Article

pubs.acs.org/IECR

Adsorption of Polycyclic Aromatic Hydrocarbons from Heavy

Naphthenic Oil Using Commercial Activated Carbons. 1. Fluid-
Particle Studies
F. Murilo T. Luna, A. Nilson Oliveira Filho, Caio C. B. Araújo,# Diana C. S. Azevedo,
and Celio L. Cavalcante, Jr.*
Departamento de Engenharia Química, Grupo de Pesquisa em Separações por Adsorçaõ , Núcleo de Pesquisas em Lubrificantes,
Universidade Federal do Ceará, Campus do Pici, Bl. 709, Fortaleza, CE 60.455-900, Brazil
*
S Supporting Information

ABSTRACT: In this study, the adsorption of polyaromatic

hydrocarbons (PAHs) from heavy naphthenic oils (HNOs) on
commercial activated carbons was evaluated. Among the aromatics,
polycyclic aromatic hydrocarbons (PAHs) are usually present in
heavy oils and are contaminants that have potential carcinogenic
and mutagenic characteristics. Oils with of PAH concentration less
than 3 wt % are labeled as noncarcinogenic. The HNO samples
used in this study had a high content of PAHs (ca. 8 wt %). Batch
experiments were carried out to evaluate the adsorption capacity of
activated carbons for PAHs (>160 mg/g), and to estimate the
mass transfer parameters of the adsorption process. The pore
diffusion model and the pore−surface diffusion model were
applied to interpret and validate the kinetic experimental results.
The results indicated the efficiency of activated carbons as potential adsorbent to adjust the polycyclic aromatics content of
HNO.

1. INTRODUCTION adsorbed and the specific carbon material. Nonpolar com-

Aromatic compounds are present in several types of hydro-
carbon streams, and their concentration is highly dependent on
the original crude oil and its refinery processing.
These streams may be used as feedstocks or solvents,
according to their aromatics nature and concentration.
Polycyclic aromatic hydrocarbons (PAH) present in these
heavy streams may cause environmental problems since they
have proven carcinogenic and mutagenic effects.1−5 These
characteristics led to the study of alternatives for mitigating the
concentration level of these compounds, particularly in streams
derived from oil feedstocks that tend to cause environmental
impacts.
PAH compounds are known to resist biological degradation
and are difficult to be removed from feedstock streams by
conventional physicochemical methods, such as coagulation,
flocculation, sedimentation, filtration, or ozonation.6,7 However,
adsorption processes may be effective for removing persistent
organic pollutants, particularly with activated carbon as
sorbent.8−13
Activated carbons can be used to adsorb almost any organic
compound. Some benefits, like low energetic demand, easy
regeneration, their wide availability and possible use both in
liquid or gas phase adsorption made these materials an
interesting field of research.10 In general, the adsorption rate
and capacity are a function of the nature of the molecules to be
pounds are normally retained due to London dispersion forces;
on the other hand, polar compounds adsorption is normally
related to particular interactions through oxygenate groups in
the surface of the material.
Several studies about the adsorption of organic compounds
present in diluted aqueous solutions have been performed using
activated carbons. In particular, the adsorption of phenol is one
of the most studied systems due to its industrial and
environmental relevance.10,14−24 Despite being largely used
for environmental remediation, mechanisms of adsorption in
activation carbons are yet not well-defined.10
The textural characteristics of activated carbons may
elucidate the different adsorption capacity of these materials.
Because of the numerous sources and treatments, activated
carbons can be prepared so that they present adequate pores
and surface chemical structure and may be specifically designed
for separating PAHs. The adsorption of naphthalene in
different carbon based materials has been studied by Ania et
al.10 showing strong dependence with pore size distribution,
microporosity, and their hydrophobic nature.
Received: March 17, 2016
Revised: June 22, 2016
Accepted: June 28, 2016

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.6b01059

Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
To predict the performance of commercial adsorption
processes, several models based on intraparticle mass transfer
resistances have been reported. These include the pore
diffusion model,25,26 the surface diffusion model26−28 and
dual-resistance (pore and surface) model.26,29,30 In fact,
adsorption processes may involve several simultaneous mass
transfer resistances.
In this study, the removal of PAHs from samples of heavy
naphthenic oils (HNO) was evaluated using commercial
activated carbons. That oil feedstock is a vacuum industrial
distillate with viscosities varying between 380 and 420 cSt (at
40 °C), obtained from different types of Brazilian crude
petroleum and mainly applied to special waxes and lubricants
formulation. Without proper treatment, HNO presents a high
PAHs concentration. Hence, it is important to reduce this
concentration in order to encompass regulatory requisitions for
commercial applications.
2. EXPERIMENT AND MODELING
2.1. Materials. The heavy naphthenic oil (HNO) sample
was kindly provided by Petrobras (Brazil). Its physicochemical
properties are shown in Table S1 (Supporting Information).
For PAHs extraction, sodium chloride (J.T. Baker, USA),
cyclohexane (>99 wt % Merck, USA), and dimethyl sulfoxide,
DMSO, (>99 wt %, J.T. Baker, USA) were used. Deionized
water was obtained using a Milli-Q system (Millipore, USA).
Naphthalene solutions (>98 wt %, Acros Organics, USA) were
used at different concentrations in cyclohexane for the
calibration of the total aromatics method. Two granular
activated carbons used in this study were 830W (AC1) and
1240 Plus (AC2), both provided by Norit (Netherlands). Prior
to use in the experiments, the activated carbons were washed
with deionized water and then thermally regenerated, first at 40
°C for 1 h, and then heated to 120 °C at 30 °C/h. After 2 h at
120 °C, the samples were cooled down to 25 °C under vacuum
and immediately used in the experiments.
2.2. Textural Properties of Activated Carbons. Nitro-
gen isotherms at 77 K were measured using an Autosorb-1 MP
(Quantachrome, USA). The BET methodology was employed
to calculate the specific surface area, and the Dubinin−
Radushkevich (DR) equation was used to determine the
micropore volume, following procedures reported in Rouquerol
et al.31 The total pore volume was estimated from the adsorbed
volume of nitrogen at relative pressure of 0.95. The mesopore
volume was calculated by the difference between the total pore
volume and the micropore volume. The pore size distribution
was obtained using the Density Functional Theory (DFT)
method.
2.3. Aromatics Content in HNO Samples. 2.3.1. Carbon
Distribution Method n-d-M-ASTM D 3238.32 This method
estimates the distribution of paraffinic, naphthenic, and
aromatic carbons in mineral oils, from refractive index
measurements, specific gravity, and estimated molecular weight.
Molecular weight can be estimated taking into account
measurements of kinematic viscosities at various temperatures,
as described in ASTM D2502.32 These results are then used for
estimating the percentage distribution of aromatic, paraffinic,
and naphthenic carbons (% CA, % CP and % CN, respectively)
in a model molecule. If the samples show a significant amount
of sulfur (>0.1 wt %), correlations with correction for total
sulfur content using X-ray fluorescence must be used as
presented in method ASTM D3238.32
B DOI: 10.1021/acs.iecr.6b01059
Article
2.3.2. Total Aromatics by FTIR. Measurements of total
aromatics concentrations were performed using an infrared
spectrophotometer Fourier transform FX-3000 (BIORAD,
USA), equipped with a DTGS detector and a KBr beam
splitter. Details on this method may be found in Luna et al.33
2.3.3. Polyaromatics Content. The determination of the
mass percentage of polycyclic aromatic hydrocarbons in the
samples was performed following the method IP 346.34 This
method is normally used for measurements of PAH content. It
is very arduous needing a high consumption of solvents in a
gravimetric procedure wherein there is a dilution of the oil
sample in cyclohexane followed by an extraction with DMSO.
Successive extractions with solvents (cyclohexane and DMSO)
are needed to separate PAH from the oil samples. After several
extraction steps, the solvent is evaporated and the residue,
mainly composed of polyaromatics, is quantified in relation to
the initially used mass of oil.
2.3.4. Polyaromatics Content Using DMSO Extraction
Followed by FTIR. For a rapid evaluation of the PAHs content
during the adsorption experiments, a recently developed
method33 was used. This method was proposed to reduce the
measurement time and the amount of samples and solvents. It
consists of initial extraction stages, followed by FTIR
measurements. Samples of approximately 0.2 g of oil were
submitted to an extraction step with DMSO pre-equilibrated
with cyclohexane and subsequently analyzed in the FTIR
equipment for PAHs quantification. Details of the method may
be found in Luna et al.33
2.4. Adsorption Equilibrium and Kinetic Studies.
Adsorption equilibrium experiments were carried out in batch
by placing a fixed amount of oil (10 g) in contact with different
amounts of adsorbent (0.2, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0 g) in a
thermostatic bath at 30 °C under stirring. After reaching
equilibrium, the oil was separated by vacuum filtration and the
total aromatic and polyaromatic contents were determined. The
equilibration time was estimated from kinetic experiments. The
same procedure was used to obtain the kinetic curves (10 g of
HNO and 3.0 g of adsorbent at 30 °C) by sampling the liquid
phase every 10 min.
Assuming that nonaromatics are negligibly adsorbed on
activated carbons, the concentration in the solid phase can be
calculated through a mass balance (eq 1), expressed in (mg) of
sorbate/(g) of adsorbent.
Msol(Ci − Ceq)
q* =
Mads(1 − Ceq) (1)
where Ci is the initial concentration of aromatics (mg/g), Ceq is
the final concentration of aromatics (mg/g), Msol is the mass of
HNO (g), Mads is the mass of adsorbent (g), and q* is the
concentration of adsorbate on the solid phase (mg/g of ads.).
Langmuir and Toth eqs (eqs 2a and 2b, respectively) were
used to fit the equilibrium experimental data for latter
calculations in modeling the batch kinetics experiments.
q* kCeq
=
qm 1 + kCeq (2a)
q* Ceq
=
qm (b + Ceq υ)1/ υ (2b)
where q* is the concentration of aromatics in the solid phase,
Ceq is the concentration of adsorbate in the fluid in equilibrium,
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k is the Langmuir constant, qm is the maximum adsorption Mass balance in liquid phase
capacity, b is a parameter related to the affinity with the ∂C b 3M
adsorbent, and υ is a parameter related to the degree of =− k f,b(C − Cp|r = R p )
heterogeneity of the surface. ∂t R p·ρp ·V (11)
2.5. Diffusion Models and Parameters Estimations.
The estimation of the mass transfer parameters in the batch Initial condition
adsorption kinetics was carried out using the Pore Diffusion t = 0, C = C0 (12)
Model (PDM) and the Pore-Surface Diffusion Model
(PSDM).26 Both models assume a spherical particle of For both models, instantaneous equilibrium is assumed
adsorbent in a finite bath containing a component to be between the concentration in the fluid phase within the
adsorbed, where Cb is bulk concentration, Cp is the intraparticle particles (Cp) and the concentration in the solid adsorbent (q),
liquid phase concentration, and q is a function of Cp calculated q = f (Cp) (13)
from the isotherm equation.
The PDM equations may be described as shown in eqs 3 and A tortuosity factor (τ), correlating the molecular bulk diffusivity
6 (solid phase and liquid phase balances), using appropriate with the pore diffusivity obtained from the experiments, was
initial and boundary conditions (eqs 4, 5, and 7): estimated using eq 14.26
Mass balance in particle Dmεp
τ=
∂Cp ∂q ⎛ ∂ 2C ∂Cp ⎞ Dp (14)
ρp = εpDp⎜⎜ 2 + 2 ⎟
p
εp +
∂t ∂t ⎝ ∂r r ∂r ⎟⎠ (3)
where Dm is the molecular diffusion coefficient (cm /min) 2

estimated using the Wilke−Chang equation,35 as shown in eq

Initial condition 15.
t = 0, Cp = 0, q=0 (4) (ϕ MM)1/2 T
Dm = 4.44·10−6
Boundary conditions ηV b0.6 (15)
∂Cp where MM is the molar mass of HNO, η is the oil viscosity, T is
r = 0, =0 the temperature, Vb is the molar volume of the diffusing
∂r (5a)
molecule at the boiling temperature, and ϕ is an association
∂Cp coefficient, assumed to be 1.0 for aromatics. The value of Vb
r = R p, εpDp,b = k f,b(C − Cp) (213.8 cm3/mol) was obtained by LeBas volumes as described
∂r (5b)
in Poling et al.,35 using pyrene as a model molecule.
Mass balance in liquid phase An estimation of the external mass transfer coefficient (kf,b)
was used as proposed by Furusawa and Smith25 for liquid batch
∂C b 3M adsorption.
=− k f,b(C − Cp|r = R p )
∂t R p·ρp ·V (6) The system of algebraic and partial differential equations
(PDM and PSDM), with the respective initial and boundary
Initial conditions conditions was implemented according to the standard
t = 0, C = C0 (7) gPROMS syntax. The domains were discretized using the
method of orthogonal collocation on finite elements (OCFEM)
where εp is the porosity of the particles, Dp is the pore diffusion with six sections and three placing spots per section. The
coefficient, kf,b is the film mass transfer coefficient, t is the time, estimative of pore and surface diffusion coefficients were
and r is the radial coordinate. performed using the heteroscedastic estimation method included
The Pore-Surface Diffusion Model may be described as in the computational package gPROMS.36
shown in eqs 8 and 11, using appropriate initial and boundary The root mean squared error (RMSE) was used to evaluate
conditions (eqs 9, 10 and 12), and Ds is the surface diffusion the fitting of the model to the experimental data, as shown in eq
coefficient: 16.
Mass balance in particle N
1
∂Cp ∂q 1 ∂⎡ ∂Cp ⎤ ρp ∂ ⎡ ∂q ⎤ RMSE = . ∑ (Csim − Cexp)2
εp + ρp = 2 ⎢Dp ·r 2 ⎥ + 2 ⎢Ds ·r 2 ⎥ N i=1 (16)
∂t ∂t r ∂r ⎣ ∂r ⎦ r ∂r ⎣ ∂r ⎦
(8)
where Csim is the concentration estimated from the model, Cexp
is the experimental concentration, and N is the number of
Initial conditions measured values. A RMSE = 0 indicates a perfect model
t = 0, Cp = 0, q=0 prediction of the experimental data.
(9)
Boundary conditions 3. RESULTS AND DISCUSSION
∂Cp 3.1. Aromatics Content in the HNO Sample. Carbon
r = 0, =0 distribution using ASTM D3238 is presented in Table 1, in
∂r (10a) terms of aromatic, naphthenic, and paraffinic carbon content.
∂Cp For this analysis, correlations for sulfur content (see Supporting
∂q Information, Table S1) were used as described in the ASTM
r = R p, Dp + ρp Ds = k f,b(C − Cp)
∂r ∂r (10b) D3238 method. Being an empirical method, based on typical
C DOI: 10.1021/acs.iecr.6b01059
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Table 1. Carbon Distribution for HNO According to ASTM

D3238
type of carbon distribution (%)
aromatic 20.7
naphthenic 45.8
paraffinic 33.5

structures and hypothetical assumptions, these values are

merely a broad indication of the composition of the oil in
terms of aromatic carbon.
For further estimation of the total aromatics content in the
HNO samples, a FTIR method was applied. The total
aromatics content of the HNO samples was thus calculated
as 21.7 wt % using this method, which is broadly consistent
with the obtained value using method ASTM D3238 for
aromatic carbon distribution.
To assess the polyaromatics content, analyses were
performed according to the IP 346 method34 and PAH
extraction with DMSO followed by quantification using
FTIR.33 The average results from three independent measure-
ments for these two methods were 8.2% and 7.3%, respectively.
As seen, the values obtained with these two methods are within
less than 10% difference and hence the DMSO/FTIR method,
as a quicker analytical measurement, was selected to evaluate
Figure 1. (a) N2 adsorption (solid symbols)/desorption (open
the subsequent kinetic experiments. symbols) isotherms at 77 K: (□) AC1; (○) AC2. (b) Pore size
The European Union37 recommends using the IP 346 for distribution obtained by the DFT method. () AC1; (---) AC2.
rating the oil streams because the PAH content relates directly
to the products carcinogenicity. Oils with PAH contents lower
than 3 wt % are rated as noncarcinogenic. As reported, the
sample presented polyaromatic content above the established,
strongly suggesting the need for using treatment processes to
obtain products with low content of PAHs and therefore less
prone to cause environmental impacts.
3.2. Textural Properties of Activated Carbons. Nitro-
gen isotherms at 77 K for our samples are shown in Figure 1a.
Differences in porosity can be clearly noted between the two
samples. The obtained isotherms can be classified as type I of
the BDDT classification, typical of microporous carbon
materials.38 The textural parameters of these materials are
reported in Table S2 (Supporting Information). AC1 presents
higher values of surface area and pore volumes if compared to
AC2.
Differences in micropore sizes can be more detailed using the
DFT method (Figure 1b). Both activated carbon samples
present wide pore size distributions (considerable volume of
pores between 1.2 and 3.5 nm). A predominant unimodal
distribution is observed for AC1 with the majority of pores
between 1.2 and 2.4 nm. In this case, PAH retention could be
favored by the overlapping of the adsorption potentials, as
previously reported.39 On the other hand, a predominant
bimodal distribution is observed for AC2, with peaks in 1.5 and
3.5 nm pore sizes.
3.3. Equilibrium Studies. The equilibrium experimental
data for the batch adsorption experiments with activated Figure 2. Equilibrium adsorption isotherms of PAH from HNO
carbons, in terms of polycyclic aromatics, are shown in Figure 2. samples on activated carbons at 30 °C. (○) AC1; (□) AC2; (a)
Equilibrium curves were fitted for each system according to the Langmuir fit; (b) Toth fit.
Langmuir (Figure 2a) and Toth (Figure 2b) equations, with
parameters listed in Table 2.
The results indicate that the Toth equation shows better
agreement with the experimental data of the equilibrium equation is empirically modified from the Langmuir equation
behavior of HPA onto the activated carbons. The Toth and normally best suited to multilayer adsorption.40
D DOI: 10.1021/acs.iecr.6b01059
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Industrial & Engineering Chemistry Research Article

Table 2. Parameters of the Langmuir and Toth Equations for

PAH Adsorption on Activated Carbons at 30 °C
Langmuir equation Toth equation
qm qm
adsorbents k (mg/g) R2 b (mg/g) υ R2
AC1 0.092 186.2 0.95 1.957 220.3 0.59 0.98
AC2 0.062 165.5 0.93 3.255 203.4 0.63 0.97

To compare the behavior of the two samples of activated

carbon used in this study, an adsorption selectivity (αPAH/A)
between polyaromatics (PAH) and single aromatics (A) was
defined as
qPAH /(qTA − qPAH) Figure 4. Kinetic adsorption experiments of HNO on activated
αPAH/A = carbons at 30 °C in terms of PAH concentration decay (C0 = 73 mg/
C PAH/(C TA − C PAH) (17) g): (○) AC1; (□) AC2; pore diffusion model (PDM) using Langmuir
equilibrium equation (dotted lines) and Toth equilibrium equation
where αPAH/A is the selectivity of PAH with respect to single (full line).
aromatics compounds, qPAH is the concentration of PAHs in the
solid phase, calculated using a mass balance, as shown in eq 1,
for the PAH concentrations in the liquid phase (CPAH); qTA is
the concentration of total aromatics in the solid phase; CPAH
and CTA are the concentrations of PAHs and total aromatics in
the fluid in equilibrium, respectively. The values obtained for
this selectivity are plotted in Figure 3 versus adsorption loading.

Figure 5. Kinetic adsorption experiments of HNO on activated

carbons at 30 °C in terms of PAH concentration decay (C0 = 73 mg/
g). (○) AC1; (□) AC2; Lines are representation of the Pore-Surface
diffusion model (PSDM) using Toth equilibrium equation.

Table 3. Estimated Mass-Transfer Parameters Using PDM

equilibrium kf,b Dp tortuosity
adsorbents model (cm/min) (cm2/min) factor RMSE
Figure 3. Equilibrium selectivities between polyaromatics (PAH) and AC1 Langmuir 1.38 8.41·10−8 158 2.5·
single aromatics (A) for activated carbons at 30 °C: (○) AC1; (□) 10−3
AC2. AC2 Langmuir 1.62 3.50·10−8 341 1.7·
10−3
AC1 Toth 1.38 8.10·10−8 164 1.1·
It may be seen that, in general, selectivities decrease with 10−3
increasing loading for both carbon samples. Also, it may be AC2 Toth 1.62 3.32·10−8 359 0.9·
10−3
noted higher selectivities for AC1 in all loadings when
compared to AC2 (10.1 and 3.7, respectively, at the higher
loading). tortuosity values may only be explained if an additional mass
3.4. Adsorption Kinetics Studies. Batch kinetics experi- transfer resistance is taking place at the same time during the
ments, showing the concentration decay (C/Co) versus time, adsorption process.
are presented in Figures 4 and 5. The Pore Diffusion Model With this observation, a surface diffusion step was added to
was first used to estimate pore diffusion coefficients and a the simulation model, as described in the modeling section. To
tortuosity factor (eq 15) was calculated as shown in Table 3. simulate the experimental data with the PSDM, a tortuosity
Both equilibrium equations (Langmuir and Toth) were factor of 5 was used as input for the pore diffusion step, and
evaluated in this model, and again lower values of RMSE (eq thus the surface diffusitvity (Ds) could be estimated using the
16) were observed when using the Toth equation. It may be model described in eqs 8−15 to fit the experimental data (see
seen in Table 3 that very high tortuosities were estimated for Figure 5 and Table S3, Supporting Information).
both activated carbons (≫ 10). Normally tortuosity factors of 2 A comparison between our estimates for the surface
to 10 should be found in systems in porous adsorbents.26,41 diffusivities and previously reported values for pure aromatic
Despite the apparent good agreement observed between the compounds (benzene, naphthalene, phenantrene, and pyrene)
experimental values and the pore diffusion model simulation in synthetic mixtures is depicted in Figure 6. It may be seen that
(Figure 4), it is clearly physically inconsistent and should not be diffusivities decrease generally with increasing number of
used for real systems calculations. Such high calculated aromatic rings in the sorbates. The diffusivity values estimated
E DOI: 10.1021/acs.iecr.6b01059
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Industrial & Engineering Chemistry Research Article

on activated carbons. Furthermore, an evaluation of the

diffusivity values reported in the open literature for synthetic
mixtures versus the number of aromatic rings in the pure
components indicates that the HNO sample used in this study
would probably present PAHs with predominantly 3−4
aromatic rings. Finally, the oil treatment showed a significant
decrease in the PAH content (from 8.2 to 3 wt % using AC1).

■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.6b01059.
Physicochemical properties of HNO; textural properties
Figure 6. Surface diffusion coefficients estimated from PSDM
compared to literature data for similar conditions: (○) Furusawa of activated carbons; surface diffusion coefficients
and Smith;25 (△) Luna et al.;42 (□) Ahn et al.43 estimated from PSDM compared to literature data for
similar conditions (PDF)
in this study, for a real mixture of PAHs in a complex medium
(HNO), follow nicely the observed trend, especially in the
range between 3 and 4 aromatic rings.
■ AUTHOR INFORMATION
Corresponding Author
3.5. Evaluation of Product Following the Batch *Tel.: +55-85-3366-9611. Fax: +55-85-3366-9601. E-mail:
Adsorption Treatment. The evaluated physicochemical celio@gpsa.ufc.br.
properties of the HNO samples after the adsorption treatment
Present Address
with activated carbons showed no significant changes, as shown #
in Table 4. However, the PAH content (IP346 method) and C.C.B.A.: IFP Training Middle East, Manama Centre,
after treatment for both materials, was significantly reduced Entrance 4, Office 506, Diplomatic Area, Manama, PO Box
(50−60 wt %), when compared to the untreated oil sample. 10813, Kingdom of Bahrain.
Notes
The authors declare no competing financial interest.

■
Table 4. Physicochemical Properties and PAH Content of
HNO after Treatment
ACKNOWLEDGMENTS
HNO treated
The authors wish to thank financial and logistic support
properties HNO fresh AC1 AC2 provided by PETROBRAS (Petróleo Brasileiro S.A.) and
specific gravity at 20 °C, g/cm3 0.940 0.938 0.940 CNPq (Conselho Nacional de Pesquisa e Desenvolvimento
kinematic viscosity at 40 °C, cSt 410.3 404.9 407.0 ́
Cientifico). The authors are also grateful to NORIT Activated
refractive index at 20 °C 1.521 1.516 1.518 Carbon (Netherlands) for providing samples.
sulfur content (FRX), wt %
PAH content (IP-346), wt %
0.75
8.2
0.18
3.0
0.23
4.2
■ SYMBOLS
b = Toth equilibrium constant
C = bulk liquid phase concentration (mg·g−1)
4. CONCLUSIONS C0 = initial concentration (mg·g−1)
A sample of heavy naphthenic oil (HNO) containing ca. 8 wt % Ceq = equilibrium concentration (mg·g−1)
of polyaromatic hydrocarbons (PAHs) was treated in an Cexp = experimental concentration (mg·g−1)
experimental batch adsorption system in liquid phase with two Cp = intraparticle liquid phase concentration (mg·g−1)
samples of commercial activated carbons. The equilibrium CPAH = concentration of PAHs in equilibrium (mg·g−1)
adsorption results indicated adsorption capacities between 160 Csim = simulated concentration (mg·g−1)
and 220 mg PAH/g of adsorbent. An equilibrium selectivity for CTA = concentration of total aromatics in equilibrium (mg·
the PAHs adsorption with respect to single aromatics showed g−1)
decreasing values with increasing adsorption loadings and Dm = molecular diffusion coefficient (cm2·min−1)
varied between 10 and 16 for sample AC1, and 3−6 for sample Dp = Pore diffusion coefficient (cm2·min−1)
AC2. DS = surface diffusion coefficient (cm2·min−1)
Subsequently, kinetics experiments were performed and k = Langmuir equation parameter (g·mg−1)
evaluated using the Pore Diffusion Model (PDM). Despite the kf,b = film mass transfer coefficient (cm·min−1)
good agreement that was observed between experimental data MM = molecular weight (g·mol−1)
and the fitting of the model, the estimated pore tortuosities q = solid phase concentration (mg·g−1)
were physically inconsistent (≫10), with estimates well above qm = maximum adsorption capacity (mg·g−1)
the usual values observed for macropore diffusion controlled qPAH = concentration of PAHs in the solid phase (mg·g−1)
systems. So a dual pore diffusion model (PSDM, pore surface qTA = concentration of total aromatics in the solid phase
diffusion model) was applied to evaluate the kinetic data fitting (mg·g−1)
the experimental values using the surface diffusivity as r = radial coordinate (cm)
adjustable parameter. The estimated surface diffusivities (ca. Rp = average particle radius (cm)
10−9 cm2/min) fell within the range of previously reported t = time (min)
values for pure polyaromatic compounds in synthetic mixtures T = absolute temperature (K)
F DOI: 10.1021/acs.iecr.6b01059
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u = superficial velocity (cm·min−1)
Vb = molar volume at normal boiling point (cm3·g mol−1)
Greek Symbols
αPAH/A = selectivity of PAH with respect to single aromatics
compounds
εp = particle void fraction
ραp = particle apparent density (g·cm−3)
ϕ = association coefficient
η = dynamic viscosity (cP)
τ = tortuosity factor
υ = dimensionless parameter related to the surface
heterogeneity in Toth equation
■
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