Environmental Technology & Innovation 20 (2020) 101092

Contents lists available at ScienceDirect

Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti

Cr (VI) adsorption in batch and continuous scale: A

mathematical and experimental approach for operational
parameters prediction
∗
Renata Farias Oliveira a , Keila Guerra Pacheco Nunes a , , Ivone Vanessa Jurado a ,
Ianka Cristine Benício Amador b , Diego Cardoso Estumano b ,
Liliana Amaral Féris a
a
Federal University of Rio Grande do Sul, Department of Chemical Engineering, Ramiro Barcelos Street, 2777, Porto Alegre -
RS, Postcode 90035-007, Brazil
b
Federal University of Pará, Faculty of Chemical Engineering, Augusto Corrêa Street, 01, Belém - PA, Postcode 66075-110, Brazil

article info a b s t r a c t

Article history: Amongst the main water pollutants, hexavalent chromium stand out, due to its carcino-
Received 6 June 2020 genic and mutagenic effects to the living organisms. The aim of this work is to study the
Received in revised form 3 August 2020 efficiency of hexavalent chromium adsorption onto granular activated carbon (GAC) and
Accepted 4 August 2020
to predict the mathematical models that best describes the adsorption behavior. The
Available online 6 August 2020
effect of pH, contact time and absorbent concentration using synthetic and industrial
Keywords: effluent were performed to evaluate the parameters of adsorption process. Fixed-bed
Chromium column tests were carried out for breakthrough curve setting. Markov Chain Monte Carlo
Activated carbon (MCMC) and Bayesian Criteria Information (BIC) were applied. Adsorption best results
Pilot plant were pH 2, 10 g L−1 of solid and 50 min of contact time. Fixed bed column tests showed
Adsorption a breakthrough time of 135 min, with 5 g of granular activated carbon and 40 mg L−1 of
Bayesian technique Cr(VI) for 92% of removal. Also, the best model fit for isotherm and breakthrough were
Markov Chain Monte Carlo
Sips and Yan model, respectively.
© 2020 Published by Elsevier B.V.

1. Introduction

The contamination of water resources resulting from the release of industrial effluents containing heavy metals is
a major concern due to the fact that the compounds are generally non-biodegradable, difficult to remove and highly
toxic (Abarca et al., 2020). The metal-mechanical and galvanic industries, in particular, generate large amounts of liquid
effluents in their processes with heavy metal concentrations (Pradhan et al., 2017). The residual chromium generated in
these processes becomes harmful to the environment since it adds toxic characteristics to soils and rivers, increasing the
amount untreated waste released. Because it is highly toxic, carcinogenic and mutagenic to animals and humans, much
importance is given to research related to the decrease in the concentration of chromium released in the receiving bodies
(Alves et al., 2019). However, this chemical element is fundamental for technological development, as it is an important
metal in the treatment of surfaces, in the production of pigments, catalysts and metal alloys, such as stainless steel, as
it is a corrosion inhibiting agent (Gita et al., 2017; Zhao et al., 2016; Liu et al., 2020; Swarnkumar and Osborne, 2020).
Therefore, it is necessary to remove chromium from waste streams before being discharged into public water sources.

∗ Corresponding author.
E-mail address: keila.nunes@ufrgs.br (K.G.P. Nunes).

https://doi.org/10.1016/j.eti.2020.101092
2352-1864/© 2020 Published by Elsevier B.V.
2 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092

Several methods have been studied for chromium removal, such as ion exchange, photochemical, electrodialysis and
electrocoagulation (Wang et al., 2020; Chen and Liu, 2020; dos Santos et al., 2019; Khan et al., 2019). These techniques
are applied with the purpose of meeting the safe environmental parameters of metals in the effluents for the discharge
of effluents in receiving water bodies, but it has as limitations the inefficiency of ion removal when present in low
concentrations (Malkoc and Nuhoglu, 2007). Thus, one of the alternatives developed for the removal of contaminating
metals, such as Cr(VI), is the adsorption process, standing out for its efficiency in removing ions in high and low
concentrations, in less time, minimizing operating costs. It method involved a surface phenomenon where the adsorbent
material with high adsorption characteristics is an important parameter due to that involves the specificity of the sorbent–
sorbate system. Several solids adsorbents are used to chromium removal such as ion-imprinted polymers, Magnetic
poly(GMA–EGDMA) beads, smectite, factory waste and zeolite (Bayramoğlu and Arica, 2008, 2011; Guerra et al., 2010;
Malkoc and Nuhoglu, 2007; Barros et al., 2004). In this work, activated carbon was the solid of interest because is the
more conventional solid used in industrial methods to water treatment due to their hydrophobicity, surface functionality,
pore structure, surface area and high adsorptive capacity (Nunes et al., 2020; Haro et al., 2017).
Adsorption using activated carbon is an efficient way for the removal of different types of pollutants such as chromium.
Usually, to study this phenomenon, is performed experiments in batch scale, however, it is also important to perform
experiments in fixed-bed column. According to Ajmani et al. (2020) adsorption in fixed bed columns is one of the most
efficient configurations for continuous processes of heavy metals removal, as it allows better use of the adsorbent. Also, it
is of great practical importance to know in advance the influence of operational parameters in the adsorption efficiency.
Therefore, mathematical models for process prediction have been widely used to foresee the behavior of adsorption
phenomena in fixed-bed column (Ajmani et al., 2020; Hayati et al., 2018; Maheshwari and Gupta, 2016). Obtaining the
main information about the adsorption process such as process rate and capacity of the adsorbent solid is relevant to
promote a more efficient system.
In this way, the objective of this work is to evaluate the adsorption technique applied for Cr(VI) removal in batch and
fixed bed column systems using synthetic and industrial effluent. In addition, this study aims to predict the mathematical
models that best describes the adsorption behavior applying Markov Chain Monte Carlo (MCMC) and BIC to select the
best models to describe solute–sorbate interactions.

2. Materials and methods

2.1. Materials

Commercial granular activated carbon (GAC), used as solid adsorbent was obtained from Synth, with a particle size
between 1 and 2 mm, and surface area of 586.4 m2 g−1 , pore volume 0.48 cm3 g−1 and pore radio of 4.826 A.

2.2. Adsorption experiments

Batch adsorption experiments were carried out using a chromium stock solution (20 mg L−1 ) and GAC as adsorbent
solid. The effect of pH was evaluated (2 to 10) with a contact time of 30 min and solid dosage of 1 g. The effect of solid
concentration was performed considering different solid concentrations (2.5 to 15 g L−1 ). For these tests, the adsorption
contact time was 30 min and the pH was used according to the best results obtained in pH study. The contact time
experiments were performed applying the best results of pH and adsorbent concentrations obtained in different times (3
to 180 min). Residual concentration was evaluated according to Standard Methods 3500-Cr (2017).
Adsorption batch experiments were performed in duplicate with an error less than 5%. Removal percentage and the
amount of metal ion adsorbed was calculated using Eqs. (1) and (2).
Ci − Cf
Remov al (%) = × 100 (1)
Ci
(Ci − Ce )
qe mg g−1 =
( )
×V (2)
Ms
Where Ci is an initial concentration of chromium in the solution and Cf represents the final concentration. Residual
concentration was evaluated to 540 nm in a spectrophotometer.

2.3. Industrial effluent experiments

The samples of industrial effluent were characterized through three parameters: turbidity, pH and initial concentration.
For the adsorption tests, the effluent was filtered in order to remove the oil present in the samples. The concentrations
used were 10–40 mg L−1 .
 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092 3

Fig. 1. Schematic flowchart of the pilot plant PTA/TI. (1) peristaltic bomb, (2) alimentation tanks, (3) adsorption column, (4) thermostatic bath, (5)
UV detector, (6) effluent disposal tanks, (7) differential pressure sensor, (8) pressure sensor, (9) flowmeter, (10) security valve, (11) sample collection
points.

2.4. Adsorption isotherms

Isotherms experiments were performed varying the chromium solution concentration (25–1000 mg L−1 ). The param-
eters pH, solid concentration and adsorption time were used according to the last item. The following isotherm models
were performed to fit the equilibrium data: Langmuir Eq. (3) (Langmuir, 1916), Freundlich Eq. (4), Sips Eq. (5), Khan
Eq. (6), (Wu et al., 2010; Nagy et al., 2014; Ayawei et al., 2017; Liu et al., 2019; Al-Ghouti and Da’ana, 2020).
qmax kL Ce
qe = (3)
1 + kL Ce
qe = KF Ce1/n (4)
n
qmax ks Ce S
qe = n (5)
1 + kS Ce S
qmax bK Ce
qe = (6)
(1 + bK Ce )aK
where qe (mg·g−1 ) is the equilibrium adsorption amount at equilibrium concentration of Ce (mg·L−1 ); qmax (mg·g−1 ) is
the maximum capacity of the adsorbent and KL (L·mg−1 ) is the Langmuir adsorption constant; KF (mg1−1/n ·L1/n ·g−1 ) is
the Freundlich constant and n is the exponent of non-linearity; KS is the Sips model isotherm constant (mg1−nS ·LnS ·g−1 ),
and nS is the Sips model exponent; bK is the Khan model constant (L·mg−1 ) and aK is the Khan model exponent.

2.5. Experiments in pilot plant-fixed bed column

Fig. 1 shows the pilot plant diagram used. It allows sorption of aqueous solutions at ambient pressure in the sorption
column.
To experimental study in the pilot plant were considered the data obtained in the adsorption batch experiments.
The parameters were adjusted to each pilot experiment. The concentration of synthetic effluent was 100 mg L−1 . The
synthetic effluent was placed in the alimentation tank and the pH of the solution was adjusted with phosphoric acid.
Then, the solution was pumped through the adsorption column in increased flow. After going through the column, the
samples were collected through the valves that conduct the flow to a standoff. Finally, the samples were analyzed by
spectrophotometry UV/Vis in 540 nm wavelength.

2.6. Analysis of data of the fixed-bed column

The fixed-bed column behavior in this study focused in the breakthrough curves, with plots of time vs. C/C0 (the ratio
of the concentration of the solute in the column outlet at a given time t to the initial concentration of the solute in the
column inlet). The effluent volume was calculated by Eq. (7) (Uddin et al., 2009).

Vff = q × ttotal (7)

4 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092

where Vff is the effluent volume, q is the flow (mL min−1 ) and ttotal is the total time of process (min).
The total mass adsorbed of chromium can be calculated by the area under the breakthrough curve through Eq. (8)
(Han et al., 2009).
∫ t =ttotal
q
qtotal = Cad · dt (8)
1000 0

Where qtotal is the total mass adsorbed (mg) and Cad is the concentration of removal chromium (mg L−1 ).
The maximum removal capacity of column can be obtained by Eq. (9)
qtotal
qeq = (9)
m
Where qeq is the maximum capacity of the column (mg g−1 ) and m is the adsorbent mass (g).
The total quantity of adsorbed ions by the column was calculated by the Eq. (10), and the efficiency of the chromium
removal by Eq. (11).

mtotal = C0 · q · ttotal (10) (10)

qtotal
Y (%) = · 100(11) (11)
mtotal

2.7. Breakthrough — mathematical model

The simulation of the breakthrough was done using the following models:
Thomas:
C 1
= ( ) (12)
C0 1 + exp
kth qth W
− kth C0 t
Q

where kth (mL mg−1 min−1 ) is the kinetic constant, qth (mg g−1 ) is the maximum quantity adsorbed, W (g) is the mass
of adsorbent and Q (mL min−1 ) is flow rate.
Yoon–Nelson
( )
C kYN t
= exp − τ kYN (13)
C0 − C Q
where kYN (min−1 ) is the kinetic constant, τ (min−1 ) is the time to achieve 50% of the breakthrough and Q (mL min−1 )
is flow rate.
Yan
C 1
=1− ( )ay (14)
C0 C0 Qt
1+ qy W

where qy (mg g−1 ) is the maximum quantity adsorbed, ay is a regression coefficient.

Clark
( ) n−1 1
C 1
= (15)
C0 1 + Aexp (−rt )
where n is the isotherm constant similar from the Freundlich, A and r are constants that involves others physical constants.

2.7.1. Inverse problem — Markov chain Monte Carlo

In many problems it is not possible to make a direct measurement, these situations can be handled using the infor-
mation from the possible measurements with mathematical formulation (direct problem) and the previous knowledge
of parameters, see Fig. 2. This is mathematically represented by Bayes’ theorem, where the posterior distribution can be
considered as πposterior (P |Data) ∝ πprior (P ) π (Data|P ), where π (P ) is the probability of prior distribution and π (Data|P )
is the likelihood (Box and Tiao, 1992; Bolstad, 2004; Kaipio and Somersalo, 2004; Pasqualette et al., 2017).
Estimation of isotherm model parameters from experimental data is necessary for adsorption process modeling.
Bayesian estimation method quantifies the discrepancy by a multiplicative factor while simultaneously obtaining the
probability distributions of a single set of isotherm parameters (Shih et al., 2020). This research was applied the inverse
problem at two classes of physical phenomena which are isotherms and breakthroughs, where was evaluated 4 different
models for isotherms (Eqs. (3)–(6)) and (4) different models for breakthrough (Eqs. (12)–(15)). The parameters from each
model are presented in Table 1.
The Bayesian technique used to estimate parameter was Markov Chain Monte Carlo (MCMC) methods, which one can
be implemented using different algorithms of acceptation/rejection, for example Gibbs and Metropolis–Hastings. In this
 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092 5

Fig. 2. Illustration of Bayes theorem.

Table 1
Parameters from isotherm and breakthrough models.
Isotherm
Model Parameters
Langmuir PT = [qmax KL ]
Freundlich PT = [KF n]
Sips PT = [qmax KS ns ]
Khan PT = [qmax bK aK ]
Breakthrough
Model Parameters
Thomas PT = [KTH qTH ]
Yoon–Nelson PT [ YN τ]]
= [K
Yan PT = Ky ay
Clark PT = [A r n]

research was used the Metropolis–Hastings algorithm to accept or reject the parameter, also was implemented a random
walk as transition kernel. The Metropolis–Hastings sampling algorithm can be implemented by repeating the following
steps (Hastings, 1970; Beck and Arnold, 1977; Gamerman, 1997; Özisik and Orlande, 2000; Gilks et al., 1996; Doucet et al.,
2001; Kaipio and Somersalo, 2004; Robert and Casella, 2004; Orlande et al., 2011):

1. Sample a Candidate Point P ∗ from the proposal distribution p(P ∗ , P i−1 ).

2. Calculate the acceptance factor:
[ ) ]
π P ∗ |Data
(
α = min 1, ( i−1 (16)
π P |Data
)

3. Generate a random value U that is uniformly distributed on [0 1].

4. If ≤ α , set P i , P ∗ . Otherwise, set P i = P i−1
5. Return to step 1

In this paper, the proposal distribution was taken as the following Gaussian distribution,

P ∗ = (I + ε) P i−1 (17)

where I is the identity matrix and ε is a diagonal matrix of Gaussian random variables with zero means and standard
deviations W (search step).
The analyzes of data from isotherm and breakthrough was performed using 4 models to isotherm and 4 models to
breakthrough. The determination of the best model to simulate the data was done using bayesian metric — Bayesian
Information Criteria (BIC) Eq. (18), which the lower value indicate the best model (Schwarz, 1978; Konishi and Kitagawa,
2008; Zhao et al., 2015).

BIC = −2Ln(π (Data|P )) + Np Ln (Nobs ) (18)

where Np is the quantity of free parameters and Nobs is the quantity of observable data.
6 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092

Fig. 3. Effect of the variation of (a) solution pH, (b) contact time, and (c) solid concentration on Cr(VI) removal onto GAC. (Conditions: Cr(VI) stock
solution = 20 mg L−1 . To effect of pH was used a contact time of 30 min and solid dosage of 1 g. To effect of solid concentration was used 30 min
of contact time was 30 min and pH = 2).

3. Results and discussion

3.1. Best operational adsorption conditions — pH, contact time and solid concentration

Fig. 3 shows the effect of pH, contact time and solid concentration for the chromium adsorption on GAC.
Analyzing Fig. 3a, it can be seen that the chromium removal decrease as the medium becomes alkaline. This fact is in
accordance with studies found in the literature that reported the reduction of Cr(VI) in aqueous solutions using activated
carbon as an adsorbent. In conditions of pH 2, the form present in the aqueous medium is anionic HCrO4− , favoring
adsorption in GAC by electrostatic interactions. The best result for adsorption occurs at acid pH, because in this condition
the surface of the activated carbon is charged with H+ cations resulting in a strong electrostatic attraction between the
adsorbent and the adsorbate, leading to greater efficiency in adsorption. While at pH greater than 6 there is less adsorption
of Cr(VI) due to the competition of anions and OH− available to be absorbed on the surfaces of the solid that predominates
the presence of OH− (Khosravi et al., 2018). Authors such as Koloczek et al. (2015) and Dehghani et al. (2016) also obtain
high rates of Cr removal from solutions with acidic pH, using different adsorbent solid.
Fig. 3b shows that in 5 min there is a sudden drop in the residual chromium concentration, reaching 71.8% of the
removal for an amount of metal ion adsorbed of 0.564 mg g−1 . After a period of 30 min, the chromium removal occurs
slowly and the concentration variation is not relevant over time. This occurs because initially, all the active sites are free
at the surface of the adsorbent solids, which results in fast adsorption. When occupied by the sorbate, these free sites
decrease, leading to the saturation of the solids. Therefore, it was determined that the most suitable condition for the
removal of chromium is at a time of 50 min. Mohamed et al. (2017) using material composite nanofibers observed that
the chromium adsorption balance was reached in 30 min
Fig. 3c shows that with the increase of the adsorbent concentration in the system, the efficiency in the chromium
removal also increases until the concentration of adsorbent solid reaches 10 g L−1 . In this condition, the removal reached
the maximum value of 99.5% for an amount of metal ion adsorbed of 1.99 mg g−1 . From this point on, it was noted
that the increasing amounts of activated carbon in the system did not cause an apparent change in the efficiency of the
process. The results obtained can be explained by evaluating the behavior of the total adsorption area. The increase in the
amount of adsorbent solid in the system makes it possible to increase the adsorption area, thus, the chromium content in
the residual solution is reduced (Khosravi et al., 2018). When the chromium concentration reaches a plateau, additional
amounts of adsorbent solid have no influence on removal, since the dispersed chromium molecules have already occupied
the available surfaces.
Rafiaee et al. (2020) reported 93.75% of chromium adsorbed onto Pomegranate peel–PPy composite. The parameters
used by the authors was initial solution concentration of 50 mg L−1 , pH 1, 90 min of contact time and 10 g L−1 of
solid concentration. Rambabu et al. (2020) reported 58.02% of chromium removal on date palm empty fruit bunch waste
biosorbent for pH 2, dosage 0.3 g, 120 min contact time and 50 mg L−1 initial feed concentration. It can be appreciated that
GAC under the conditions reported in this work presents better results for chromium removal in comparison with other
solids. It which confirm that GAC continues to be one of the solids with the best results for the elimination of different
contaminants due to its physicochemical properties.

3.2. Adsorption isotherms

Adsorption isotherms assist to clarify the adsorption mechanisms representing the equilibrium relationship between
the solute in the solution and the adsorbate retained in the adsorbent, at a certain temperature (Langmuir, 1916). In order
to establish the most appropriate correlation for the equilibrium curves and to estimate the parameters for an adsorption
system, it is important to establish the most appropriate correlation for the equilibrium curves. To predict whether the
 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092 7

Table 2
Estimation of parameters for models isotherms regarding levels of uncertainties of measurements represented by mean
± standard deviation.
Model Parameter 1 % 5 % 10 %
KL (L · mg−1 ) 0.0077 ± 0.0002 0.0080 ± 0.0008 0.0081 ± 0.0014
Langmuir
qmax (mg · g−1 ) 28.72 ± 0.04 28.29 ± 0.29 28.22 ± 0.29
KF (mg1−1/n · L1/n · g−1 ) 1.504 ± 0.06 1.493 ± 0.11 1.49 ± 0.143
Freundlich
n 2.24 ± 0.03 2.24 ± 0.07 2.24 ± 0.091
qmax (mg · g−1 ) 28.70 ± 0.03 28.29 ± 0.29 28.20 ± 0.30
Sips KS (mg1−nS · LnS · g−1 ) 0.01 ± 0.001 0.007 ± 0.006 0.001 ± 0.0001
ns 0.89 ± 0.02 1.064 ± 0.14 1.37 ± 0.092
qmax (mg · g−1 ) 27.92 ± 0.2 28.17 ± 0.299 28.19 ± 0.298
Khan bK (L · mg−1 ) 0.0063 ± 0.0001 0.0061 ± 0.0009 0.005 ± 0.0015
aK 0.89 ± 0.009 0.88 ± 0.0461 0.834 ± 0.104

Table 3
Values to BIC for each model considering different levels of uncertainties..
σmeas
Model
1% 5% 10%
1. Langmuir 997.95 45.21 14.79
2. Freundlich 271.63 15.30 8.30
3. Sips 1320.1 594.73 201.86
4. Khan 66778 2692.1 722.04

adsorption of the chromium in aqueous solution was efficient or not, the shape of the isotherm, the statistical parameters
and the values of the constants for each non-linearized model were taken into consideration. The experimental value
to maximum capacity of the adsorbent qexp is 28.2 mg.g−1 , this parameter is an important information to verify the
precision of estimated parameter comparing the estimated and experimental value of this parameter. The evaluation of
the isotherms models was done considering three levels of uncertainties (σmeas ) 1%, 5% and 10% from the measurement,
the estimation of parameters are shown in Table 2.
In general, it was verified that the parameters do not significantly variation considering different levels of uncertainties.
Beyond it, the parameter qmax estimated from isotherm models Langmuir, Sips and Khan shows relative error lower than
1% in comparison to qexp , therefore the estimations of parameters has a good precision. The value of n > 1 (for Freundlich)
shows the adsorption of Cr(VI) in this solid as favorable physical process. In this way, this was the model that best applies
to concentrations of Cr(VI) in solution up to 1000 mg L−1 . The adsorbent with the greatest prominence in adsorption is
activated carbon, but there is research in search of a better adsorbent or the use of a new material or residue that is
applied as an alternative adsorbent in the sorption process. Consequently, the adsorption capacity is commonly studied.
Based on the mean of posterior distribution (see Table 2) was evaluate the metric statistic BIC to define the best model,
such values are presented in Table 3.
The values in Table 3 reveal the model that best fitted the experimental data was the Freundlich model. Hence, the
order of best to worst model defines the following sequence: Freundlich > Langmuir > Sips > Khan.
The Langmuir isotherm deals with heterogeneous reactions and assumes that all the available sites are filled as
a monomolecular layer (Langmuir, 1916). In contrast, the Freundlich isotherm is applicable for multilayer adsorption
processes that occur on heterogeneous surfaces. However, the Sips isotherm model that reduces to the Freundlich type
for small adsorbate concentration, but predicts the well-known Langmuir model for large concentrations.
In this way, Freundlich isotherm was the model that best applies to concentrations of Cr(VI) in solution up to 1000 mg
L−1 . Therefore, the adsorption of Cr(VI) in GAC adsorbent represent a combinations of both mechanism, that is, between
multilayer adsorption on heterogeneous surfaces and chemisorption process. The Khan model is another combination of
the same isotherms applied for the pure solutions, but it is not fit the experimental data as well as the Freundlich model.
Fig. 4 shows the comparison between the estimated and measured isotherms, for the Freundlich model, where it is
possible to observe a good agreement between the estimated and measured isotherms.

3.3. Industrial effluent

Samples from Stihl Machine Motorized Ltda effluent containing Cr(VI) were collected twice from the wastewater
industrial plant. The characteristics of the lots are shown in Table 4.
Tests of LOT 1 were performed at pH 2 and tests in LOT 2 were performed at the pH of the sample as received. Fig. 5
shows the effect of the adsorbent concentration (Css) on the residual concentration of Cr(VI) in (a) Lot 1 and (b) Lot 2 and
the removal percentage.
Fig. 5 shows that the removal of Cr(VI) increases with increasing GAC concentration, confirming the results obtained
with the synthetic solution (Fig. 3a). For Lot 1 sample, a concentration of 40 g L−1 of activated carbon removed 78% of
8 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092

Fig. 4. Shows the experimental adsorption isotherms and compared with models of Freundlich considering (a) 1, (b) 5 and (c) 10% of uncertainties
in the measurement for the chromium removal on GAC.

Fig. 5. Effect of the adsorbent concentration in the Cr(VI) removal for (a) Lot 1 and (b) Lot 2.

Table 4
Parameters of the collected effluent.
Parameters Lot 1 Lot 2
pH 0.4 0.1
Initial concentration (mg L−1 ) 1193 1502
Turbidity (NTU) 3200 2200

the chromium contained in the effluent. For Lot 2, a sample without pH adjustment, 98% removal was obtained, using
the same concentration of activated carbon. In view of the industrial application, this result would bring greater ease of
operation and savings in product chemicals, as it is not necessary to adjust the pH as is done in the industrial plant.
 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092 9

Table 5
Parameters of Fixed-bed.
Parameter Lot 1 Lot 2
Vff (mL) 2700 3000
qtotal (mg) 191.5 277.8
qeq (mg g−1 ) 38.3 55.6
Mtotal (g) 260 300
Y (%) 73.6 92.6

Table 6
The estimation of the parameters for breakthrough from the Thomas, Yoon–Nelson, Yan and Clark models.
σmeas = 1% σmeas = 5% σmeas = 10%
Model Parameter
Lot - 1 Lot - 2 Lot - 1 Lot - 2 Lot - 1 Lot - 2
kTH 2.16 1.52 2.02 1.53 1.75 1.48
(mL mg−1 min−1 ) (2.04; 2.31) (1.43; 1.63) (1.61; 2.70) (1.17; 2.10) (0.99; 2.68) (0.92; 2.28)
Thomas
qTH 7.37 8.13 7.56 1.48 7.56 8.12
(mg g−1 ) (7.24; 7.49) (7.91; 8.22) (6.37; 9.12) (0.91; 2.28) (6.37; 9.12) (6.80; 9.70)
kYN (min−1 ) 0.22 0.21 0.22 0.23 0.29 0.16
(0.20; 0.23) (0.20; 0.23) (0.16; 0.33) (0.17; 0.32) (0.14; 0.59) (0.08; 0.41)
Yoon–Nelson
τ (min ) −1
18.41 18.41 18.37 18.31 17.90 19.96
(18.10; 18.71) (18.10; 18.72) (16.80; 19.89) (16.80; 9.91) (15.42; 20.86) (16.85; 3.96)
qy (mg g−1 ) 7.19 7.72 7.19 7.70 7.13 7.68
(7.06; 7.30) (7.58; 7.87) (6.60; 7.88) (6.97; 8.39) (5.85; 8.86) (6.45; 8.86)
Yan
ay 2.92 2.426 2.98 2.43 2.73 2.58
(2.74; 3.11) (2.31; 2.54) (2.18; 3.89) (1.91; 3.09) (1.73; 4.41) (1.73; 3.95)
A 0.53 0.27 1.04 0.82 0.85 0.85
(0.29; 0.95) (0.16; 0.58) (0.53; 1.83) (0.35; 1.53) (0.36; 1.51) (0.36; 1.51)
−1
Clark r (min ) 0.15 0.10 0.13 0.11 0.11 0.11
(0.14; 0.16) (0.09; 0.11) (0.10; 0.17) (0.08; 0.14) (0.07; 0.16) (0.07; 0.16)
n 1.05 1.05 1.12 1.13 0.11 1.14
(1.03; 1.09) (1.03; 1.09) (1.06; 1.23) (1.04; 1.26) (0.07; 0.16) (1.05; 1.33)

Fig. 6. Breakthrough curve to Lot 1 and Lot 2. (Conditions: Lot 1: pH 2, initial concentration 1193 mg L−1 , volume 100 mL, time 40 min. Lot 2: pH
natural, initial concentration 1502 mg L−1 , volume 100 mL, time 40 min).

3.4. Experiments in adsorption plant — fixed-bed column

The solution with an initial concentration of 100 mg L−1 had its pH corrected to two and the flow rate was maintained
at 20 mL min−1 . The mass of adsorbent used was 5 g, resulting in a bed height of 2.3 cm. The Qmax of 24.9 mg L−1
to estimate the theoretical rupture time was calculated using the Langmuir equation. The theoretical break time was
62 min. With these conditions, a break time of 10 min was obtained and a saturation time of 135 min for lot 1. For lot 2,
the saturation time was 150 min. It was observed that the experimental pause intervals were longer than the theoretical
time. At the beginning of the process, the adsorption of Cr(VI) occurred quickly due to the arrangement of free active sites
for the adsorption of the metal in the GAC.
10 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092

Fig. 7. Comparison between experimental and simulated data using Yan model for both Lots.

Samuel et al. (2019) investigated the adsorption of hexavalent chromium using chitosan grafted graphene oxide (CS-
GO) nanocomposite in batch mode. The authors reported an adsorption capacity of 104.16 mg g−1 at pH 2.0 and contact
time of 420 min.
The behavior of these breakthroughs is very close to the ideal behavior, as, over time, there is an almost instantaneous
jump from the concentration of the effluent from zero to the concentration of feed when the capacity of the column
is reached. Fig. 6 shows that this curve has a very sharp concavity, indicating that the diffusion effects have been
minimized for this process condition. According to Ajmani et al. (2020), the shape and slope of the curve, depending
 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092 11

Table 7
Values to BIC for each model considering different levels of uncertainties.
σmeas = 1% σmeas = 5% σmeas = 10%
Model Lot - 1 Lot - 2 Lot - 1 Lot - 2 Lot - 1 Lot - 2
Thomas 755.3786 1194.13 32.9784 50.59 10.6395 14.87
Yoon–Nelson 755.3763 755.38 32.8211 32.89 10.9368 14.89
Yan 470.8230 583.11 21.4463 26.16 7.4290 8.81
Clark 609.7998 912.47 29.1913 41.81 10.9792 10.98

on the relationships between the equilibrium phases and the mechanisms of mass transfer. Ahmad and Hameed (2010)
affirm that the narrower the dispersion, the greater the approximation to an ideal breakthrough, in which resistance to
diffusion is minimized.
Table 5 shows that in Lot 1 the processing time was shorter than Lot 2. The processing time also influenced the mass of
adsorbed metal, the maximum capacity of the column and the total mass retained by the adsorbent. The results showed
that the removal of Cr(IV) achieved 73.6% for Lot 1 and 92% for Lot 2. This study proves that the value of the adsorption
capacity of this adsorbent used in a fixed bed has great potential for industrial application.
Table 6 shows the results for the simulation of the breakthrough using the Thomas, Yoon–Nelson, Yan and Clark models.
Based on the results presented in Table 6, the BIC metric statistic was evaluated to define the best model, these values
are presented in Table 7.
The values in Table 7 reveal the model that best fitted the experimental data was the Yan model. The compari-
son between the curve breakthrough using the Yan model and experimental measurements under different levels of
uncertainties is shown in Fig. 7.
The Fig. 7 reveals that increasing the uncertainties from the measurements the uncertainties of curve breakthrough
increasing also, in general is possible verify a good agreement between the estimated and measurement considering 1, 5
and 10% of uncertainties measurements.

4. Conclusion

The experiments showed a removal of chromium above 95% of the industrial effluent, using a Cr(IV) concentration of
100 mg L−1 and a flow rate of 20 mL min−1 . Considering the treatment of effluent at large scale, the wastewater plant
will use 1 kg of solid for each 100 L of contaminated water treated. Since, due to high mass of activated carbon needed
to process it is necessary to consider a way to regenerate the solid. Therefore it can be reused and the process would
become technically and economically viable.
The application of Bayesians Techniques Markov Chain Monte Carlo (MCMC) and Bayesian Criteria Information (BIC)
for estimate the parameters and select the best model, respectively reveals that among the models used to predict the
column breakthrough time and the isotherm considering 1, 5 and 10% of the measurement uncertainties to both physical
phenomena. The best models were Sips for isotherm and Yan for breakthrough, and it was possible to verify a good
agreement between estimated and experimental measured.

CRediT authorship contribution statement

Renata Farias Oliveira: Methodology, Investigation, Validation. Keila Guerra Pacheco Nunes: Writing - review &
editing. Ivone Vanessa Jurado: Writing - original draft. Ianka Cristine Benício Amador: Writing - original draft. Diego
Cardoso Estumano: Software, Resources, Formal analysis. Liliana Amaral Féris: Resources, Writing - review & editing,
Project administration.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

Acknowledgments

The authors thank the National Council of Technological and Scientific Development (CNPq) and the Coordination for
the Improvement of Higher Education Personnel (CAPES) of the Brazilian Government for the financial support granted
to carry out this work.
12 R.F. Oliveira, K.G.P. Nunes, I.V. Jurado et al. / Environmental Technology & Innovation 20 (2020) 101092

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