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Chemical Engineering Journal 321 (2017) 510–520

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Chemical Engineering Journal


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3D modeling of overall adsorption rate of acetaminophen on activated


carbon pellets
R. Ocampo-Perez a,⇑, C.G. Aguilar-Madera b, V. Díaz-Blancas a
a
Center of de Investigation and Postgraduate Studies, Faculty of Chemical Sciences, Autonomous University of San Luis Potosí, 78260 San Luis Potosí, Mexico
b
Earth Sciences Faculty, Universidad Autónoma de Nuevo León, Linares N.L, México 67700, Mexico

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 The overall adsorption rate of


acetaminophen on activated carbon
pellets was studied.
 3D diffusional model was applied to
predict the concentration decay
curves.
 Surface and pore volume diffusion are
important on the adsorption of
acetaminophen.
 Desorption zones of acetaminophen
were identified from 3D modeling.

a r t i c l e i n f o a b s t r a c t

Article history: In this work the overall adsorption rate of acetaminophen on activated carbon pellets (ACP) was analyzed
Received 6 February 2017 in deep. The concentration decay curves were interpreted by a 3D diffusional model because the intra-
Received in revised form 27 March 2017 particle diffusion of acetaminophen inside ACP in radial and axial directions are important in this form
Accepted 28 March 2017
of activated carbon. The 3D diffusional model considers the external mass transfer, intraparticle diffusion
Available online 1 April 2017
(pore volume and surface diffusion) and the adsorption on an active site. The results demonstrated that
the application of 3D diffusional model based on pore volume diffusion interprets clearly the kinetic
Keywords:
curves, however values of effective diffusion coefficient (Dep) higher than molecular diffusivity are
Acetaminophen
Adsorption kinetics
obtained indicating superdiffusion phenomenon. On the other hand, the application of a general diffusion
3D modeling model evidenced that during the whole time interval, the acetaminophen diffuses consecutively by sur-
Surface diffusion face diffusion followed by pore volume diffusion. In short times the surface flux is higher than the pore
Poro volume diffusion volume flux, but at higher intervals of time, the relevance of both fluxes reverts. Finally, from 3D simu-
lation it is clear that at longer times, the solute mainly enters from the solution through the pellet bor-
ders, and acetaminophen desorption signs are even evident at the center of the pellet covers, due to the
inverse concentration gradient established between the pellet and the solution.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction pounds from water due to its physicochemical and textural proper-
ties [1]. The activated carbon is mainly commercialized in the
Activated carbon (AC) is the most employed adsorbent for granular (GAC), powdered (PAC), cloth, and pellets forms, and their
industrial applications, especially for eliminating aromatic com- applications depend on the required residence time, available pres-
sure drop, capacity of regeneration, type and phase of process, and
the cost of the adsorbent.
⇑ Corresponding author. Adsorption on activated carbon has been recommended by the
E-mail address: raul.ocampo@uaslp.mx (R. Ocampo-Perez). USA Environmental Protection Agency as the best available

http://dx.doi.org/10.1016/j.cej.2017.03.137
1385-8947/Ó 2017 Elsevier B.V. All rights reserved.
R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520 511

technology for removing non-biodegradable toxic organic com- range from several hundred ng/L to 23.2 mg/L [24]. During the
pounds from drinking water and industrial wastewater [2], and chlorination processes significant amounts of acetaminophen are
in the last decade has been extensively used to remove pharma- transformed into 1,4-benzoquinone and N-acetyl-p-benzoquinone
ceutical compounds from aqueous solutions [3–7]. From literature, imine increasing the toxicity of water. Furthermore, reports in
it is well known that the adsorption mechanism of pharmaceutical the literature suggest that acetaminophen-induced hepatotoxicity
compounds on carbonaceous materials is governed by interactions was a major cause of acute liver failure in the United States and
between p electron from aromatic rings of adsorbate and p elec- that reactive metabolites of acetaminophen may have contributed
tron of graphenic planes of surface of activated carbon [8–10]. Fur- to the pathogenesis of drug-induced toxicity [25,26].
thermore, these interactions are favored depending on the content
of activating groups. Additionally, the electrostatic interactions and 2. Experimental method and mathematical model
formation of hydrogen bond can play and important role on the
adsorption of aromatic compounds [8]. 2.1. Adsorbate
To design appropriate packed adsorption columns, it is not only
necessary to know the adsorption mechanism; it is also critical to Acetaminophen was used in this study, and was supplied by
obtain the adsorption rate and to identify the mass transfer mech- Sigma-Aldrich. The physicochemical properties of this analgesic
anism that governs the overall adsorption rate. Empirical models are listed in Table 1. The concentrations of acetaminophen in aque-
as pseudo first order [11] and pseudo second order [12] are gener- ous solution were determined by a spectrophotometric method,
ally the most common kinetics models used for describing adsorp- and the absorbance was assessed in a double-beam, UV 2600 Shi-
tion kinetics of several pollutants onto various adsorbents duo to madzu spectrophotometer. The absorbance of the acetaminophen
their simplicity together with the good fit generally obtained in a water sample was measured at a wavelength of 244.1 nm.
[13–15], however, the application of these models does not provide
information about the influence of operational variables on mass
2.2. Adsorbent
transfer resistances. On the other hand, the diffusional models con-
sider the external mass transfer, intraparticle diffusion and adsorp-
The activated carbon pellets (ACP) used in this work are dis-
tion on an active site, yielding a more realistic prediction of the
tributed by Carbotecnia (Mexico), it is commercially available as
phenomena [16].
Carvapur and is produced from coconut shell. The average dimen-
We want to stress that the diffusional model is more complex
sions of ACP were obtained by measuring one hundred pellets with
when it is used to interpret experimental results. Its mathematical
an optical microscopy, obtaining an average diameter of
solution is less trivial than kinetic models, and may be it is one of
3.6 ± 0.032 mm and height of 6.5 ± 0.212 mm. The ACP were previ-
the reasons for its unpopularity in the literature. As kinetic models
ously washed several times with deionized water, dried in an oven
contain empirical coefficients, then their predictive abilities under
at 110 °C during 24 h, and stored in a plastic container.
other operative conditions or scales, are diminished. The nature
The ACP was chemically and texturally characterized, determin-
and physics involved in the coefficients of kinetic models is
ing their surface area, pore size distribution, solid density, void
unclear, and furthermore their use for conditions different to those
fraction, surface groups, and pH of the point of zero charge.
used in the fitted experiment is compromised [17]. Several authors
Detailed descriptions of techniques and methods used for this
have employed diffusional models to predict the adsorption rate of
characterization were previously reported [27].
pollutants on activated carbon [16,18–22]. Mendez-Diaz et al. [18]
investigated the adsorption kinetics of dimetridazole, metronida-
zole, ronidazole, and tinidazole onto activated carbon. The results 2.3. Method for obtaining the adsorption equilibrium data
evidenced that pore volume diffusion governs the adsorption pro-
cess for four nitroimidazoles and the values of Dep varied from The experimental data for the adsorption equilibrium of aceta-
5.84  107 to 20.3  107 cm2/s. Leyva-Ramos et al. [19] studied minophen on ACP were obtained in a batch adsorber, which con-
the adsorption rate of pentachlorophenol onto granular activated sisted of a centrifugal vial of 50 mL. The procedure is described
carbon, and the concentration decay data were predicted by a dif- as follows: Aqueous solutions of acetaminophen were prepared
fusional model which takes into account adsorption, external mass in 50 mL volumetric flasks with concentrations ranging from 100
transfer, and intraparticle diffusion. The results indicated that the to 1000 mg/L. A portion of 10 mL of the solution was taken out
overall rate of adsorption is mainly controlled by surface diffusion, from each flask to corroborate the initial concentration of acetami-
and the external mass transfer can be considered negligible. nophen. A certain mass of ACP and 40 mL of the acetaminophen
In references cited above, the adsorbent particles have been solution were poured into the batch adsorber. Afterwards, the
considered spherical and isotropic, and, therefore, the concentra- batch adsorber was placed in a constant temperature water bath,
tion of pollutant inside the particle is only a function of time and and the ACP and the solution were left in contact for 12 days. Once
radial position, which allows reducing the complexity of mathe- equilibrium was attained, a sample of 10 mL was withdrawn and
matical modeling. However, it is evident that these assumptions analyzed to determine the concentration of the acetaminophen
are not valid when the adsorbent particles have different shapes at equilibrium.
such as activated carbon pellets. Thus, this work aims modeling
the overall adsorption rate of acetaminophen as a model com- 2.4. Method for obtaining the rate of adsorption data
pound on activated carbon pellets in aqueous solution through
the application of a three-dimensional diffusional model that takes A rotating basket batch adsorber was used to obtain the exper-
into account the external mass transport, intraparticle diffusion, imental concentration decay curves for the acetaminophen adsorp-
and adsorption on active sites. A detailed analysis is given for the tion on ACP. This adsorber was composed of a 1 L three-neck
intraparticle concentration profiles and the magnitude and direc- reaction flask and an impeller with its blades replaced with stain-
tion of mass fluxes over time. less steel baskets. An acetaminophen solution was poured into the
Acetaminophen was selected as a model pollutant since it is one adsorber and the ACP particles were placed in the stainless steel
of the top prescription medicines worldwide [23]. Acetaminophen mesh baskets, which were attached to a shaft connected to a vari-
cannot be completely removed in wastewater treatment plants, able speed motor. The adsorber was partially immersed in a con-
and the detected residual concentrations in aqueous solutions stant temperature water bath controlled by a recirculator. A
512 R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520

Table 1
Molecular structure and physicochemical properties of acetaminophen.

Compounds Molecular structure Molecular weight (g mol1) Size X, Y, Z (Å) Log(Kow) pKa DAB  106a (cm2/s)
Acetaminophen 151.17 X = 10.74 0.46–0.49 9.86 6.27
C8H9NO2 Y = 6.58
Z = 3.76

a
Experimental value Ribeiro et al. [33].

dCA  
mass of 2 g of ACP was placed in the baskets and put in contact
V ¼ mSkL CA  CAP jBps ð1Þ
with 995 mL of a known concentration solution of acetaminophen dt
at pH 7. This pH was obtained by mixing proper volumes of 0.01 M
@CAP @q  
HCl or NaOH solutions. The concentration decay curves were
ep þ qp ¼ r  Dep rCAP þ Ds qp rq ð2Þ
obtained at initial concentrations of acetaminophen from @t @t
100 mg/L to 700 mg/L, and a stirring speed of 200 rpm. The solu-
tion was periodically sampled (1 mL) and analyzed to determine t ¼ 0 min; CA ¼ 0 mg=L; CAP ¼ 0 mg=L ð3Þ
the acetaminophen concentration at different times.    
nps  Dep rCAP jBps þ Ds qp rq ¼ kL CA  CAP jBps ð4Þ
2.5. Diffusional model
where CA and CAP are the solute concentration in the solution and
Fig. 1 shows a general scheme of ACP where it is evident that, inside the particle, respectively, while q represents the mass
due to its dimensions and geometry, the mass transfer of acetami- adsorbed of acetaminophen; Dep and Ds are the effective and surface
nophen in radial and axial directions should be taken into account. diffusion coefficients, respectively, ep is the void fraction of ACP and
Besides, the mathematical model includes the following assump- qp represents the particle density. In Eq. (1), CAP jBps denotes the
tions: i) intraparticle diffusion occurs by pore volume diffusion
solute concentration inside the pellet evaluated at the pellet-
and surface diffusion, ii) the rate of adsorption on an active site
solution (p-s) boundary. The Eq. (4) represents continuity condi-
is instantaneous, iii) the particles are rigid, homogeneous and iso-
tions of mass flux at the pellet-solution boundary. Finally, if the rate
tropic, and iv) the convective transport inside the porous particle is
of adsorption on an active site is instantaneous, then we assume
negligible in comparison with diffusion. The latter two considera-
that local equilibrium is taking place between the acetaminophen
tions imply that diffusion coefficients correspond for isotropic
concentration in the solution inside the pore and the mass of acet-
effective diffusion tensors, while dispersion effects are discarded.
aminophen adsorbed on the pore surface. This equilibrium is nor-
The model equations and initial and boundary conditions are as
mally represented by the adsorption isotherm, which is the
follows:
mathematical relationship between q and CAP :

q ¼ f ðCAP Þ ð5Þ
It is important to clarify that, in our formulation, the solute con-
centration computed with Eq. (1) is apparently just time-
dependent. However, a deeper inspection will show that CA is also
surface-position-dependent since CAP is involved in Eqs. (1) and (4),
and it is a position and time-dependent variable. This is an impor-
tant feature of our formulation that is not commonly explored in
other works where spherical geometries for porous adsorbents
are considered [18,19]. For non-symmetrical particles, the
non-uniformity of intraparticle concentration provokes different
driving forces for mass flux around the porous particle, and fur-
thermore variations of solute concentration at the vicinity of solid
are expected.
The model represented by Eqs. (1)–(4) is the general diffusional
model (PVSDM). The general model can be simplified considering
that only the intraparticle diffusion mechanism may exist either
 
by pore volume diffusion (PVDM) Dep – 0; Ds ¼ 0 cm2 =s or sur-
 
face diffusion (SDM) Dep ¼ 0; Ds – 0 cm2 =s .

3. Results and discussion

3.1. Textural and chemical characterization of activated carbon pellets

According to the IUPAC classification, the N2 adsorption iso-


therm provides information about the type of porosity in materials
[28], as well as the form and geometry of pores. Fig. 2 shows the
adsorption isotherm of N2 at 77 K for ACP, which has a I(b)-type
behavior according to the IUPAC classification, indicating the pres-
Fig. 1. Scheme of ACP showing dimensions, domains of governing equations, and ence of a wide distribution in the size of micropores, and also the
specific nodes. presence of narrow mesopores. The N2 adsorption data were used
R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520 513

equilibrium to obtain the mathematical relation between q and


0.5 CAP must be evaluated (Eq. (5)).
The external mass transfer coefficient, kL , was assessed by the
procedure proposed by Furusawa and Smith [31], based on the fact
0.4 that when t ! 0 min, then CAP ! 0 mg=L and CA ! CA0 . Substitut-
0.8 ing these conditions in Eq. (1), the following equation can be
Vliq (cm3/g)

0.7 derived:
0.3 dV(r), cm3/(g nm)
0.6
2  C 3
0.5 d A mSkL
0.4
4 CA0 5 ¼ ð6Þ
0.2 dt V
0.3 t¼0min
0.2
The term at the right end of Eq. (6) is the slope of the concentra-
0.1
0.1 tion decay at t ¼ 0 min, and was estimated by using the first two
0.0
Adsorption 0.0 0.4 0.8 1.2 1.6 2.0 data points of the concentration decay curve, at t ¼ 0 and
Desorption Pore radious, nm t ¼ 1 min. The values of kL estimated with Eq. (6) are given in
0.0 Table 3, and ranged from 2.30  103 to 0.88  103 cm/s. These
0.0 0.2 0.4 0.6 0.8 1.0 values are within the range of kL values reported by other authors
P/P0 for rotating basket adsorbers [16,19].
The values of Dep and Ds were simultaneously estimated from
Fig. 2. Adsorption isotherm of N2 at 77 K on ACP, and distribution of pore size using the diffusional model fit to the experimental data using one evolu-
DFT. tionary algorithm. Such algorithm tries to minimize the error func-
tion (Eq. (7)) through stochastic procedures. This method might
develop slower convergence in comparison with gradient-based
to estimate the ACP texture properties, listed in Table 2. ACP have a methods, but a larger lookup field can be set ensuring the finding
specific area similar at those found for granular activated carbons of global minimum. Besides, our first simulations showed that
[3,6], with a pore volume of 0.53 cm3/g. Furthermore, the volume gradient-based methods resulted in numerical errors caused by
of micropores, Vmic , obtained from the application of the rapid gradient changes of the objective function being minimized:
Dubinin-Radushkevich isotherm [28], demonstrated that ACP are
Z
mainly composed of micropores, with their volume representing tf  2
86% of the total pore volume. The distribution of pore size was esti- error ¼ CA;num  CA;lab dt ð7Þ
0
mated by applying the density functional theory (DFT), also shown
in Fig. 2, where the average radius of the ACP pore is between 0.4 The mathematical relation q ¼ f ðCAP Þ was obtained from the
and 1.6 nm. Finally, ACP had a value of pHPZC = 8.4, meaning their evaluation of the adsorption equilibrium of acetaminophen on
nature is slightly basic due to the presence of a greater amount ACP at pH 7 and 25 °C. Fig. 3 shows this equilibrium, as well as
of basic groups in the surface of ACP (See Table 2). the fact that the adsorption isotherm had an ‘‘L”-type behavior,
according to the Giles classification [32], confirming that the acet-
aminophen aromatic rings are adsorbed in parallel on the ACP sur-
face, and that the solute and the water do not compete for the
3.2. Concentration decay curves and estimation of mass transport
active sites available on the surface of adsorbent. This mechanism
parameters
has been validated by Lladó et al. [30], who also establish that
interactions from hydrogen bonding play an important role in
Concentration decay curves for acetaminophen on ACP were
the adsorption of acetaminophen on activated carbons with high
obtained under the experimental conditions shown in Table 3.
contents of phenol groups. This figure also shows that the adsorp-
These experiments were carried out at pH 7, and at rotating speeds
tion capacity reached at an equilibrium concentration of 240 mg/L
of 200 rpm. This rotating speed was chosen after previous experi-
was 190 mg/g, which is 25% lower than that obtained by Lladó
ments demonstrated that external mass transport does not affect
et al. [30] using F400 granular activated carbon.
the overall adsorption rate at rotating speeds greater than
Experimental data were interpreted using the Langmuir iso-
200 rpm. It should be noted that the time required to reach equilib-
therm model, represented by the following equation:
rium was a function of the initial concentration of acetaminophen,
ranging from 3000 min for an initial concentration of 105 mg/L up qm KCAP
to 10,000 min for initial concentrations above 400 mg/L. García- q¼ ð8Þ
1 þ KCAP
Mateos et al. [29] and Lladó et al. [30] determined that the time
to reach equilibrium of acetaminophen on granular activated car- where qm represents the maximum adsorption capacity in mg/g, and
bons was between 2000 and 3000 min at a temperature of 25 °C. K is an isotherm constant in L/mg. The qm and K values were calcu-
To solve the PVSDM, PVDM and SDM models, the values of kL , Ds lated using nonlinear regression, obtaining values of qm = 198.9
and Dep must be estimated. Furthermore, the adsorption mg/g and K = 0.107 L/g. The prediction of the Langmuir model is also

Table 2
Chemical and textural properties of granular activated carbon.

Material SBET (m2 g1) VPa (cm3 g1) dPb (nm) Vmicc (cm3 g1) L0d (nm) epe Total acidic sites (meq g1) Total basic sites (meq g1) pHPZC
ACP 1096 0.53 2.2 0.456 1.38 0.49 0.287 0.304 8.5
a
Total pore volume.
b
Average pore diameter.
c
Micropore volume.
d
Average micropore width.
e
Void fraction of ACP.
514 R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520

Table 3
Experimental conditions for acetaminophen concentration decay curves during adsorption on pellets of activated carbon at pH = 7, T = 25 °C and 200 rpm.

Exp. No. CA0 (mg/L) m (g) CAe (mg/L) qe (mg/g) kL  103 (cm/s) PVSDM PVDM
8 2 6 2
Ds  10 (cm /s) Dep  10 (cm /s) Dep  105 (cm2/s)
1 105.5 2 1.22 52.16 2.30 0.59 1.94 6.12
2 209.5 2 9.68 99.9 1.80 0.79 6.31 2.16
3 322.4 2 38.19 142.11 1.90 1.39 4.64 1.91
4 417.7 2 71.06 173.33 1.40 1.09 6.29 1.40
5 501.1 2 131.02 185.03 1.20 1.18 5.71 1.10
6 633.3 2 240.6 196.35 0.90 1.29 3.95 0.69
7 708.1 2 292.86 207.63 0.88 1.36 3.09 0.77

PVDM model, using an optimum value of Dep = 7.75  106 cm2/s.


200 This value of Dep was obtained by minimizing Eq. (7) using the evo-
Mass of acetaminophen adsorbed, mg/g

lutionary algorithm method. On the other hand, Fig. 5 depicts the


variation of concentration profiles within the particle, CAP, at
160 2000, 4000, and 6000 min for Exp. 7.
Fig. 4 shows that the PVDM prediction drastically depends on
the position in the pellet-solution boundary where CA is being eval-
120 uated because, as mentioned before, CA = f(t,r,z). To analyze this
aspect in detail, nodes A, B, and C from Fig. 1 were chosen. The pre-
diction of the PVDM model in Node B did not interpret the data and
80 clearly overestimated the concentration decay curve, indicating
that a much higher value of Dep is required to obtain a better pre-
diction of experimental data. The slow adsorption rate at this point
40 is due to the solute is transported both in r and z directions (see
Fig. 5), causing a rapid increase of concentration at this point,
and drastically decreasing the driving force between the acetami-
0 nophen concentration in the solution and the concentration of
0 40 80 120 160 200 240 acetaminophen in node B, resulting in a very slow adsorption rate
Concentration of acetaminophen at equilibrium, mg/L at this point. The evaluation in node C produces an adequate pre-
diction of experimental data for times of less than 2000 min, but
Fig. 3. Adsorption isotherm of acetaminophen on ACP at pH 7 and 25 °C. The line predicts an adsorption capacity higher than that observed experi-
represents the prediction of the Langmuir model.
mentally. Finally, the prediction in node A shows a two-stage
behavior, the first of which ranges from t = 0 to t = 4000 min, and
shown in Fig. 3, where, except for one experimental data, the Lang- shows a gradual drop of concentration similar to that observed in
muir model adequately interprets the experimental data. node C, until reaching a minimum closer to 4000 min; the second
stage shows an increase of the solution concentration, that is, the
solute initiates a phase of partial desorption from the pellet. These
3.3. Application of pore volume diffusional model
results derive from the fact that, at times of less than 2000 min, the
solute reaches node A mainly from direction z, and, as time
The pore volume diffusion model assumes that Ds = 0, that is,
increase, higher quantities of solute diffusing from the radial direc-
that the solute is exclusively diffused by pore volume diffusion both
tion reach this point, causing an increase in concentration. Simul-
in r and z directions. Fig. 4 exemplifies the experimental data of the
taneously, the concentration of solute in the solution decreases
concentration decay curve for Exp. 7 and the prediction of the
significantly, reverting the mass flux direction from the pellet
towards the solution. The authors emphasize that these phenom-
ena have not been described previously because it is difficult to
measure it in the experiments, hence the importance of carrying
out rigorous mathematical modeling as well.
Based on these observations, the interpretation of experimental
data must be clearly carried out by averaging the value of CA
throughout the external surface of the pore. This average value
was obtained from the following equation:
R 2p R R R H R 2p
ðCA jz¼0 þ CA jz¼H Þrdrdh þ R CA jr¼R dhdz
Cav
A ¼
0 0 0 0
ð9Þ
2pR2 þ 2pRH
Fig. 4 also includes the prediction of the PVDM model with
Dep = 7.75  106 cm2/s using Cav A . This figure clearly reveals that
the model satisfactorily predicts the experimental data; however,
the value of Dep was higher than the experimental molecular diffusion
coefficient of acetaminophen on water (DAB = 6.27  106 cm2/s)
[33], which has no physical significance, as it means that acetamino-
phen diffuses faster within the pores than in the solution. To
Fig. 4. Concentration decay curves of acetaminophen on ACP. The lines represent verify this result, experiments 1–6 from Table 3 were also interpreted
the prediction of PVDM using different positions on the particle. with the PVDM model, and optimum Dep values are listed in Table 3,
R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520 515

mg/L
2000 min 4000 min 6000 min
560.7

500

400

300

200

100

Fig. 5. Evolution of the intraparticle profiles of acetaminophen on ACP as a function of time for Exp. 7.

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
and predictions shown in Fig. 6, highlighting that the PVDM model  2  2
notably interprets the concentration decay curves; however, all val- kNAP k ¼ Dep rCAP jr-component þ rCAP jz-component ð12Þ
ues of Dep showed that Dep > DAB. It is therefore concluded that the
PVDM adequately interprets the experimental data, but the value of rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2  2
effective diffusion has no physical meaning. kNAS k ¼ Ds qp rqjr-component þ rqjz-component ð13Þ

3.4. Application of pore volume and surface diffusional model The values of ||NAP|| and ||NAS|| for experiment 7 are shown in
Fig. 8a and b, respectively. The arrows in both figures indicate
The preceding results revealed that surface diffusion might play the direction of NAP and NAS, with colors representing the magni-
an important role in the intraparticle diffusion of acetaminophen tude. From these figures, the following may be established: (i)
on ACP. Also, considering that ACP have a high adsorption capacity, The direction of both fluxes along time converge at the center of
concentration gradients in the solid phase may be more important the pellet, as expected; (ii) During the whole time interval, the
than those in the fluid phase within the pores, boosting surface dif- acetaminophen diffuses consecutively by surface diffusion, fol-
fusion. To corroborate this hypothesis, experimental results were lowed by pore volume diffusion; (iii) At short intervals
then interpreted by applying the general diffusional model (t < 83.3 h), the surface flux is higher than the pore volume flux,
(PVSDM). Dep and Ds values were optimized simultaneously until but at higher intervals, the relevance of both fluxes reverts; (iv)
the minimum global of the objective function was obtained. At short intervals of time, the magnitude of NAP and NAS on the pel-
Fig. 7 depicts the PVSDM prediction for Exp. 1–7, with practically let corners is less when compared to the magnitude at other posi-
every decay curve being interpreted satisfactorily, and the opti- tions on the pellet; however, at longer intervals, both magnitudes
mum Dep and Ds values are listed in Table 3. Clearly, the optimum are higher than those shown on other positions of the particle; and,
values of Dep proved to be an order of magnitude less than values (v) At long intervals of time, the direction of both fluxes at the cen-
of DAB, while the values of Ds proved to be an order of magnitude ter of covers of pellet reverts, starting a desorption process towards
less than the values of Ds reported for the diffusion of pyridine the solution.
on granular activated carbon [16], but are, in turn, an order of mag- From the values of NAP and NAS, it is possible to calculate the
nitude greater than those obtained in the diffusion of dyes on gran- surface diffusion contribution percentage (SDCP) with respect to
ular activated carbon [34]. Such difference in the values of Ds are the total intraparticle diffusion by using the following equation:
attributed mainly to the size of the pollutants molecules, because
kNAS k
the acetaminophen molecule is slightly larger than pyridine, but SDCP% ¼  100 ð14Þ
smaller than methylene blue. It is also important to emphasize that kNAS k þ kNAP k
this is the first work where values of Ds are reported for the diffu- As an example, Fig. 9 shows the SDCP% variation as a function of
sion of pharmaceutical compounds on activated carbon pellets. time and position for Exp. 7. This figure clearly shows that both
The surface diffusion is the movement of the adsorbate mole- mechanisms of intraparticle diffusion are important, depending
cules along the pore surface of the AC, and its driving force is the of contact time. In short time intervals, the surface diffusion
surface concentration gradient, q, whereas pore volume diffusion reaches close to 100% of the total intraparticle diffusion, while
refers to the movement of the adsorbate due to concentration gra- the pore volume diffusion is the mechanism governing the intra-
dients in the fluid-phase (i.e., molecular mechanisms), and is particle diffusion of acetaminophen on ACP at longer time inter-
affected by the geometry of pore. To corroborate the mechanism vals; such result may be explained considering that, for Exp. 7,
governing the intraparticle diffusion of acetaminophen on ACP, 90% of acetaminophen has been adsorbed during the first 83.3 h,
the contribution of flux in the volume of pore, NAP, and the contri- causing high concentration gradients in the solid phase, therefore
bution of flux corresponding to the surface diffusion, NAS, were enhanced the driving force of surface diffusion. Finally, closer to
both calculated using the following equations: the equilibrium time, the solid phase concentration gradients
NAP ¼ Dep rCAP ð10Þ decrease, drastically boosting the pore volume diffusion. These
results confirm that both mechanisms of intraparticle diffusion
NAS ¼ Ds qp rq ð11Þ are important in the diffusion of acetaminophen on ACP.
Do [35] and Suzuki [36] pointed out that surface diffusion is the
Moreover, the point-wise norm of these mass fluxes are given most important mechanism of intraparticle transportation in
by the following equations: adsorbents with a large specific area, like activated carbons. They
516 R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520

Fig. 6. Concentration decay curves of acetaminophen on ACP at different experimental conditions. The lines represent the prediction of the PVDM model.

also found that the surface diffusion coefficient increases directly on sites requiring higher energy, and these adsorbed molecules do
when the mass of the adsorbed solute is increased. An explanation not have enough energy to be desorbed from a site and diffuse to
for this behavior is that, at the beginning, molecules are adsorbed another adsorption. Once the active sites with the higher adsorp-
R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520 517

Fig. 7. Concentration decay curves of acetaminophen on ACP at different experimental conditions. The lines represent the prediction of the PVSDM model.

tion energy are occupied, the molecules will be adsorbed on the diffusion coefficient increases as the adsorbed amount of solute
sites with lower adsorption energy so more molecules can be des- is increased.
orbed and move from one site to another causing the Ds value is However, it is important to mention that an increase in the sur-
increased with the adsorbed mass. Such phenomenon is evident face diffusion coefficient does not necessarily mean that the sur-
in the values of Ds reported in Table 3, where, in general, the face diffusion mechanism is more relevant than its pore volume
518 R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520

Fig. 8. Evolution of magnitude and direction of (a) NAP and (b) NAS during the adsorption of acetaminophen on ACP for Exp. 7.

16.7 h 83.3 h 133.3 h 183.3 h


100

90

80

70
SDCP%

60

50

40

30

20

10

r=0 r=R

Fig. 9. Evolution of SDCP% for acetaminophen transport inside ACP as a function of time.
R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520 519

diffusion counterpart. As the adsorbed amount increases, the num- 4. Conclusions


ber of available adsorption sites decreases and, consequently,
higher amounts of solutes are transported through the pores of In this paper, we modeled the concentration decay curves of
the porous pellet. Such phenomenon would indicate that the mass acetaminophen on activated carbon pellets by using a three-
flux due to pore volume diffusion would be more relevant as the dimensional diffusion model, which considers the pore volume dif-
adsorbed solute amount increases. To evidence this issue, Fig. 10 fusion and surface diffusion mechanisms. Mathematical models
depicts the SDCP% variation for experiments 1, 2 and 7 at a contact based on pore volume diffusion, or surface diffusion, were found
time of 83.3 h. In these three experiments, the adsorbed mass of to be equally capable of predicting the concentration decay curves.
acetaminophen at 83.3 h were 52, 92, and 185 mg/g, respectively. However, such models calculate values of Dep and Ds that lack
Fig. 10 clearly shows that, with an adsorbed mass of 52 mg/g, sur- physical relevance suggesting two scenarios: 1) values of Dep
face diffusion governs the total intraparticle diffusion throughout higher than the molecular diffusivity, indicating superdiffusion
the whole particle. Conversely, when the adsorbed mass is phenomena (still unreported in these types of systems), or 2) val-
increased to 92 mg/g, areas of high contribution to surface diffu- ues of Dep equal to zero, indicating that the pore volume diffusion
sion are visible at the center of the particle, as well as areas where is irrelevant when compared to the surface diffusion of
the pore volume contribution is increasingly important. Finally, at acetaminophen.
high adsorbed amounts, the contribution front of surface diffusion The application of a mathematical model including both diffu-
becomes more delimited, allowing the pore volume diffusion to sion mechanisms corroborated that acetaminophen diffuses both
become more relevant. In general, these results prove that, as the by pore volume diffusion and by surface diffusion, and that the rel-
adsorbed mass increases, the surface flux increases too, allowing evance of both diffusion mechanisms depends on the adsorbed
for faster transportation of acetaminophen molecules towards mass and contact time. Surface diffusion is favored under short
the inside of the ACP pores. Finally, the application of the PVSDM contact time conditions, because the solid phase concentration
evidenced that acetaminophen diffusion on ACP is both controlled gradients are more important than the fluid phase concentration
by surface diffusion and pore volume diffusion, depending on the gradients within pores.
adsorbed amount and contact time. Therefore, the application of Finally, it is mentioned that the use of geometries representing
an SDM that exclusively considers surface diffusion, and puts aside better the adsorbent material during the modeling stage, allows
pore volume diffusion, would derive in the incorrect calculation of establishing accurately the concentration profiles and direction of
the values of Ds; for this reason the SDM was not applied to inter- intraparticle mass fluxes. The results of 3D-numeric simulations
pret the adsorption rate of acetaminophen on ACP. indicate that there are internal delimited areas in the pellet domi-

Exp. 1 Exp. 2 Exp. 7


qe = 52 mg/g qe = 92 mg/g qe = 185 mg/g

100

90

80

70
SDCP%

60

50

40

30

20

10

r=0 r=R
83.3 h
Fig. 10. Evolution of SDCP% for acetaminophen transport inside ACP as a function of mass adsorbed of acetaminophen for Exp 1, 2 and 7 at a contact time of 83.3 h.
520 R. Ocampo-Perez et al. / Chemical Engineering Journal 321 (2017) 510–520

nated by surface diffusion, as a form of advancing front. At longer [16] R. Ocampo-Perez, R. Leyva-Ramos, P. Alonso-Davila, J. Rivera-Utrilla, M.
Sanchez-Polo, Modeling adsorption rate of pyridine onto granular activated
times, the solute mainly enters from the solution through the pel-
carbon, Chem. Eng. J. 165 (2010) 133–141.
let borders, and acetaminophen desorption signs are even evident [17] A.E. Rodriguez, C.M. Silva, What’s wrong with Lagergreen pseudo first order
at the center of the pellet covers, due to the inverse concentration model for adsorption kinetics, Chem. Eng. J. 306 (2016) 1138–1142.
gradient established between the pellet and the solution. [18] J.D. Méndez-Díaz, G. Prados-Joya, J. Rivera-Utrilla, R. Leyva-Ramos, M.
Sánchez-Polo, M.A. Ferro-García, N.A. Medellín-Castillo, Kinetic study of the
adsorption of nitroimidazole antibiotics on activated carbons in aqueous
phase, J. Colloid Interface Sci. 345 (2010) 481–490.
Acknowledgement [19] R. Leyva-Ramos, L.A. Bernal-Jacome, J. Mendoza-Barron, M.M.G. Hernandez-
Orta, Kinetic modeling of pentachlorophenol adsorption onto granular
This work was funded by Consejo Nacional de Ciencia y Tec- activated carbon, J. Taiwan Inst. Chem. Eng. 40 (2009) 622–629.
[20] R. Ocampo-Pérez, M.M. Abdel Daiem, J. Rivera-Utrilla, J.D. Méndez-Díaz,
nologia, CONACYT, Mexico, through grants Nos. CB-2013-01
Manuel Sánchez-Polo, Modeling adsorption rate of organic micropollutants
221757, PN-I000/513/2016. present in landfill leachates onto granular activated carbon, J. Colloid Interface
Sci. 385 (2012) 174–182.
[21] K.K.H. Choy, G. McKay, Sorption of cadmium, copper, and zinc ions onto bone
References char using Crank diffusion model, Chemosphere 60 (2005) 1141–1150.
[22] K.K.H. Choy, J.F. Porter, G. McKay, Film–pore diffusion models—analytical and
[1] J. Rivera-Utrilla, M. Sánchez-Polo, V. Gómez-Serrano, P.M. Álvarez, M.C.M. numerical solutions, Chem. Eng. Sci. 59 (2004) 501–512.
Alvim-Ferraz, J.M. Dias, Activated carbon modifications to enhance its water [23] C. Liang, Z. Lan, X. Zhang, Y. Liu, Mechanism for the primary transformation of
treatment applications. An overview, J. Hazard. Mater. 187 (2011) 1–23. acetaminophen in a soil/water system, Water Res. 98 (2016) 215–224.
[2] USEPA, Granular Activated Carbon Treatment: Report EPA-540/2-91/024, US. [24] R. Rosal, A. Rodríguez, J.A. Perdigón-Melón, A. Petre, E. García-Calvo, M.J.
Environmental Protection Agency U.S. Government Printing Office, Gómez, A. Agüera, A.R. Fernández-Alba, Occurrence of emerging pollutants in
Washington, DC, 1991. urban wastewater and their removal through biological treatment followed by
[3] A.S. Mestre, R.A. Pires, I. Aroso, E.M. Fernandes, M.L. Pinto, R.L. Reis, M.A. ozonation, Water Res. 44 (2010) 578–588.
Andrade, J. Pires, S.P. Silva, A.P. Carvalho, Activated carbons prepared from [25] A.M. Larson, J. Polson, R.J. Fontana, T.J. Davern, E. Lalani, L.S. Hynan, J.S. Reisch,
industrial pre-treated cork: sustainable adsorbents for pharmaceutical F.V. Schiodt, G. Ostapowicz, A.O. Shakil, W.M. Lee, Acetaminophen-induced
compounds removal, Chem. Eng. J. 253 (2014) 408–417. acute liver failure: results of a United States multicenter, prospective study,
[4] B.N. Bhadra, P.W. Seo, S.H. Jhung, Adsorption of diclofenac sodium from water Hepatology 42 (6) (2005) 1364–1372.
using oxidized activated carbon, Chem. Eng. J. 301 (2016) 27–34. [26] B.K. Park, N.R. Kitteringham, J.L. Maggs, M. Pirmohamed, D.P. Williams, The
[5] R. Mailler, J. Gasperi, Y. Coquet, C. Derome, A. Buleté, E. Vulliet, A. Bressy, G. role of metabolic activation in drug induced hepatotoxicity, Annu. Rev.
Varrault, G. Chebbo, V. Rocher, Removal of emerging micropollutants from Pharmacol. Toxicol. 45 (2005) 177–202.
wastewater by activated carbon adsorption: experimental study of different [27] A.I. Moral-Rodríguez, R. Leyva-Ramos, R. Ocampo-Pérez, J. Mendoza-Barron, I.
activated carbons and factors influencing the adsorption of micropollutants in N. Serratos-Alvarez, J.J. Salazar-Rabago, Removal of ronidazole and
wastewater, J. Environ. Chem. Eng. 4 (2016) 1102–1109. sulfamethoxazole from water solutions by adsorption on granular activated
[6] F.J. García-Mateos, R. Ruiz-Rosas, M.D. Marqués, L.M. Cotorruelo, J. Rodríguez- carbon: equilibrium and intraparticle diffusion mechanisms, Adsorption 22
Mirasol, T. Cordero, Removal of paracetamol on biomass-derived activated (2016) 89–103.
carbon: modeling the fixed bed breakthrough curves using batch adsorption [28] F. Rodriguez-Reinoso, A. Linares-Solano, Microporous structure of activated
experiments, Chem. Eng. J. 279 (2015) 18–30. carbons as revealed by adsorption methods, in: Chemistry and Physics of
[7] P. Iovino, S. Canzano, S. Capasso, A. Erto, D. Musmarra, A modeling analysis for Carbon, New York, 1988.
the assessment of ibuprofen adsorption mechanism onto activated carbons, [29] F.J. García-Mateos, R. Ruiz-Rosas, M.D. Marqués, L.M. Cotoruelo, J. Rodríguez-
Chem. Eng. J. 277 (2015) 360–367. Mirasol, T. Cordero, Removal of paracetamol on biomass-derived activated
[8] L.R. Radovic, C. Moreno-Castilla, J. Rivera-Utrilla, Carbon materials as carbon: modeling the fixed bed breakthrough curves using batch adsorption
adsorbents in aqueous solutions, Chem. Phys. Carbon 27 (2001) 227–405. experiments, Chem. Eng. J. 279 (2015) 18–30.
[9] C. Moreno-Castilla, Adsorption of organic molecules from aqueous solutions on [30] J. Lladó, C. Lao-Luque, B. Ruiz, E. Fuente, M. Solé-Sardans, A.D. Dorado, Role of
carbon materials, Carbon 42 (2004) 83–94. activated carbon properties in atrazine and paracetamol adsorption
[10] R.W. Coughlin, F.S. Ezra, Role of surface acidity in the adsorption of organic equilibrium and kinetics, Process Saf. Environ. Prot. 95 (2015) 51–59.
pollutants on the surface of carbon, Environ. Sci. Technol. 4 (1968) 291–297. [31] T. Furusawa, J.M. Smith, Fluid-particle and intraparticle mass transport rates in
[11] Y.S. Ho, G. Mckay, Kinetic models for the sorption of dye from aqueous solution slurries, Ind. Eng. Chem. Fundam. 12 (1973) 197–203.
by wood, Process Saf. Environ. Prot. 76 (1998) 183–191. [32] C.H. Giles, D. Smith, A. Huitson, A general treatment and classification of the
[12] G. Blanchard, M. Maunaye, G. Martin, Removal of heavy metals from waters by solute adsorption isotherm. I. Theoretical, J. Colloid Interface Sci. 47 (1974)
means of natural zeolites, Water Res. 18 (1984) 1501–1507. 755–765.
[13] S. Mondal, K. Sinha, K. Aikat, G. Halder, Adsorption thermodynamics and [33] A.C.F. Ribeiro, M.C.F. Barros, L.M.P. Veríssimo, C.I.A.V. Santos, A.M.T.D.P.V.
kinetics of ranitidine hydrochloride onto superheated steam activated carbon Cabral, G.D. Gaspar, M.A. Esteso, Diffusion coefficients of paracetamol in
derived from mung bean husk, J. Environ. Chem. Eng. 3 (2015) 187–195. aqueous solutions, J. Chem. Thermodyn. 54 (2012) 97–99.
[14] M.A. Chayid, M.J. Ahmed, Amoxicillin adsorption on microwave prepared [34] R. Ocampo-Pérez, R. Leyva-Ramos, M. Sanchez-Polo, J. Rivera-Utrilla, Role of
activated carbon from Arundo donax Linn: isotherms, kinetics, and pore volume and surface diffusion in the adsorption of aromatic compounds
thermodynamics studies, J. Environ. Chem. Eng. 3 (2015) 1592–1601. on activated carbon, Adsorption 19 (2013) 945–957.
[15] G. Nazari, H. Abolghasemi, M. Esmaieli, Batch adsorption of cephalexin [35] D.D. Do, Adsorption Analysis: Equilibria and Kinetics, first ed., Imperial College
antibiotic from aqueous solution by walnut shell-based activated carbon, J. Press, London, UK, 1998.
Taiwan Inst. Chem. Eng. 58 (2016) 357–365. [36] M. Suzuki, Adsorption Engineering, first ed., Elsevier, Japan, 1990.