ mol1)
Salicilic acid Filtrasorb F400 19.69
Purkait et al. (2005) Enthalpy change of adsorption, Entropy change of adsorption, Free energy of adsorption,
(DH) (kJ mol1) (DS) (J mol1 K1) (DG) (kJ mol1)
Eosin dye Commercial 26.98 52.62 9.9811.03
activated carbon
This work Enthalpy change of adsorption, Entropy change of adsorption, Free energy of adsorption,
(DH) (kJ mol1) (DS) (J mol1 K1) (DG) (kJ mol1)
Ethyl 2,4-decadienoate Aquasorb 2000 38.35 120 1.075.33

tion experiments, carried out in batch mode, the kinetic 1.00E-07

model is able to predict the evolution with time of the con- 3 3.1 3.2 3.3 3.4 3.5 3.6

centration of the adsorbate in the stirred tank. The model

equations are detailed in the Appendix A.
1.00E-08
Dp* (m2 s-1)

The adjustable parameter in this model is the eective

diusion coecient Dp . The best value of Dp was obtained
by comparing the experimental adsorption/desorption data
with the simulated results in order to provide the minimum 1.00E-09
value of the standard deviation, based on the minimization
of theP ordinary least squares coecient (OLS),
OLS C exp  C sim 2 . The software tool available in
the Aspen Custom Modeler process simulator, that uses 1.00E-10

nite dierences for the discretization of dierential equa-
tions, was used to solve the set of model equations. The
estimated values of Dp are reported in Table 4, and the
comparison between the experimental and simulated
results is shown in Fig. 1. In this work, the values of eec-
tive pore diusivity, Dp , were plotted against the reciprocal
of temperature, Fig. 4. It is observed that the higher the
temperature, the higher the value of eective pore diusiv-
ity, Dp , in agreement with previous works (Ruthven, 1984).
Dp is a lumped parameter that according to a parallel
mechanism of diusion inside the particle pore ts to the
dq
expression given by Eq. (A.5), Dp ep Dsm qp Ds dC . The
rst term of the expression corresponds to the diusion
mechanism of the solute in the liquid phase inside the pore
that depends on the molecular diusivity, Dm, parameter
1/T x 10-3 (K-1)
Fig. 4. Dependence of the eective pore diusivity with temperature.
that follows a dependence with temperature as given by
the correlation of WilkeChang, Table 4, with particle
porosity, ep = 0.62, and with tortuosity, s = 4, as refer-
enced previously (Diban et al., 2007). The second term
refers to the surface diusion mechanism of the adsorbed
compound being the characteristic parameter the solid-
phase surface diusivity, Ds. Surface diusivity, Ds, was
calculated from the estimated value of the eective pore
diusivity, Dp , the particle density, qp, and the slope of
the isotherm, dq/dC, that was assumed to remain constant
in the range of concentrations studied. The values esti-

Table 4
Intraparticle diusion parameters
.
D m ep dq
T (K) Dp m2 s1 (estimated) Dm (m2 s1) (WilkeChang) s m2 s1 Ds (m2 s1) qp dC Ds Dm ep =s
283 0.47  109 4.40  1010 0.68  1010 0.18  1012 5.9
298 1.28  109 6.74  1010 1.04  1010 0.46  1012 11.3
310 3.89  109 8.75  1010 1.36  1010 1.28  1012 27.6
322 6.14  109 11.3  1010 1.75  1010 24.4  1012 34.1
88 N. Diban et al. / Journal of Food Engineering 84 (2008) 8291
mated for Dp fall into a range that agrees with the results
obtained in other works using activated carbon as adsor-
bent of organic compounds at room temperature in a glass
agitated batch adsorber (Calleja, Serna, & Rodriguez,
1993; Fritz, Merk, & Schlunder, 1981; Neretnieks, 1976)
as shown in Table 5.
The relative contribution of surface diusivity increases
with increasing temperature. This behaviour can be
observed in the change of the ratio of the surface
 diusion
dq
term to the pore diusion term, qp dC Ds Dm ep =s, as a
function of temperature. In Table 4 it is observed that
the value of this ratio is higher as the temperature increases
indicating that temperature has higher inuence on the sur-
face diusion rate than on the pore diusion rate. Surface
transport is related to the presence of micropores in the
particle (Ruthven, 1984). In the granular activated carbon
used in this study, approximately 50% of the porous struc-
ture corresponds to micropores and the other 50% corre-
sponds to mesopores. The importance of surface diusion
can be associated to the high percentage of micropores
present in the particle. Surface diusivity becomes the lim-
iting resistance to the transport of the adsorbate at low
temperatures, but this resistance decreases when tempera-
ture rises facilitating the intraparticle transport rate.
Although the adsorption capacity of the GAC is
favoured at low temperatures, as it was seen in the previous
section, the kinetics are limited by the decrease of temper-
ature. Therefore, a mild adsorption temperature such as
room temperature becomes a good option, not only
because it leads to a compromise between capacity and
kinetics but also because it saves energy costs of cooling
or heating.
3.3. Desorption experiments
Scarce literature exists on the desorption of organic
compounds from activated carbon mainly due to the fact
that this technology is mainly employed to remove organic
contaminants from wastewaters that are of no economical
value; once the carbon is saturated it is dumped and the
adsorption system is replenished with fresh carbon (Coo-
ney, 1999). When the adsorbed compound is valuable
(Otero, Zabkova, Grande, & Rodrigues, 2005) or when
Table 5
Comparison of diusivities at room temperature for organic compounds onto activated carbon in the literature
Calleja et al. (1993) Eective pore diusivity, Dp m2 s1
p-Nitrophenol 350  109
Phenol 1.33.6  109
D m ep
Fritz et al. (1981) Pore diusivity, s m2 s1
p-Nitrophenol 110  109
Phenol 311  109
D m ep
Neretnieks (1976) Pore diusivity, s m2 s1
2,4-Dichlorophenoxyacetic acid 1.4  1010
Diban et al. (2007) Eective pore diusivity, Dp m2 s1
Ethyl 2,4-decadienoate 2.47  109
the recovery of the activated carbon is protable (Salvador
& Sanchez Jimenez, 1999) the study of the GAC desorption
process becomes necessary.
Ethyl 2,4-decadienoate is a valuable compound with
applications in food and cosmetic industry. For that rea-
son, after separation of the aroma compound from the
aqueous solution, it is necessary to be recovered and con-
centrated into an organic phase in order to avoid microbi-
ological activity. Di Cesare and Polesello (1987) and
Bitteur and Rosset (1988) desorbed aroma compounds
from dierent types of resins by eluting with absolute
ethanol.
From the previous thermodynamic study, the exother-
mic nature of the adsorption process was manifested.
Therefore, higher temperatures favour the desorption of
the adsorbed ethyl 2,4-decadienoate, so in this work, ther-
mal desorption using absolute ethanol as stripping solvent
was selected to recover and concentrate the aroma
compound.
As previously mentioned, aroma compounds are very
sensitive to thermal treatments, which cause the loss of
its quality and properties. Due to this fact, thermal desorp-
tion was carried out at 322 K, a mild temperature that
causes no damage to the compound. The temperature
restrictions were compensated by the fact that ethyl 2,4-
decadienoate feels much more anity for ethanol than
for water, because of its lower polarity, and the fact that
the adsorption capacity of the GAC using ethanol as sol-
vent becomes strongly reduced.
Several desorption experiments were performed to ana-
lyse the behaviour of the equilibrium and kinetics. The
experimental set-up and runs have been described previ-
ously in this work and the experimental conditions are
included in Table 1. The obtained results are shown in Figs.
1d and 2 and in Table 3.
A concentration factor was dened as the ratio of the
equilibrium concentration reached in the ethanol during
the desorption process (Cd) to the feed concentration (C0)
of the solution used in the adsorption process, (Cd/C0).
The values of this concentration factor, (Cd/C0), versus
the feed solution concentration, C0, are presented in
Fig. 5. The data were obtained after adsorption runs at
310 K and ethanol volumes of 2.5  104 and
Surface diusivity, Ds (m2 s1)
14  1012
315  1012
Surface diusivity, Ds (m2 s1)
0.14  1012
Dm ep
Pore diusivity, s m2 s1 Surface diusivity, Ds (m2 s1)
1.04  1010 0.97  1012
 N. Diban et al. / Journal of Food Engineering 84 (2008) 8291 89

ex p2.5
exp x 10-4m3
2.5x10-3 m3 4. Conclusions
12 -4 3
exp
ex p5.0 x 10 m3
5.0x10-3 m
10
In this work, a study of the removal of the main pear
sim
aroma compound, ethyl 2,4-decadienoate, from a model
8 aqueous solution and its posterior concentration by
Cd /C0

6 means of an adsorption/desorption process onto granular

4
2 on the equilibrium and kinetic parameters was experimen-
0
0 0.1 0.2 0.3 0.4
-3
C0 (mol m )
Fig. 5. Experimental and simulated curves of the concentration ratio (Cd/
C0) versus feed concentration (C0) using ethanol volumes of 2.5  104 m3
and 5.0  104 m3. GAC beds previously loaded at 310 K.
5.0  104 m3 in the elution process. Solid lines in Fig. 5
correspond to simulated curves that t quite well to the
experimental data. The experimental values of the concen-
tration factor, (Cd/C0), in the range 106, shown in Fig. 5
check the viability of the recovery of ethyl 2,4-decadienoate
from a synthetic solution of this aroma compound by
means of an adsorption/desorption process onto granular
activated carbon.
The inuence of the temperature of adsorption on the
concentration reached during the desorption step is ana-
lysed in Fig. 6. Simulated curves that correspond to
adsorption temperatures of 283, 298 and 310 K using a vol-
ume of absolute ethanol of 1.25  104 m3 are represented.
The pear brandy concentration of ethyl 2,4-decadienoate
usually falls between 0.24 and 0.34 mol m3, (Kralj-Cigic
& Zupancic-Kralj, 1999). In Fig. 6 a wider range was stud-
ied, because the concentration varies depending on the type
of juice or beverage and the state of ripening of the fruit
employed for the juice processing. The lower the tempera-
ture of adsorption the higher the value of the concentration
factor, (Cd/C0), reaching values up to 40, showing adequate
results of the concentration process.
45
40
35
30
Cd / C0
activated carbon was made. The experiments were carried
out in a xed-bed set-up. The inuence of the temperature
tally studied. From the analysis of the equilibrium results,
0.5 it is concluded that the best description of the equilibrium
data is obtained with the Freundlich isotherm. However,
the theoretical basis of the Langmuir isotherm allowed
the calculation of the thermodynamic parameters. DG
falls in the range 1.07 to 5.33 kJ mol1, being
(DH) = 38.35 kJ mol1 and DS =  120 J mol1 K1.
These values conrm that the process is spontaneous
and exothermic and that the adsorption proceeds by
means of physical interactions. The percentage of ethanol
present in the solution has a big inuence on the maxi-
mum capacity of adsorption of the system, qmax, that
drops from 3.42 0.25 kg mol1 to 0.48 kg mol1 when
the ethanol content rises from 30% to 100% v/v. A math-
ematical model accounting for external mass transport
and internal pore resistances was developed to t the
kinetic data for both adsorption and desorption experi-
mental curves. The estimated values of the eective pore
diusivity, Dp , ranged between 0.47  109 and 6.14 
109 m2 s1 when the temperatures changed from 283 to
322 K. The inuence with temperature of the two
transport mechanisms present inside the GAC particle
was studied observing an increase of the diusion rate
with increasing temperature mainly due to the relative
importance of the surface diusion mechanism. The ratio
of surface  diusion rate to pore diusion rate
dq
qp dC Ds Dm ep =s, varies from approximately 6 to 34 as
the temperature increases. Temperature favours kinetics
due to the decrease of the mass transport resistances,
but the capacity of adsorption of the GAC is reduced,
and so that equilibrium is limited. Therefore, room tem-
perature seems to be a compromising option for both
equilibrium and kinetics, together with the consequent
283 K
saving of energy costs. Recovery of the valuable aroma
298 K
compound is necessary and thermal desorption using eth-
anol as stripping phase gives good results observing that
310 K
in the range of studied variables the concentration of

25 the aroma after desorption can be increased up to 40

20 times its initial feed value.
15
10 Acknowledgements
5
0
Financial support of the Spanish Ministry of Education
and Science (MEC) under projects PPQ2003-00934 and
0 0.1 0.2 0.3 0.4 0.5
CTQ2005-02583/PPQ and F.P.I. grant is gratefully
C0 (mol m -3)
acknowledged. The authors are also thankful to Prof.
Fig. 6. Simulated curves of concentration ratio (Cd/C0) versus feed Francisco Salvador (University of Salamanca) for the sam-
concentration (C0) at dierent adsorption temperatures (T). ples of GAC and recommendations.
90 N. Diban et al. / Journal of Food Engineering 84 (2008) 8291

Appendix A. Modeling equations t 0; 0 6 r 6 Rp ; c 0; q0

 
oc 
This model is based on the following main assumptions: t > 0; r Rp ; K m C  cjrRp Dp
or rRp A:4
(i) fast intrinsic adsorption kinetics, and therefore, instan- 
taneous local equilibrium is considered and (ii) both the oc
t > 0; r 0; 0
external resistance of solute mass transfer from the bulk or r0
liquid phase to the particle surface and the internal resis-
The full expression for the eective pore diusivity is,
tance associated to solute diusion within the particle pores
are considered (Ruthven, 1984). Dm dq
The column mass balance in the interstitial liquid is Dp ep qp D s A:5
s dC
given in the following equation:
where Ds is the solid-phase surface diusivity, dq/dC is the
oC oC oC 2 slope of the adsorption equilibrium isotherm, and s is the
ee K m ap C  cjrRp ee u0 E Dm 2 A:1 tortuosity factor of the pores of the GAC particles.
ot oz oz
A mass balance to the stirred tank must be added to the
where C is the concentration of the solute in the interstitial previous set of equations to complete the model describing
uid, c the concentration of the solute inside the GAC par- the desorption system. The sampling volume is considered
ticle, t the time, z the axial coordinate, the external mass negligible, so the volume of the tank is approximated to be
transfer coecient, E the axial dispersion coecient, the constant (V), and Eq. (A.6) is obtained:
molecular diusivity of the solute, ap the supercial area dC t
of the particle, u0 the interstitial uid velocity, ee the bed V F CjzL  C t A:6
dt
porosity and Rp the radius of the particle, for spherical
GAC particles, ap = 3/Rp. The values of Dm, E, and Km, This balance is connected to the column mass balance
corresponding to the operating conditions of this work by means of following equation:
have been calculated using standard correlations. The rst 8t; C t Cjz0
term of Eq. (A.1) represents the accumulation of solute in
the mobile uid; the second term is the transfer rate of sol- t 0; Ct 0 A:7
ute across the liquid lm around the particle, the third term Eqs. (A.1), (A.3) and (A.5) are valid for batch desorp-
accounts for the change in concentration along the bed tion experiments, and in this case the initial and boundary
length due to forced convection and the last term accounts conditions for Eq. (A.1) are:
for dispersion.
The initial and boundary conditions of Eq. (A.1) for the t 0; 0 6 z 6 L; C0

case of adsorption experiments are: 
oC 
t > 0; z L; 0 A:8
t 0; 0 6 z 6 L; C C0 oz zL
 t > 0; z 0; C Cjz0
oC 
t > 0; z L; 0
oz zL A:2 and for Eq. (A.3):
oC t 0; 0 6 r 6 Rp ; c 0; q q0
t > 0; z 0; E Dm u0 C 0  Cjz0  
oz
oc 
t > 0; r Rp ; K m C  cjrRp Dp
where L is the length of the xed bed of granular activated or rRp A:9
carbon and C0 is the concentration of the solute in the feed 
oc
solution that enters into the GAC bed. t > 0; r 0; 0
Mass transfer of the adsorbate inside the particles or r0
occurs by combination of Fickian diusion in the liquid
phase lling the pores and surface diusion. For spherical References
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