Arabian Journal of Chemistry (2021) 14, 103001

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Steam-activated carbon from malt bagasse:

Optimization of preparation conditions and
adsorption studies of sunset yellow food dye
Greice K.P. Lopes, Heloisa G. Zanella, Lucas Spessato, Amanda Ronix,
Patrı́cia Viero, Jhessica M. Fonseca, Jéssica T.C. Yokoyama, André L. Cazetta *,
Vitor C. Almeida *

Department of Chemistry, State University of Maringá, Av. Colombo 5790, CEP 87020-900 – Maringá, Paraná, Brazil

Received 24 October 2020; accepted 7 January 2021

Available online 14 January 2021

KEYWORDS Abstract In this work the malt bagasse was used as precursor for preparation of activated carbon
Physical activation; (AC) via physical activation with steam. The variables involved in the preparation process as tem-
Chemometric tools; perature and time of activation, and steam flow, were evaluated and optimized from rotatable cen-
Porous carbon material; tral composite design, response surface methodology and desirability function. The variables
Dye removal showed significant effects on the responses BET surface area (SBET) and yield of the AC. The acti-
vated carbon obtained in the optimal conditions (ACMop) of temperature 841 °C, time 82 min and
steam flow 164 cm3 min
1, showed SBET of 917 m2 g
1 and yield 9.45%, in addition to surface acid
groups and pHpzc 3.92. The ACMop was applied in the adsorption of food dye sunset yellow (SY)
from the aqueous solution, showing fast adsorption kinetics and the adsorption equilibrium around
the 240 min. The kinetic data were better described by Elovich model, while the fit of Weber and
Morris model showed that intraparticle diffusion is not the rate-limiting step. The Redlich-
Peterson isotherm model was that better fitted to experimental data, being that the g parameter near
to 1 suggested the Langmuir assumptions as the more suitable to describe the adsorption of SY onto
ACMop. Additionally, monolayer adsorption capacity of ACMop was found to be 199.7 mg g
1 at
temperature of 55 °C. The thermodynamic study showed the spontaneity of adsorption process,
with increase of randomness on the solid/liquid interface, nevertheless occurring from an endother-
mic process.
Ó 2021 The Authors. Published by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding authors.
E-mail addresses: andrecazetta@yahoo.com.br (A.L. Cazetta), vcal-
meida@uem.br (V.C. Almeida). 1. Introduction
Peer review under responsibility of King Saud University.
Activated carbons (ACs) are amorphous carbonaceous materi-
als with well-developed porous structures, attributing them
high adsorption capacities. This characteristic has been
Production and hosting by Elsevier
responsible by its wide application in the removal of organic
https://doi.org/10.1016/j.arabjc.2021.103001
1878-5352 Ó 2021 The Authors. Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 G.K.P. Lopes et al.
and inorganic species from drinking waters, wastewaters and
air (Danish and Ahmad 2018). The ACs are produced com-
mercially from a wide range of precursors, wherein the resul-
tant surface properties (chemical composition, surface area
and pore size) are dependent of the raw material selected as
precursor, as well as the preparation procedure (activation
method, temperature, etc.) (Yeganeh et al., 2006). Thereby,
the preparation of high-performance activated carbons from
renewable sources (biomass residues) is currently studied by
researchers around the word (Wong et al., 2018). These renew-
able precursors have high amounts of C, O and H, which are
the main elements that make up the natural polymers (cellu-
lose, hemicellulose and lignin) (González-Garcı́a, 2018). A lit-
erature reports the use such as coconut shell (Zhang et al.,
2020), rice husk (Raza et al., 2019), peanut shell (Wang
et al., 2020), stevia residues (Yokoyama et al., 2019) and euca-
lyptus residues (Han et al., 2020).
The activation processes for preparation of ACs can be
classified as chemical or physical. In the chemical activation,
reagents (acids, bases and some salts) are mixed with the pre-
cursors (from a wet or dry way) and pyrolyzed at temperatures
ranging from 500 to 900 °C. On the other hand, the physical
activation consists in the use of oxidant gases (CO2, air), steam
or a mixture of them, that flows throughout the system con-
taining the precursor, and which is heated at temperatures
between 800 and 1000 °C (Marsh et al., 2006). Although the
physical activation requires temperature higher than that used
in the chemical activation, it is considered an environmentally-
friendly of lowest cost process, since no chemical reagent is
used (Lee et al., 2018). Additionally, the activating agent
selected to perform the physical activation also contributes
in the final textural properties of material, while CO2 tends
to develop a greater portion of micropores, steam leads the
formation of pores distributed in a wide range of sizes (micro-
pores and mesopores) (Selvaraju et al., 2017).
In addition to the choice of the activating agent, parameters
such as temperature, time and flow of gas/steam are considered
important for carrying out the process of obtaining the ACs
(Son and Park, 2020; Pallarés et al., 2018, Selvaraju &
Bakar, 2018). However, their effects toward the surface area
development, yields, adsorption capacities of ACs are com-
monly studied from the method that varies one variable at a
time. Although the experiments can be optimized, this method
results in a large number of runs, in addition to neglecting the
interactions between the variables, which can significantly
influence the final results. Alternatively, the use of chemomet-
ric tools has been highlighted in the last years. The main design
chosen to study the influence of the variables in the prepara-
tion of AC has been the Central Composite Design (CCD),
while the analysis of interactions and optimization has been
performed via Response Surface Methodology (RSM) and
desirability function(Masoumi and Dalai, 2020; Charola
et al., 2019; Bedin et al., 2018; Sulaiman et al., 2018).
In this sense, this work has as aims to optimize, via CCD
and RSM, the preparation of steam-activated carbon from
malt bagasse, and evaluate the performance of the activated
carbon obtained under the conditions considered optimal
(ACMop) regarding its adsorption capacity of sunset yellow
(SY) food dye.
The beer production generates large amounts of solid resi-
dues, and it is estimated that 100 L of beer results in 20 kg malt
bagasse (Cordeiro et al., 2012). The malt bagasse is mainly
composed by cellulose and hemicellulose, besides lignin and
proteins (Bando et al., 2013), what makes it a potential and
sustainable precursor for preparation of ACs. This byproduct
has been used as precursors of biosorbent (Tsai et al., 2008;
Han et al., 2006) and CO2-AC (Franciski et al., 2018;
Wakizaka et al., 2016). In addition to the importance of
preparing adsorbent materials from high-available and renew-
able sources, testing their performances on removal of inor-
ganic and/or organic species from aqueous solution is
indispensable to know the efficiency of material and under-
stand the dynamic of adsorption (Anastopoulos et al., 2020).
SY is a water-soluble synthetic dye, widely used in the food
industries because its uniform color, low-cost and high stabil-
ity, and that can be used to investigate the adsorption perfor-
mances of ACs. The SY consumption in large amounts by
humans can cause allergies, diarrhea and even cancer, while
its accumulation in the body is associated with kidney and liver
damages (Mittal, 2020; Ding et al., 2019). Studies of toxicolog-
ical effects of SY in albino rats have shown that the increasing
in the dosage up to 10 times the acceptable daily intake
resulted in an increase of aminotransferases, ALP and urea
concentration in serum. Effects of SY in meristematic cells
indicated also cytotoxic activity on Allium cepa L. It is esti-
mated around 1–2% of all dyes produced are lost during the
production processes, while 10–15% are discharged as efflu-
ents from some industrial processes. Trace concentrations of
dyes (<1.0 mg/L) into aquatic environmental can inhibited
the light penetration, affecting directly the photosynthesis,
besides increases the chemical oxygen demand, resulting in sev-
eral damages to the environment (Hussain et al., 2020; Ahmad
et al., 2019).
2. Materials and methods
2.1. Precursor and centesimal analysis
The malt bagasse was supplied by a local brewery. Firstly, the
precursor was dried in oven at 100 °C overnight, ground and
the particles with diameter between 425 and 250 mm were
stored for further use. The percentage of moisture, volatile
matter, ash and fixed carbon contents were estimated via cen-
tesimal analysis, according to the methodology D1762-84 of
American Society for Testing and Materials (ASTM-D1762-
84). The results were 7.03, 79.42, 1.68 and 11.87%, for mois-
ture, volatile matter, ash and fixed carbon contents,
respectively.
2.2. Preparation of AC
The main parameters that have influence in the preparation of
AC (temperature, time and gas flow) were optimized from
Central Composite Design (CCD) and Response Surface
Methodology (RSM). It is worth pointing out here that steam
flow was established being the same of N2 used as carrier gas.
The real and coded levels of the variables are presented in
Table 1.
Central Composite Design was composed by three blocks; a
23 full-factorial design, 6 axial points and 3 central points,
totalizing 17 runs. The resulting design is presented in
Table S1. Second-order polynomial model (Eq. (1)) was fitted
to the experimental responses in order to understand the effect
Steam-activated carbon from malt bagasse 3

Table 1 Coded and real levels of the variables (factors) studied from central composite design (CCD).
Coded levels

a (
1.68)
1 0 +1 + a (+1.68)
Factors Real levels
Temperature (°C); X1 608 660 735 810 861
Time (min); X2 40 60 90 120 140
Flow (cm3 min
1); X3 52 80 120 160 187

of main variables and their interactions toward the responses.
The experimental responses evaluated were BET surface area
(SBET) and yield. To improve the fit of
polynomial
 equation,
1
the inverse of BET surface area values
SBET
and used (vide Table S1). The variance analysis (ANOVA) at
95% confidence and 3D-response surfaces were obtained from
Design-ExpertÒ 7.1.3 software (Stat-Ease Inc., Minneapolis,
MN).
X
k X
k X
k 2.3. Characterization of precursor and AC
yi ¼ b0 þ bi xi þ bii x2i þ bij xi xj þ e
i¼1 i¼1 i<j
1
where yi is the experimental response (SBET and yield percent-
age), xi and xj are the studied variables, b0 is the constant term;
bi, bii and bij are the regression coefficients associated to linear,
quadratic and interactions terms, respectively, k is the number
of factor and e is the residues of the model.
The steam used as physical activating agent was generated
from a round-bottom flask accommodated in a hot plate. The
water was heated and the steam carried inside the system by N2
flow that ranged according to conditions displayed in Table 1.
For preparation of ACs, 5.00 g of precursor (malt bagasse)
were placed into a porcelain crucible with lids (inlet and outlet
of gases) and heated in a muffle furnace. The procedure was
performed using heating rate of 10 °C min
1 and in two steps:
(i) carbonization under N2 flow of 100 cm3 min
1 at temper-
ature of 500 °C for 2 h, and (ii) activation step according to
the experimental conditions displayed in Table 2. After allow-
ing the material to cool, they were washed with HCl solution
(0.1 mol L
1) and distilled water. The yields were calculated
from equation as follows (Eq. (2)):
were calculated MAC
Yieldð%Þ ¼  100 ð2Þ
Mprecursor
where MAC corresponds the mass of AC, and Mprecursor is the
initial mass of malt bagasse.
ð1Þ
The textural properties of porous material were evaluated
from N2 adsorption and desorption isotherms at 77 K using
a surface area and pore size analyzer Quantachrome, Nova
1200e. BET surface area (SBET) was calculated from the linear
fit of Brunauer-Emmett-Teller (BET) equation to the relative
pressure (p/p°) range of 0.05–0.20 in the adsorption branch.
The total pore volume (Vt) was considered the maximum
amount of N2 adsorbed at relative pressure of 0.99; while the
micropore volume (Vm) was estimated from deBoer method
and mesopore volume (Vm) via Barrett, Joyner and Halenda
method (Schneider, 1995). Finally, the average pore size
(Aps) was obtained from 4Vt/SBET equation and the pore size
distribution estimated via the Non-Local Density Functional
Theory (NLDFT) (Landers et al., 2013). The morphological
features of precursor and AC were evaluated from the images
obtained using a scanning electron microscope (SEM) Quan-
taTM FEG 250. All samples were metalized with gold to

Table 2 Experimental design with real and coded levels and the respective experimental responses values.
Run X1a (x1)b X2a (x2)b X3a (x3)b SBET (m2 g
1) 1/SBET (10
3) Yield (%)
1 660 (

1) 120 (+1) 160 (+1) 381 2.62 18.35
2 735 (0) 40 (
1.68) 120 (0) 406 2.46 19.56
3 735 (0) 90 (0) 120 (0) 584 1.71 13.97
4 735 (0) 90 (0) 187 (+1.68) 537 1.86 12.12
5 810 (+1) 60 (
1) 160 (+1) 676 1.50 15.16
6 810 (+1) 60 (
1) 80 (
1) 488 2.05 17.11
7 861 (+1.68) 90 (0) 120 (0) 661 1.51 11.94
8 735 (0) 90 (0) 120 (0) 530 1.89 13.39
9 660 (
1) 60 (
1) 160 (+1) 429 2.33 17.64
10 735 (0) 90 (0) 120 (0) 588 1.70 14.62
11 735 (0) 140 (+1.68) 120 (0) 320 3.13 18.58
12 660 (
1) 60 (
1) 80 (
1) 297 3.37 23.36
13 810 (+1) 120 (+1) 160 (+1) 671 1.49 11.84
14 660 (
1) 120 (+1) 80 (
1) 442 2.26 16.34
15 609 (
1.68) 90 (0) 120 (0) 389 2.57 18.68
16 810 (+1) 120 (0) 80 (
1) 795 1.26 6.39
17 735 (0) 90 (0) 53 (
1.68) 454 2.20 17.54
a, b
are the real and coded levels of temperature, time and N2/steam flow, respectively.
4 G.K.P. Lopes et al.

1
Table 3 Analysis of variance (ANOVA) of quadratic regression model for experimental responses SBET
and yield.
1 Yield
SBET

SQ DF MS F-value p-value SQ DF MS F-value p-value

6
7
Model 4.69  10 9 5.22  10 4.07 0.039 213.46 9 23.72 5.16 0.021
Residual 8.99  10
7 7 1.28  10
7 32.17 7 4.60
Lack of fit 8.77  10
7 5 1.75  10
7 16.14 0.059 31.41 5 6.28 16.59 0.058
Pure error 2.17  10
8 2 1.09  10
8 0.76 2 0.38
Total 5.59  10
6 16 245.63 16
R2 = 0.8395 C.V. (%) = 16.97 R2 = 0.8690 C.V. (%) = 13.67
M.E.V. = 99.61% Adeq. Precision = 7.05 M.E.V. = 99.69% Adeq. Precision = 8.61
SQ is the sum of squares; DF is the degrees of freedom; MS is the mean of square; M.E.V. is the maximum percentage explainable variation.

improve the conductivity. The pH in the point of zero charge
(pHpzc) of AC was estimated according to the methodology
described by Prahas et al. (2008), while the acidic and basic
groups of surface were quantified via Boehm titration
(Boehm, 1994).
2.4. Batch adsorption studies
Firstly, a stock solution of SY food dye (1000 mg L
1) was
prepared and stored for further dilution. To perform the
adsorption studies, 25 mg of ACMop was mixed with 25 mL
of SY solution and shaken in polypropylene tubes (50 mL of
total volume) at 200 rpm and 25 °C. After shaking, the ACMop
was separated from solution by vacuum filtration (Millipore
membrane of 0.45 mm) and the remaining SY concentration
in solution was determined spectrophotometrically at the max-
imum absorption wavelength of 482 nm, using an UV/Vis
spectrophotometer, Cary 50. The amount of SY adsorbed
per gram of ACMop for pH effect (Qm), in the equilibrium
(qe) and in time t (qt) were calculated from Eq. (3):
ðC0
Ce;t ÞV
Qm ¼ qe ¼ qt ¼
M
where C0 (mg L
1) is the initial concentration of SY solution;
Ce (mg L
1) is the SY remaining concentration remaining in
solution at equilibrium, Ct is SY concentration in solution at
the time t, M (g) is the mass of adsorbent and V (L) the volume
of solution.
The effect of solution pH was studied using SY solutions
with concentrations of 500 mg L
1 and pH values ranging of
and shown in the Table S1. The Gibbs free energy change
(DG) was calculated from equation displayed in Table S1,
while the enthalpy (DH) and entropy (DS) changes were deter-
mined from van’t Hoff equation (Table S1) by plotting lnK0e vs.
1/T.
The experimental data obtained from the equilibrium and
kinetic studies of adsorption were evaluated fitting on them,
nonlinear theoretical models (Table S1). To find the models
which best describe the experimental data, the values of deter-
mination coefficient (R2) and normalized standard deviation
(Dq) were considered. The models that showed the highest
R2 and lowest Dq values were considered the best ones to
describe the adsorption kinetic and isotherm curves. The Dq
(%) values were calculated from Eq. (4).
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uP h 
u ðq;exp
q;cal =q;exp 
2
t
q ¼ 100 ð4Þ
N
1
where N is the total number of experiments, qcal and qexp are
the calculated and experimental adsorption capacities in the
equilibrium (isotherms) or at each time t (kinetic curves),
ð3Þ respectively.
3. Results and discussion
3.1. Analysis of regression models and optimization
Table 2 presents the responses (SBET and yield), as well as
1
value of each activated carbon prepared from the condi-
SBET

3.0–11.0, which were adjusted with NaOH or HCl solutions
(0.10 mol L
1). The shaking time of solutions containing the
ACMop was of 4 h. The adsorption capacity values of SY
for pH study (Qm) were determined using Eq. (3). The adsorp-
tion kinetic study was carried out with initial concentrations of
100, 300 and 500 mg L
1 of SY in the optimum pH value, and
times ranging from 0 to 420 min. The adsorption capacities at
the time t (qt) were determined using the Eq. (3). The adsorp-
tion equilibrium study was performed at different tempera-
tures (298, 308, 318 and 328 K) with SY solutions of
concentrations ranging from 25 to 500 mg L
1 in optimal
pH values and shaking time of 4 h. The adsorption capacities
in the equilibrium (qe) were determined from the Eq. (3).
The thermodynamic parameters (DG, DH and DS) were
estimated using adsorption constant of the best isotherm
model, which was converted to dimensionless constant,
according to the equation described by Lima et al. (2019)
tions displayed in the experimental design. The SBET values
ranged from 297 (run 12) to 795 m2 g
1 (run 16), while the
yields were found in the range of 6.39 (run 16) and 23.36%
(run 12). These results demonstrate the antagonistic correla-
tion between SBET and yield responses. The oxidant conditions
and high temperatures, during the pyrolysis process, promote
the release of volatile matters and the oxidation of some
organic groups from the precursor; consequently, the porous
structures is developed and the yield values decrease (Reed
and Williams, 2004).
The significance of the model, main variables and their
interactions were evaluated from the analysis of variance
(ANOVA) at 95% confidence from Fisher test (F-value) and
p-values. The model is significant when F calculated (Fcal) is
higher than F tabulated (Ftab) for respective degrees of free-
dom. On the other hand, the lack of fit is non-significant for
Fcal < Ftab, considering the adequate degrees of freedom.
Steam-activated carbon from malt bagasse 5

Additionally, the parameter is significant if p < 0.05. Table 3
compiles the ANOVA of second-order models fitted to both
1 Fig. S1a and b present the predicted vs. experimental values
experimental responses (SBET and yield).
As can be seen from results obtained (Table 3), the second-
order model was significant for describing both responses with
1
Fcal values of 4.07 (SBET ) and 5.16 (yield), which are higher than
the tabulated values for the respective freedom degrees
(F9,7 = 3.68). Additionally, the p-values were 0.039 and
0.021, respectively; satisfying the condition of significance.
On the other hand, the data demonstrate the non-
1 randomness distribution of residuals, confirming that both
significance of the lack of fit. The value of Fcal for SBET response
was 16.14 and yield 16.59. The Ftab of respective freedom
degrees (F5,2) is 19.30, which is higher than those herein
reported; besides p-values are higher than 0.05 (0.059 and
0.058, respectively).
The determination coefficients (R2) for both second-order
1 of temperature (x1) and time (x2), interaction term of time
models (Table 4) were 0.8395 and 0.8690 for SBET and yield
2
responses, respectively. As important as the R value is the
maximum percentage of explainable variation (M.E.V.), which
was calculated from Eq. S1 (vide SI), and values were of
1
99.61% for SBET response and 99.69% for yield response. This
parameter indicates the real capacity of the model describes the
variance. Additionally, coefficients of variation (C.V.) and
adequate precision values of both models were determined
(Table 4). The C.V. measures the standard deviation percent-
age of the mean, i.e., it provides an analysis of dispersion,
and its acceptable range is between 0.5 and 13.5%
(Dastkhoon et al., 2017). The C.V. values herein determined
1
were 16.97% for SBET response and 13.67% for yield response.
Although the values are out of the optimum range (3.5% for
1
SBET
and 0.2% for yield), the adequate precision that measures
the signal-to-noise ratio was 7.05 for model build from SBET
response and 8.61 for yield (Table 3). It is reported a desirable
signal-to-noise ratio must be higher than 4 (Dastkhoon et al.,
Table 4 Monolayer adsorption capacity (Qm) of different
adsorbent materials applied on removal of SY from aqueous
solution.
Adsorbent Qm (mg Experimental Reference
g
1) conditions
2017), and the results herein obtained demonstrate that the
models are suitable to navigate in the design space.
of both responses studied. As shown, the values are distributed
close to best lines, indicating good correlation between the
data predicted and the results experimentally obtained. In
addition, Fig. S1c and d show the Normal plots and Studen-
tized plots of residuals of both responses. As can be seen,
the residuals had normal distributions throughout the normal
lines, while the Studentized plots (Fig. S1e and f) showed a
models are statistically significant.
The analysis of variance ANOVA for factors are shown in
Table S2 and S3. According to the results, the linear term of
temperature (x1) and quadratic term of time (x22) were signifi-
1
cant for response SBET (Table S2). Additionally, linear terms
and flow (x2x3), and quadratic term of time (x22) were signifi-
cant for response yield (Table S3). The regression models of
the responses excluded the non-significant terms and consider-
ing the coded levels are shown in the Eqs. (5) and (6):
1
¼ 1:79  10
3
4:49  10
4 x1 þ 3:13  10
4 x22 ð5Þ
SBET
yield ¼ 14:08
2:70x1
1:62x2 þ 1:88x2 x3 þ 1:61x22 ð6Þ
The model equations (Eqs. (5) and (6)) show the antagonist
behavior between linear terms and their interactions toward
the responses. In the Eq. (5), the negative coefficient of x1 indi-
cates that an increase in temperature results in a decrease of
1
SBET
, and consequently, in higher SBET values. This tendency
can be seen from the 3D-response surface displayed in
1 Fig. 1a. On the other hand, the positive coefficient of quadratic
term (x22 ) indicates that an increase in the time promote an
1
increase in the response (SBET ), resulting in a decrease of SBET.
The convex curvature of response surface (Fig. 1a) is associ-
ated with the significance of term x22 , demonstrating that SBET
values are obtained maintaining time in the region of central
point (minimum response is the vertex point of parabola).
The antagonism effect between temperature and time can be
understood from the mechanism of biomass activation with
steam, which is presented below (Bergna et al., 2020).
Cx ðH2 OÞ ! xCðsÞ þ yH2 O ð7Þ

Activated 199.7 55 °C; pH = 3.0; This work

C þ H2 O ! CO þ H2 DH ¼ 130:29 kJ mol
1 ð8Þ
carbon dads = 1.0 g L
1
Chitin 88.1 55 °C; pH = 4.0; Lima et al.
dads = 1.5 g L
1 (2019) CO þ H2 O ! CO2 þ H2 DH ¼
40:38 kJ mol
1 ð9Þ
Modified 93.3 55 °C; pH = 4.0; Lima et al.
chitin dads = 1.5 g L
1 (2019) C þ CO2 ! 2CO DH ¼ 170:67 kJ mol
1 ð10Þ
Mesoporous 204.1 25 °C; pH = 6.5 Ahmad et al.
carbon (2019) C þ 2H2 ! CH4 DH ¼
74:77 kJ mol
1 ð11Þ
Graphene 243.3 55 °C; pH = 6.0; Coros et al.
oxide dads = 0.5 g L
1 (2020) The enthalpy change (DH) values demonstrate the influence
Cu:ZnS-NPs- 85.4 25 °C; pH = 6.0 Agarwal of temperature in the gasification reactions. The positive DH
AC et al. (2016) values in Eqs. (8) and (10) suggest the need to perform the acti-
CaAl-LDH- 398.4 27 °C; pH = 4.0; Sá et al. vations under high temperatures to ensure a partial release of
NO3 dads = 1.0 g L
1 (2013) carbon element from precursors (as CO and CO2) and, conse-
Fe3O4- 22.31 25 °C; pH = 5.88; Cazetta et al. quently promoting the development of well-developed porous
activated dads = 1.0 g L
1 (2016)
structures. Although the conversion of the carbon from pre-
carbon
cursor into CO and CO2 is reported as a slow kinetic process
dads: adsorbent dosage. (Bergna et al., 2020), if the carbon precursor is maintained
6 G.K.P. Lopes et al.
1
Fig. 1 3D-surfaces of SBET (a–c) and yield (d–f) responses. The response surface is obtained by changing two variables and maintaining
the third at its central point.
by many hours under oxidant atmosphere at high temperature,
the lignocellulosic structure undergoes oxidation and high
amounts of ash are formed, which decreases significantly the
surface area. Moreover, extended time of pyrolysis may pro-
motes the collapse of pore walls, decreasing the surface area
(Chowdhury et al., 2013). In this sense, Fig. 1a demonstrates
that high temperatures and intermediary times can be a good
option to prepare steam-activated carbons with well-
developed surface area. Additionally, although the steam flow
factor does not have significant terms, as can be seen in Eq. (5)
and Fig. 1b and c, it is important to keep it at its high levels,
since the steam is an oxidant agent that promotes the release
of carbon monoxide and carbon dioxide, and acts as carrier
gas for these species outside the activation system.
The antagonistic behaviors of factors toward yield response
can be seen in Eq. (6). The coefficients of linear terms of tem-
perature (x1) and time (x2) have negative signals, suggesting
that highest response values are obtained maintaining factors
at lowest levels, as evidenced in the Fig. 1d. This behavior is
expected, since longer times of pyrolysis under high tempera-
tures enhance the ash formation (Bergna et al., 2020). On the
other hand, interaction term (x2 x3 ), and quadratic term (x22 )
presented positive coefficients in Eq. (6). The significance of
quadratic term for time (x22 ) indicates the presence of a maxi-
mum region of the response. Fig. 1f shows that the highest
yield values are obtained when both factors are kept at their
lowest levels. Additionally, while the linear term of time has
negative effect toward response, the quadratic term (x22 ) has
opposite one, which is associated with the positive character
of quadratic function. The maximum response (higher yield)
is not obtained in the vertex of parabola, but in the branch
of parabola associated with the lowest levels, as displayed in
the response surfaces of Fig. 1e and Fig. 1f.
The optimization the preparation conditions of AC from
malt bagasse has as aim to obtain a material with high SBET
and yield values. However, the results obtained show the
antagonistic effects of the factors toward the responses,
becoming difficult to determine the optimum condition from
the 3D-response surfaces. In this condition, desirability
Steam-activated carbon from malt bagasse
function (D), developed by Derringer and Suich, (1980) is a
suitable tool to help find the optimum condition. Desirability
values can range from 0 to 1, where D = 0 indicates the
response is outside an acceptable region, while D = 1 means
that response is at its goal or target condition. The numerical
optimization was performed maintaining all parameters in the
1 be evaluated from Fig. 2b. The NLDFT-based pore size distri-
range of studied values, aiming minimize the SBET response (and
consequently maximizing SBET response), while the yield was
target at 12%. The yield of 12% is commonly reported for
physical activation of lignocellulosic precursors (Fu et al.,
2020). The optimum condition with D = 1.00 was: tempera-
ture of 841 °C, activation time of 82 min and steam flow of
164 cm3 min
1, resulting in a SBET1
values of 1.00  10
3 and
yield of 12%. The confirmation experiment was performed
from the mentioned conditions and the responses for ACMop
were 1.09  10
3 (SBET = 917 m2 g
1) and 9.45%, respec-
tively; demonstrating the robustness of the models to predict
the responses. Although the yield presented high variation,
the precursor is a cellulose-rich material, which has low ther-
mal stability and undergoes decomposition at relatively low
temperatures (in the range of 230–310 °C) (Selvaraju et al.,
2018), resulting in the release of considerable fraction of car-
bon as CO and CO2 and therefore, affecting directly the yield
value.
3.2. Characterization of precursor and ACMop
Fig. 2a shows the N2 adsorption and desorption isotherms of
ACMop. As can be seen, the ACMop adsorbed high volume
of N2 at low relative pressures, indicating the presence of high
amount of micropores. The interaction forces in cavities with
small diameters are high because the walls of the pores are
close, generating an increase in the adsorbent-adsorbate inter-
action forces, resulting in high adsorption even at low relative
pressure values (Sing et al., 1985). According to the Interna-
tional Union of Pure and Applied Chemistry (IUPAC), the
N2 adsorption isotherm can be classified from its profile, and
Fig. 2a evidences a type IVa isotherm, characteristic of mate-
rials with micropores and mesopores, wherein the capillary
condensation is accompanied by hysteresis (Thommes et al.
2015). Similar profile of adsorption branch was also reported
by Son and Park, (2020) and Zhang et al., (2016), who pre-
Fig. 2 N2 adsorption and desorption isotherms at 77 K (a) and NLDFT-based pore size distribution (b) of ACMop.
7
pared AC from steam activation. From the desorption branch
of ACMop isotherm (Fig. 2a), it is identified the formation of
hysteresis with H4 profile, characteristic of slit-like pores that
can be found in AC with well-developed micro and meso-
porous structure (Sing et al. 1985; Thommes et al. 2015).
The presence of micro and mesoporous on the ACMop can
bution profile (Fig. 2b) shows the maximum number of pores
distributed around 1.8 nm, corroborating the predominance of
micropores on the ACMop surface. On the other hand, there is
a significant number of pores distributed in the range of 2.5–
4.0 nm, corresponding the region of mesopores.
The SBET value of ACMop was calculated from adsorption
branch of isotherm and it was of 917 m2 g
1, while the total
pore volume (Vt) was 0.53 cm3 g
1. The isotherm profile and
NLDFT-based pore size distribution suggested the predomi-
nance of micropores, which was confirmed from its volume
of 0.39 cm3 g
1, corresponding around 73% of the total vol-
ume. On the other hand, the significant contribution of meso-
porous identified in the Fig. 2b was confirmed from its value
estimated by BJH-based method, with a volume of 0.14 cm3
g
1. Furthermore, the average pore size of 2.2 nm comprises
the range of mesoporous materials (2–50 nm), confirming its
hybrid porosity (presence of micro and mesopores).
The physical activations are performed using CO2 or steam
as activating agents; while the former is responsible for the
development of porous structure consisting mainly of microp-
ores, the activation with steam results in materials with pores
distributed over a wide range of sizes. This characteristic of
steam can be seen in the work of Pena et al. (2020), who pro-
moted the activation of buckwheat husks and reported a Vm of
0.42 cm3 g
1 and Vm of 0.18 cm3 g
1, besides SBET of 997 m2
g
1. Bardestani and Kaliaguine (2018) also evaluated the
steam-activation of biochar and obtained SBET of 1025 m2
g
1, Vm of 0.43 cm3 g
1 and average pore size of 3.0 nm.
The morphology of precursor and ACMop were investi-
gated from SEM images, which are displayed in Fig. 3.
Fig. 3a–b present the SEM images of precursor, from which
it is possible to observe an irregular and rough surface, charac-
teristic of the structural arrangements of raw materials com-
monly used as precursors for preparation of ACs
(Yokoyama et al., 2019). After preparation process, the
ACMop obtained (Fig. 3c–d) showed a morphology of its
8 G.K.P. Lopes et al.
Fig. 3 SEM images of malt bagasse precursor (a–b) and ACMop (c–d).
surface with significant changes, increase in the heterogeneity
of particles, as well as formation of channels that can be asso-
ciated to the internal pores.
The chemical groups present over the ACMop surface were
quantified from Boehm titration. The total concentration of
acidic groups was 0.87 mmol g
1, which are distributed in phe-
nolics (0.18 mmol g
1) and carboxylic (0.69 mmol g
1) groups.
The concentration of total alkali groups was 0.08 mmol g
1,
indicating the presence of about 10-fold more acidic groups
than alkali ones. The predominance of acidic groups over
the surface of AC prepared via steam activation was also
reported by Bardestani and Kaliaguine (2018) and
Muthmann et al. (2020). The effect of these groups was evalu-
ated from pH in the point of zero charge, and graphic of the
solution pH before and after the contact with ACMop is shown
in Fig. S2. The Figure shows pHpzc of 3.92, corroborating with
the high concentration of acidic groups obtained from Boehm
titration. Klinghoffer et al. (2015) reported that carbonaceous
materials prepared under oxidant atmosphere deliver a large
number of active acidic sites.
3.3. Adsorption of SY dye onto ACMop
3.3.1. Solution pH effect
The solution pH is an important parameter in the adsorption
studies, since its change alters the charge distributions of the
adsorbate molecules and adsorbent surfaces. Therefore, the
pH study allows to evaluate the best experimental condition
in which the electrostatic interactions between the active sites
of ACMop and the chemical groups of SY molecule are
favored, and thus enhancing the adsorption capacity. Consid-
ering the pHpzc of 3.92 for ACMop (vide Fig. S2), it is possible
to infer that its surface has predominance positive charges for
solutions with pH < pHpzc, while that for solutions with
pH > pHpzc, its surface has predominance of negative charges.
Fig. 4 shows the adsorption capacity of ACMop, as well as
the distribution of SY species vs. the solution pH. SY is an azo
anionic dye that has sulfonic groups and pKa of 10.4 (Zhang
et al., 2020a; Floriano et al., 2018). The sulfonic groups are
responsible by high solubility of SY and for provide to it neg-
ative charges in solution over a large pH range. For solutions
with pH values higher than pKa value of dye can occur depro-
tonation of hydroxyl groups of SY molecules, and conse-
quently increase its density of negative charge. As can be
seen from Fig. 4, the maximum adsorption of SY onto ACMop
(qm = 156.77 mg g
1) was obtained at pH 3.0. In this pH, the
surface of ACMop is positively charged (since solution
pH < pHpzc), while sulfonic groups of SY show negative
charges, favoring the electrostatic interactions. Additionally,
it is possible to occurs hydrogen bonds between hydroxyl
groups of SY and surface groups of ACMop. From the condi-
tion that solution pH > pHpzc (pH = 4.0), the adsorption
capacity of ACMop decreased (vide Fig. 4) due to an enhance-
ment of repulsion between SY molecules charged negatively
and the negative surface of ACMop, remaining favorable only
the hydrogen bonds up to near pH = pKa condition. In the
region of pKa, the adsorption capacity decreased significantly
(qm around 100.00 mg g
1), since the hydroxyl group is depro-
tonated, enhancing the repulsion between SY molecules and
active sites of ACMop. Thus, the further adsorption studies
were carried out at pH 3.0.
3.3.2. Adsorption kinetic
The adsoprtion kinetic study of SY on the ACMop was carried
out with different initial dye concentrations (100, 300 and
500 mg L
1) and the experimental data were evaluated from
the nonlinear fits of pseudo-first order, pseudo-second order
Steam-activated carbon from malt bagasse
Fig. 4 Adsorption capacity of ACMop, as well as the distribu-
tion of SY species vs. the solution pH.
and Elovich models, and the adsorption mechanism from the
intraparticle diffusion model (vide Table S1). Fig. 5a–c show
the adsorption kinetic curves for three diferrent concnetra-
tions, from which it is possible to observe that equilibriums
are reached around 240 min. The kinetic parameters obtained
from the nonlinear fits are compiled in Table S4. According to
Fig. 5 Adsorption kinetic curves obtained from initial SY concentrations of 100 mg L
1 (a), 300 mg L
1 (b) and 500 mg L
1 (c), as well
as the nonlinear fits of pseudo-first order, pseudo-second order and Elovich models. The mechanism of adsorption was evaluated from the
linear fit of Weber and Morris intraparticle diffusion model (d).
9
the results, the models showed R2 values higher than 0.71 and
Dq values lower than 19.31%, which indicate good fits of all
them. Among the models fitted, the pseudo-first order model
was that showed the lowest R2 (from 0.7099 to 0.8730) and
highest Dq values (from 12.52 to 19.31%). The Lagergren
pseudo-first order kinetic model has been reported as suitable
to describes the initial interactions that occurs up to 20 or
30 min, and not the whole range of contact time (Gupta and
Bhattacharyya, 2011). The pseudo-second order kinetic model
showed better fit than the pseudo-first order model, with R2
ranging from 0.8616 to 0.9555 and Dq from 11.90 to 7.03%.
The pseudo-second order model has been interpreted as a spe-
cial kind of Langmuir kinetic, assuming the adsorbate concen-
tration constant in time and the total number of binding sites
depend of the amount of adsorbate adsorbed at equilibrium
(Gupta and Bhattacharyya, 2011). The Elovich model is that
better described the behavior of experimental data, showing
the highest values of R2 (0.9968; 0.9914 and 0.9813) and the
lowest values of Dq (4.56, 4.48 and 3.92). The Elovich model
assumes the solid surface as being energetically heterogeneous
and neither desorption nor interactions between adsorbed
molecules could affect the adsorption kinetic (Gupta and
Bhattacharyya, 2011). The a and b parameters of Elovich
equation are associated with initial adsorption rate and des-
orption rate, respectively. The values of both parameters
10
(Table S4) demonstrate the stability of ACMop–SY system,
since a values ranged from 32.72 to 53.54 g mg
1 min
2, while
b ranged from 0.04 to 0.08 mg g
1 min
1.
The adsorption mechanism was investigated from Weber
and Morris intraparticle diffusion model (Weber and Morris,
1963). The linear fits are shown in Fig. 4d, while the resulting
parameters are displayed in Table S5. From the results, it can
be seen a multilinear plot with three distinct regions for three
initial SY concentrations investigated. Additionally, it can be
inferred the intraparticle diffusion is not the rate-limiting step,
since the linear plots did not pass through the origin, as
demonstrated from Ci values of the first stage (C1 ranging from
11.19 to 28.28 mg g
1) (Mitrogiannis et al., 2015; Ronix et al.,
2017).
3.3.3. Equilibrium and thermodynamic of adsorption
The adsorption equilibrium is represented from the isotherms
that correlate the amounts of adsorbate adsorbed per gram
of adsorbent vs. the adsorbate concentrations into the bulk
solution. The equilibrium is reached when adsorbent and
adsorbate are in contact by sufficient time to establish a
dynamic balance between the concentration in the solution
bulk and interface concentration (Foo and Hameed, 2010).
Fig. 6 displays the adsorption isotherms of SY onto ACMop
in the temperatures of 25, 35, 45, and 55 °C, as well as the non-
linear fits of Langmuir, Freundlich and Redlich-Peterson mod-
Fig. 6 Adsorption isotherms obtained at temperatures of 25 °C (a), 35 °C (b), 45 °C (c) and 55 °C (d), as well as the nonlinear fits of
Langmuir, Freundlich and Redlich-Peterson models.
G.K.P. Lopes et al.
els. The experimental profiles of isotherms can be classified as
type H2, characteristics of adsorption processes with total
removal of adsorbate molecules for initial values of concentra-
tion, indicating good affinity between SY molecules and
ACMop surface (Giles et al., 1960).
The isothermal parameters determined from the nonlinear
fits of theoretical models to the experimental data are shown
in Table S6. As can be observed, models showed R2 values
higher than 0.90 and Dqe lower than 13.8%, suggesting they
fit well to the experimental data. The Langmuir model
describes monolayer adsorption over a surface with sites
energetically equivalents, where there is not lateral interac-
tion or steric hindrance between the adsorbed molecules,
even on adjacent sites (Vijayaraghavan et al., 2006; Foo
and Hameed, 2010). The fits of Langmuir model to the
experimental data obtained at temperatures of 25, 35, 45
and 55 °C resulted in R2 values ranging from 0.9026 to
0.9485, while Dqe were found in the range of 7.75–13.80%.
Although Langmuir model has not shown the better data
to describes the experimental data, it provides important
information about the adsorption process. The monolayer
adsorption capacity (Qm) of ACMop increased from 166.10
to 199.70 mg g
1, changing the temperature from 25 to
55 °C. Table 4 presents the SY maximum adsorption capac-
ities (Qm) and adsorption parameters of various adsorbent
materials, from which it is possible to see that Qm values
Steam-activated carbon from malt bagasse
of the ACMop are similar or higher than other materials
reported in the literature.
From the Langmuir model constants (KL), it is possible
estimate the Langmuir separation factor (RL) for each initial
SY concentration investigated in three temperatures. The RL
indicates the adsorption nature, where 0 < RL < 1 is associ-
ated with a favorable adsorption, while RL > 1 is characteris-
tic of an unfavorable adsorption, RL = 1 with a linear process
and RL = 0 an irreversible adsorption (Foo and Hameed,
2010; Spessato et al., 2020). From the graphs displayed in
Fig. S4a–d, it can be seen that separation factor ranged in
the interval between 0 and 1, evidencing the high affinity of
ACMop-SY system.
The fits of Freundlich model provided the better R2 and Dqe
values than those obtained for Langmuir model, with R2 val-
ues ranging of 0.9585–0.9788 and Dqe between 4.04 and
7.65%. Freundlich model is an empirical model that describes
multilayer adsorption over heterogeneous surfaces with non-
uniform distribution of adsorption heat and affinities
(Adamson and Gast, 1967; Foo and Hameed, 2010). From
the nF values, the adsorption intensity or surface heterogeneity
(1/nF) can be estimated. Its value can range between 0 and 1,
and the surface becomes more heterogeneous for 1/nF values
closer to zero. The 1/nF values were found in the range of
0.15–0.18, indicating a high degree of heterogeneity of ACMop
surface (Haghseresht and Lu, 1998; Foo and Hameed, 2010).
Redlich-Peterson model showed the best fit to the experi-
mental data, with highest R2 (0.9886–0.9946) and lowest Dqe
(1.62–2.70) values (vide Table S6) Redlich-Peterson model
has three parameters, which feature both Langmuir and Fre-
undlich assumptions. The exponent g can assume values in
the range of 0–1, where in the limit of g ? 0, the model
approaches to Freundlich model and Henry’s law. On the
other hand, g close to 1 indicates ideal condition of Langmuir
predictions (Foo and Hameed, 2010; Brdar et al., 2012). From
the g values (0.85–0.90), the fits of Redlich-Peterson model evi-
dences that adsorption of SY onto ACMop is better described
by Langmuir assumptions.
Considering the results obtained from the fits of Redlich-
Peterson model, the KL values from Langmuir equation were
used to calculate the dimensionless K0e constant and estimate
the thermodynamic parameters. The van’t Hoff equation plot
(lnK0e vs. 1/T) and thermodynamic parameters are shown in the
Fig. S5 and Table S7, respectively. According to the results,
the DG showed negative values, ranging from
42.83 to

47.56 kJ mol
1, which indicates the spontaneity of SY
adsorption onto ACMop. Additionally, the adsorption process
is considered endothermic, since the determined DH was
4.07 kJ mol
1, corroborating with Qm values that increase with
the increasing the temperature (vide Table S6). Delle Site,
(2001) reported that the energies of interactions during adsorp-
tion process are associated with van der Waals interactions (4–
8 kJ mol
1), hydrophobic bond (4 kJ mol
1), hydrogen bond
(2–40 kJ mol
1), charge transfer, ligand-exchange and ion
bonding (40 kJ mol
1), direct and induced ion–dipole and
dipole–dipole interactions (2–29 kJ mol
1), and chemisorption
(covalent bond) (60–80 kJ mol
1). The DH value
(4.07 kJ mol
1) suggests that different interactions play signif-
icant role in the SY adsorption onto ACMop. Additionally, the
DH was of 157.38 J K
1 mol
1, indicating an increase of ran-
domness on the liquid/solid interface.
11
4. Conclusion
Activated carbon from malt bagasse was successfully prepared
via physical activation with steam. The optimization of exper-
imental parameters involved in its preparation (via experimen-
tal design, Response Surface Methodology and Desirability
Function) showed the influence of the temperature on the SBET
value, and the influence of activation time and temperature on
the yield. The activated carbon obtined in the optmized condi-
tions (ACMop) showed well-developed BET surface area
(917 m2 g
1) and yield of 9.45%. Additionally, the ACMop
showed high concentration of acidic groups on its surface,
which was confirmed by its pHpzc (3.92). The efficiency of
ACMop on removal of sunset yellow food dye (SY) from aque-
ous solution was successuful investigated. Kinetic study demo-
strates the fast removal of SY for ACMop, being the
equilibrium reached around 240 min. Additionally, it showed
that intraparticle diffusion is not the rate-determinining step;
while the isotherms obtained from different temperatures
demostrated the dependence between the monolayer adsorp-
tion capacity and temperature. Finally, the thermodinamic
parameters confirmed the spontaneity of SY adsorption onto
ACMop (DG < 0), although the interactions between SY mole-
cules and ACMop active sites are improved by increases the
temperature (DH > 0). These results demonstrates the poten-
tial of malt bagasse as a highly-available and environmentally-
friendly precursor for preparation of steam-activated carbon
to be applied on removal of organic molecules from aqueous
solution.
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.
Acknowledgements
The authors acknowledge the Coordenação de Aperfeiçoa-
mento de Pessoal de Nı́vel Superior (CAPES–Brazil), Con-
selho Nacional de Desenvolvimento Cientı́fico e Tecnológico
(CNPq–Brazil) and Fundação Araucária (Brazil) for the finan-
cial support (fellowships). V.C.A. would also acknowledge the
CNPq for his research project (Grant Number: 426890/2016-
7).
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.arabjc.2021.103001.
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