Journal of Molecular Liquids 268 (2018) 365–370

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Journal of Molecular Liquids

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

Electrospun chitosan/poly(ethylene oxide) nanofibers applied for the

removal of glycerol impurities from biodiesel production by biosorption
Bruna Silva de Farias, Évelin Mendes Vidal, Natália Torres Ribeiro, Nauro da Silveira Jr., Bruna da Silva Vaz,
Suelen Goettems Kuntzler, Michele Greque de Morais,
Tito Roberto Sant'Anna Cadaval Jr., Luiz Antonio de Almeida Pinto ⁎
School of Chemistry and Food, Federal University of Rio Grande (FURG), km 8 Itália Avenue, 96203-900 Rio Grande, RS, Brazil

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

Article history: Electrospun chitosan/poly(ethylene oxide) nanofibers were synthetized, characterized and applied as alternative
Received 13 February 2018 biosorbents to remove pigments from pretreated crude glycerol. The pigments removal efficiency of electrospun
Received in revised form 5 July 2018 nanofibers was examined by comparing the adsorption capacity of nanofibers with other chitosan–based
Accepted 18 July 2018
biosorbents. Pseudo–first order, pseudo–second order and Elovich models were used to estimate kinetic parameters.
Available online 19 July 2018
The nanofibers exhibited continuous fibers, with the average fibers diameter of 526 ± 101 nm. The results also in-
Keywords:
dicated interactions between chitosan and poly(ethylene oxide) molecules, without changing the main adsorptive
Biomaterial sites of chitosan. Furthermore, chitosan/poly(ethylene oxide) nanofibers exhibited higher relative adsorption capac-
Biosorption ity (120 g−1) than chitosan powder (35 g−1) and chitosan biopolymeric film (58 g−1). The pseudo–first order and
Glycerol purification Elovich models were the most suitable models to represent the kinetic behavior of the composite nanofiber.
Nanomaterial © 2018 Elsevier B.V. All rights reserved.

1. Introduction Chitosan is a biopolymer composed by 2–acetamido–2–deoxy–β–D–

Biodiesel has been gaining attention because it can be manufactured
by renewable and low-cost raw materials. Transesterification is the most
common method for biodiesel production. The process comprises a chem-
ical reaction between a fatty acid (fat or oil) and a short chain alcohol
(methanol or ethanol), in the presence of an acid or basic catalyst. Glycerol
is a by-product of the reaction, and each kilogram of biodiesel produces
0.10 kg of glycerol. This crude glycerol contains several compounds, such
as esters, alcohol, salts, glycerides and pigments [1–3]. While crude glyc-
erol has limited applications because of its impurities, pure glycerol has
a huge market in pharmaceutical, food and chemical products [4].
Traditionally, crude glycerol purification involves three steps. The first
step is performed by neutralization reaction, which removes some salts
and free fatty acids. The second step occurs by evaporation, whereby alco-
hol is removed. The third step is the refining, which allows achieving the
desired degree of purity, reducing even more the color, fatty acids and
traces of other components. Among the techniques that can be applied
in the last step, adsorption is recognized as an economical and efficient
operation to remove organic molecules from aqueous solution [5, 6].
However, only activated carbon has already been applied to drastically re-
duce the pigments compounds from crude glycerol [7–9].
⁎ Corresponding author.
E-mail address: dqmpinto@furg.br (L.A. de Almeida Pinto).
glucopyranose and 2–amino–2–deoxy–β–D–glucopyranose residues,
which is produced by partial deacetylation of chitin. Among the proper-
ties of chitosan, its polycationic character stands out for biosorption appli-
cations [10, 11]. In fact, a variety of chitosan–based biosorbents has been
efficiently applied to remove pigments from food and textile dyes
[12–16]. Moreover, it is well established that enhancing specific surface
area of an adsorbent results in higher adsorption capacity, so the develop-
ment of chitosan–based nanomaterials can improve its characteristics [17,
18]. This objective can be obtained via electrospinning, which is one of the
most versatile and promising techniques for generating continuous and
ultrathin nanofibers [19–21]. The electrospun nanofiber has also the ad-
vantages of a bulk material, which allows the separation of the adsorbent
from solution [22, 23]. However, chitosan is considered a challenging bio-
polymer to electrospun due to its complex chemical structure [24]. In fact,
the addition of other polymers such as poly(ethylene oxide) (PEO) can
enhance the spinnability of chitosan by wrapping and unwinding the
polysaccharide chains, which facilitates flow and orientation of chitosan
molecules [25–27].
However, there were not cited works in the literature reporting the
use of biomaterial in nanoscale to adsorb impurities from the glycerol.
Thus, the aim of this study was to synthesize and characterize
electrospun chitosan/poly(ethylene oxide) nanofibers (CP–EN) for
biosorption of pigments from pretreated industrial glycerol. The CP–
EN were characterized by scanning electron microscopy (SEM), Fourier
transform infrared spectroscopy (FT–IR), thermogravimetric analysis

https://doi.org/10.1016/j.molliq.2018.07.081
0167-7322/© 2018 Elsevier B.V. All rights reserved.
366 B.S. de Farias et al. / Journal of Molecular Liquids 268 (2018) 365–370
(TGA), differential thermal analysis (DTA) and differential scanning cal-
orimetry (DSC). Furthermore, the pigments removal efficiency of CP–EN
was examined by comparing the adsorption capacity of CP–EN with
other conventional chitosan physical forms (powder and biopolymeric
film). The kinetic study was obtained by using the pseudo–first order
(PEO), pseudo–second order (PSO) and Elovich models.
2. Material and methods
2.1. Materials
Chitosan in powder (CH–P) (molecular weight (MW) = 150.3 ±
1.4 kDa; deacetylation degree (DD) = 85.2 ± 1.1%; particles size (PS)
= 100 ± 10 μm) was obtained from shrimp wastes (Penaeus
brasiliensis). The shrimp wastes went through the steps of deminerali-
zation, deproteinization and deodorization. Then, deacetylation reac-
tion was performed followed by the purification and drying steps,
according to our previous works [28, 29]. Poly(ethylene oxide) powder
(PEO–P) (MW = 900 ± 5.5 kDa) was purchased from the Sigma–Al-
drich (Sigma-Aldrich®, USA). The industrial pretreated glycerol (pH of
4.6 ± 0.1, yellowness index of 15.0 and redness index of 7.5) was ob-
tained from a local biodiesel production plant in Brazil. The industrial
pretreatment of the crude glycerol aimed to remove salts, free fatty
acids, catalyst and methanol by neutralization and vacuum distillation.
2.2. Development of chitosan biopolymeric films
The filmogenic solution was obtained by dissolving CH–P (1.5 g) into
50 mL of acetic acid solution (0.1 mol L−1) at 25 ± 1 °C, under magnetic
stirring (300 rpm) (Fisatom, 752, São Paulo, SP, Brazil) for 12 h. The so-
lution was poured onto a level Plexiglas plate, and then, the chitosan
biopolymeric films (CH–F) were obtained by solvent evaporation in an
oven, with air circulation at 40 ± 2 °C for 24 h [29, 30].
2.3. Development of electrospun nanofibers
Firstly, CH–P (5% w/v) was dissolved in acetic acid (90% v/v) and, then,
PEO–P (3% w/v) was added into the solution. The polymeric solution was
prepared at 25 ± 1 °C under magnetic stirring (300 rpm) (Fisatom, 752,
São Paulo, SP, Brazil). The complete mixing was achieved in 12 h. The chi-
tosan/poly(ethylene oxide) nanofiber (CP–EN) were produced using
electrospinning technique. Briefly, the solution was transferred into a cap-
illarity, and electrospun under the capillary diameter, capillarity–collector
distance, electric potential and feed rate of 0.55 mm, 150 mm, 25 kV and
600 μL h−1, respectively (based on preliminaries tests). The nanofiber
synthesis was carried out at 25 ± 1 °C and relative humidity of 65 ± 1%.
2.4. Characterization of the nanofibers
The diameter of the nanofibers and the surface morphology of CP–
EN, prior and after biosorption process, were obtained by scanning elec-
tron microscope (SEM) (JEOL, JSM–6610, Akishima–shi, Tokyo, Japan).
The analysis was operated at 10 kV, with different magnifications.
Prior to SEM imaging, the samples were placed on stainless steel sup-
ports and coated with 1 nm of gold layer [31]. The average fibers diam-
eter was calculated by the randomly selected diameter of 50 nanofibers
from each sample.
Differential scanning calorimetry (DSC) analysis (Shimadzu, DSC–
60, Nakagyo–ku, Kyoto, Japan) was carried out to analyze endothermic
and exothermic structural transitions of the materials. Approximately,
3 mg of each sample (CH–P, PEO–P and CP–EN) were weighted in an
aluminum pan hermetically sealed. The tests were performed under a
nitrogen atmosphere (50 mL min−1) from 25 °C to 275 °C, with a
heating rate of 10 °C min−1 [32].
The thermal stability of the samples was evaluated by thermogravi-
metric analysis (TGA) and differential thermal analysis (DTA),
simultaneously (Shimadzu, DTG-60, Nakagyo–ku, Kyoto, Japan) [33].
The thermal study was performed by weighing 3 mg of each sample
(CH–P, PEO–P and CP–EN) in an aluminum pan. The analysis was car-
ried out from 25 °C to 500 °C under a nitrogen atmosphere (30 mL
min−1) at a heating rate of 10 °C min−1.
The functional groups, as well as possible structural changes on the
nanofibers surface, were characterized by Infrared analysis (FTIR) with
attenuated total reflectance (Shimadzu, Prestige 21, Nakagyo–ku,
Kyoto, Japan). In order to identify the functional groups involved in
the biosorption process, the CP–EN were also evaluated after the
biosorption of glycerol pigments. The samples (CH–P, PEO–P and CP–
EN) were submitted to the spectroscopic determination at 20 °C, with
wavenumber in the range from 500 to 4000 cm−1 [34].
2.5. Equilibrium study
The equilibrium biosorption study was performed with different
physical shape of chitosan–based biosorbents (CH–P, CH–F and CP–
EN). The assays were carried out in a thermostatic shaker (Fanem, 315
SE, São Paulo, SP, Brazil) with the following conditions: biosorbent dos-
age of 250 mg kg−1 and temperature of 60 ± 1 °C. Aliquots were mea-
sured when the equilibrium was reached. The pigments removal was
detected by UV–visible spectrophotometry (Shimadzu, UV–2550,
Nakagyo–ku, Kyoto, Japan), with a wavelength of 265 nm. All assays
were performed in triplicate (n = 3). The amount of pigments
adsorbed, qe (g−1), is presented by Eq. (1):
mo −m f
qe ¼ ð1Þ
mad
where mo and mf (g) are, respectively, the amounts of glycerol pigments
in the initial and after the equilibrium, and mad (g) is the amount of
adsorbent.
Even though the types of pigments present in glycerol are not
known, the pigments can still be quantified using a relative adsorption
capacity (qr) (Eq. (2)), associated to Lambert–Beer law (Eq. (3)) [35].
mo −m f
qr ¼ ð2Þ
mad mo
A
m ¼ CV ¼ Vf ð3Þ
εc
where A is the glycerol pigments absorbance, ԑc is a constant, which de-
pends on analyte nature, as well as of cuvette size, V is the volume and f
is the dilution factor.
The insertion of Eq. (3) into Eq. (2) leads to Eq. (4).
 
1 Ae
qre ¼ 1− ð4Þ
mad A0
where qre (g−1) is the equilibrium relative adsorption capacity, Ao and
Ae are, respectively, the initial and equilibrium pigments absorbances.
2.6. Kinetic study
The biosorption kinetic assays were also executed with different
physical shape of chitosan–based biosorbents (CH–P, CH–F and CP–
EN). The assays were conducted in a jar–test (Nova Ética, 218 MBD,
SP, Vargem Grande Paulista) with the following conditions: biosorbent
dosage of 250 mg kg−1 and temperature of 60 ± 1 °C. Aliquots were
measured at predetermined time intervals (from 0 to 3600 s). The pig-
ments removal was detected by UV–visible spectrophotometry
(Shimadzu, UV–2550, Nakagyo–ku, Kyoto, Japan), with a wavelength
of 265 nm. All assays were performed in triplicate (n = 3). The amount
 B.S. de Farias et al. / Journal of Molecular Liquids 268 (2018) 365–370 367

Fig. 1. Photograph of electrospun chitosan/poly(ethylene oxide) nanofibers: (a) before biosorption process; (b) after biosorption process.

of pigments adsorbed at each time, qr (g−1), is shown in Eq. (5): The Elovich model (Eq. (8)) is based between PFO model and
intraparticle diffusion model.
 
1 At
qr ¼ 1− ð5Þ
mad A0 1
qr ¼ ln ð1 þ αbtÞ ð8Þ
α
where Ao and At are, respectively, the pigments absorbance at initial and
at predetermined time intervals. where α (g) is the initial velocity due to dq/dt with qr = 0, b (g−1 s−1) is
The pseudo–first order (PFO), pseudo–second order (PSO) [36] and the desorption constant of the Elovich model.
Elovich [37] models were fitted to the experimental data, to verify the
adsorption kinetic behavior, by nonlinear Quasi–Newton estimation 3. Results and discussion
method (Statistic 7.0, Statsoft, USA).
The PFO (Eq. (6)) and PSO (Eq. (7)) models are based in the relative 3.1. Characterization of the nanofibers
adsorption capacity.
Fig. 1 shows the macroscopic nature of CP–EN before and after
biosorption process.
qr ¼ q1 ð1− expð−k1 tÞÞ ð6Þ
Electrospun chitosan/poly(ethylene oxide) nanofibers prior to
biosorption process (Fig. 1(a)) were easy to handle, with white to
t
qr ¼   ð7Þ creamy color; in addition, the CP–EN have demonstrated smooth and
1 t homogenous surface. Nevertheless, the nanofiber after biosorption pro-
ð þ
k2 q22 q2 cess (Fig. 1(b)) revealed a dense structure, brightness and heteroge-
neous surface, with yellow to orange color, which can be related to
where k1 (s−1) and k2 (g s−1) are the rate constants of PFO and PSO the glycerol pigments adsorbed over nanofiber structure.
models, respectively, q1 (g−1) and q2 (g−1) are the theoretical values The morphology of electrospun chitosan/poly(ethylene oxide) nanofi-
for the relative adsorption capacity. bers (CP–EN) before and after biosorption process is shown in Fig. 2.

Fig. 2. SEM images of electrospun chitosan/poly(ethylene oxide) nanofibers (CP-EN) before biosorption: (a) ×500; (b) ×5,000 and, after biosorption of glycerol pigments: (c) ×500; (d)
×2,500.
368 B.S. de Farias et al. / Journal of Molecular Liquids 268 (2018) 365–370
Fig. 3. DSC analysis: (a) electrospun chitosan/poly(ethylene oxide) nanofibers (CP–EN),
(b) chitosan powder (CH–P) and (c) poly(ethylene oxide) powder (PEO–P).
The SEM images (Fig. 2(a, b)) demonstrated that the electrospun
nanofibers were continuous and beadles, with average fibers diameter
of 526 ± 101 nm. The CP–EN also exhibited branched fibers, in which
instabilities in the primary jet led to the formation of branches over
the fibers [38]. Moreover, CP–EN morphology has significantly changed
after biosorption of glycerol pigments. The structure modification can
be attributed to the swelling behavior of CP–EN caused by the mass
transfer of glycerol into nanofiber structure.
The thermal profiles are shown in Figs. 3, 4 and 5, respectively, DSC,
TGA and DTA curves for the samples of CP–EN, CH–P and PEO–P.
The DSC curve of the CP–EN (Fig. 3(a)) showed an endothermic peak
at 53 °C, which can be related to evaporation of adsorbed water in TGA
curve (Fig. 4(a)) between 25 and 60 °C, with maximum evaporation
rate (Temax) in DTA curve (Fig. 5(a)) at 52 °C.
Fig. 3(a), DSC curve of the CP–EN, also pointed out an endothermic
peak at 113 °C. However, it was not observed any amount of weight
loss on TGA curve (Fig. 4(a)) in this temperature range (from 75 to
175 °C). Therefore, this fact can be attributed to the melting point of
PEO, in which the peak was shifted toward a temperature higher than
the melting point of PEO–P (72 °C) (Fig. 3(c)). Furthermore, the melting
enthalpy related to PEO (ΔHm) in the CP–EN (41.3 J g−1) decreased
when compared to neat PEO–P (183.8 J g−1). This can be associated to
the reduction of spherical semicrystalline regions of PEO caused by the
increment of chitosan; in addition to the high evaporation rate of the
Fig. 4. TGA analysis: (a) poly(ethylene oxide) powder (PEO–P), (b) chitosan powder (CH–
P) and (c) electrospun chitosan/poly(ethylene oxide) nanofibers (CP–EN).
Fig. 5. DTA analysis: (a) electrospun chitosan/poly(ethylene oxide) nanofibers (CP–EN),
(b) chitosan powder (CH–P) and (c) poly(ethylene oxide) powder (PEO–P).
solvent in the electrospinning technique, which may limit the complete
formation of the crystals [39, 40].
The plot also shifted upward over a temperature range (from 125 to
137 °C) in the DSC curve of the CP–EN (Fig. 3(a)). The onset of the step
could be associated with the glass transition of chitosan, which enables
the mobility among amorphous polymer networks. Indeed, a similar
change in inclination of the baseline also appeared in the DSC curve of
CH–P (Fig. 3(b)), however, the peak was slightly shifted toward a
lower temperature range (from 110 to 121 °C).
The maximum degradation rates (Tdmax) of CH–P, PEO–P and CP–EN
were found in the DTA curves (Fig. 5). Tdmax of CH–P was obtained at
365 ± 1 °C, while Tdmax of PEO–P was at 425 ± 1 °C. Tdmax of CP–EN
showed both degradation steps related to chitosan and PEO at 348 °C
and 412 °C, respectively, with a slight change in the temperature. The
thermal characteristics shifting of the pure chitosan and PEO when com-
pared to chitosan/PEO nanofiber suggests the interaction between chi-
tosan and PEO molecules, thereby altering thermal properties of the
polymers.
The FTIR spectra of CH–P, PEO–P and CP–EN are shown in Fig. 6.
The FTIR spectrum of CP–EN (Fig. 6(a)) pointed out the
characteristic bands of chitosan (Fig. 6(b)). The bands at 3319 and
3188 cm−1 are related to the N\\H and O\\H stretching vibration. The
band at 1660 cm−1 is due the stretching vibration of C_O from the
amides. Moreover, C\\O\\H deformation was identified at 1413 cm−1.
Fig. 6. FTIR Spectroscopy analysis: (a) electrospun chitosan/poly(ethylene oxide)
nanofibers (CP–EN), (b) chitosan powder (CH–P) and (c) poly(ethylene oxide) powder
(PEO–P).
 B.S. de Farias et al. / Journal of Molecular Liquids 268 (2018) 365–370 369

The FTIR spectrum of CP–EN also detected some typical PEO bands (Fig.
6(c)). The band at 2876 cm−1 is attributed to \\CH2 stretching. The
bands assigned to C\\O\\C stretching vibration were observed at
1085 and 950 cm−1. In summary, the FTIR spectrum identified impor-
tant adsorptive sites,\\NH2 and\\OH groups, which belong to chitosan
[10, 41]. Furthermore, the addition of PEO did not shift the peak of the
hydroxyl and amine groups, besides to insert other functional groups
in nanofiber structure.
Fig. 7 shows the FTIR spectra of CP–EN before and after biosorption
process. In fact, the analysis highlights some important changes. The
comparison between Fig. 7(a) and (b) allowed to identify a great reduc-
tion in the bands at 3309 and 3188 cm−1, which could suggest that
\\NH2 and \\OH groups acted as adsorptive sites over biosorption of
glycerol pigments.

3.2. Biosorption equilibrium

The potential of CP–EN for pigments removal from glycerol was

evaluated and compared with the other chitosan–based biosorbents.
The equilibrium relative adsorption capacities (qre) for CP-EN, CH–P
and CH–F were, respectively, 120.0 ± 6.0, 35.1 ± 4.2, and 58.1 ± 4.2
g−1. The great difference in the relative adsorption capacity of CP–EN
could be attributed to the enhanced surface area available for
biosorption, as a result of chitosan on nanoscale, which promoted
more protonated amino groups (pKa ~6.3) being occupied by glycerol
pigments under acid conditions (glycerol pH of 4.6 ± 0.1). Furthermore,
the higher relative adsorption capacity of CP–EN can also be associated
with the interactions between chitosan and PEO functional groups. The
decreasing in the intermolecular distance among their molecules can in-
crease the adsorptive sites over the internal pore structure of the nano-
fibers, which allows a deeper migration of glycerol pigments.
3.3. Biosorption kinetics
Fig. 8 shows the adsorption kinetic curves for glycerol pigments onto
CP–EN, CH–F and CH–P.
For all chitosan–based biosorbents, the kinetic curves pointed out
that the adsorption rate (dqr/dt) occurred quickly at the first 60 s of op-
eration, reaching approximately 70, 90 and 60% of saturation for CP–EN,
CH–F and CH–P, respectively. Then, the adsorption rate started to slow
down until the biosorbents achieved the equilibrium adsorption around
0.5 h of process.
For further comprehension about glycerol pigments adsorption onto
chitosan–based biosorbents (CP–EN, CH–P and CH–F), pseudo–first
order (PFO), pseudo–second order (PSO) and Elovich models were
Fig. 8. Kinetic curves for biosorption of glycerol pigments onto (■) electrospun chitosan/
poly(ethylene oxide) nanofibers (CP–EN), (●) chitosan biopolymeric films (CH–F) and
(▲) chitosan powder (CH–P).
fitted to the experimental data. The kinetic parameters results are pre-
sented in Table 1. The lowest value of average relative error (ARE) asso-
ciated to the highest value of the coefficient of determination (R2)
indicate which model was the most suitable to represent biosorption
of glycerol pigments onto chitosan–based biosorbents.
The PSO and Elovich were the most appropriate models for CP–EN
and CH–F, while PFO and PSO were for the CH–P. The PSO and Elovich
models suggest that chemisorption might be the rate controlling mech-
anism through biosorption of glycerol pigments using CP–EN and CH–F
biosorbents. Probably, in the glycerol acid medium, the amino groups of
chitosan became protonated, as well as, part of adsorbate dissociated
into anionic ions, then the biosorption proceeded due to ion–exchange.
On the other hand, for CH–P biosorbent, the PFO and PSO models may
indicate that physical and chemical interactions occurred
simultaneously.
4. Conclusion
Electrospun chitosan/poly(ethylene oxide) nanofibers (CP–EN)
were successfully synthetized for biosorption removal of pigments
from industrial pretreated glycerol. The CP–EN presented continuous fi-
bers. The thermal profiles of the nanofibers showed alterations when
compared to pure polymers, which could suggest the interactions

Table 1
Kinetic parameters for the biosorption of glycerol pigments onto chitosan–based
biosorbents (CP–EN, CH–P and CH–F).

Biosorbent

CP–EN CH–P CH–F

Pseudo-first order
q1 (g−1) 116.16 ± 11.61 35.47 ± 4.81 56.35 ± 5.63
k1 × 10−2 (s−1) 2.58 ± 0.01 1.79 ± 0.16 13.24 ± 0.01
R2 0.99 ± 0.01 0.99 ± 0.01 0.99 ± 0.01
ARE (%) 4.28 ± 0.12 4.34 ± 0.24 2.59 ± 0.07

Pseudo-second order
q2 (g−1) 118.07 ± 11.8 36.98 ± 5.26 57.49 ± 5.76
k2 × 103 (g−1 s−1) 73.53 ± 24.34 1.36 ± 0.94 64.06 ± 21.21
R2 0.99 ± 0.01 0.99 ± 0.01 0.99 ± 0.01
ARE (%) 1.40 ± 0.37 3.37 ± 0.65 1.52 ± 0.09

Elovich
α × 10−2 (g) 9.96 ± 0.90 25.16 ± 1.66 50.66 ± 5.81
b × 10−7 (g−1 s−1) 477.00 ± 47.69 18.21 ± 19.09 640.92 ± 288.13
Fig. 7. FTIR Spectroscopy analysis: (a) electrospun chitosan/poly(ethylene oxide)
R2 0.99 ± 0.01 0.97 ± 0.01 0.99 ± 0.01
nanofibers (CP–EN) before biosorption process; (b) electrospun chitosan/poly(ethylene
ARE (%) 2.64 ± 0.18 7.47 ± 0.72 1.03 ± 0.15
oxide) nanofibers (CP–EN) after biosorption process.
370 B.S. de Farias et al. / Journal of Molecular Liquids 268 (2018) 365–370
between chitosan (CH) and poly(ethylene oxide) (PEO) molecules. The
CP–EN also remained with the main reactive functional groups of chito-
san. Moreover, CP–EN demonstrated higher relative adsorption capacity
(120 g−1) than the chitosan powders (CH–P) of 35 g−1 and the chitosan
films (CH–F) of 58 g−1. These results reveal the potential of chitosan to
adsorb pigments from glycerol, demonstrating the impact of the nano-
scale into chitosan–based nanofibers. Furthermore, the kinetic curves
evidenced that adsorption rate (dqr/dt) reached more than 50% of satu-
ration in the first minute of operation for all chitosan–based biosorbents
(CP–EN, CH–F and CH–P). The PSO and Elovich models were the most
suitable to represent kinetic behavior of the CP–EN, which could indi-
cate that chemical interactions were predominant in the biosorption
of glycerol pigments onto nanofibers. Therefore, this study brings a
new nanobiomaterial, which can be a potential biosorbent to adsorb im-
purities from industrial glycerol as a green and efficient alternative.
Declarations of interest
None.
Acknowledgements
The authors would like to thank CAPES (Brazilian Agency for Im-
provement of Graduate Personnel) and CNPQ (National Council of Sci-
ence and Technological Development) for the financial support.
References
[1] J. Chen, S. Yan, X. Zhang, R.D. Tyagi, R.Y. Surampalli, J.R. Valério, Waste Manag. 71
(2018) 164–175.
[2] M. Hájek, F. Skopal, Bioresour. Technol. 101 (2010) 3242–3245.
[3] M.F. Milazzo, F. Spina, A. Vinci, C. Espro, J.C.J. Bart, Renew. Sust. Energ. Rev. 18 (2013)
350–389.
[4] M. Pagliaro, M. Rossi, The Future of Glycerol, second ed. RSC Publishing, Cambridge,
2010.
[5] M.S. Ardi, M.K. Aroua, N.A. Hashim, Renew. Sust. Energ. Rev. 42 (2015) 1164–1173.
[6] R.S. Pohndorf, T.R.S. Cadaval Jr., L.A.A. Pinto, J. Food Eng. 185 (2016) 9–16.
[7] R. Dhabhai, E. Ahmadifejani, A.K. Dalai, M. Reaney, Sep. Purif. Technol. 168 (2016)
101–106.
[8] M. Hunsom, C. Autthanit, Chem. Eng. J. 229 (2013) 334–343.
[9] R. Manosak, S. Limpattayanate, M. Hunsom, Fuel Process. Technol. 92 (2011) 92–99.
[10] G. Crini, P.M. Badot, Prog. Polym. Sci. 33 (2008) 399–447.
[11] G.L. Dotto, S.P. Campana-Filho, L.A.A. Pinto, Frontiers in Biomaterials, first ed. Ben-
tham Science Publishers, Sharjah, 2017.
[12] V.M. Esquerdo, T.R.S. Cadaval Jr., G.L. Dotto, L.A.A. Pinto, J. Colloid Interface Sci. 424
(2014) 7–15.
[13] J.O. Gonçalves, J.P. Santos, E.C. Rios, M.M. Crispim, G.L. Dotto, L.A.A. Pinto, J. Mol. Liq.
225 (2017) 265–270.
[14] V.S. Munagapati, V. Yarramuthi, D.S. Kim, J. Mol. Liq. 240 (2017) 329–339.
[15] J.M. Silva, B.S. Farias, D.D.R. Gründmann, T.R.S. Cadaval Jr., J.M. Moura, G.L. Dotto, L.A.
A. Pinto, J. Appl. Polym. Sci. 134 (2016) 44580.
[16] A. Zahir, Z. Aslam, M.S. Kamal, W. Ahmad, A. Abbas, R.A. Shawabkeh, J. Mol. Liq. 244
(2017) 211–218.
[17] C. Li, T. Lou, X. Yan, Y.Z. Long, G. Cui, X. Wang, Int. J. Biol. Macromol. 106 (2018)
768–774.
[18] L.L. Min, Z.H. Yuan, L.B. Zhong, Q. Liu, R.X. Wu, Y.M. Zheng, Chem. Eng. J. 267 (2015)
132–141.
[19] N. Bhardwaj, S.C. Kundu, Biotechnol. Adv. 28 (2010) 325–347.
[20] A. Baji, Y.W. Mai, S.C. Wong, M. Abtahi, P. Chen, Compos. Sci. Technol. 70 (2010)
703–718.
[21] U.A. Qureshi, Z. Khatri, F. Ahmed, A.S. Ibupoto, M. Khatri, F.K. Mahar, R.Z. Brohi, I.S.
Kim, J. Mol. Liq. 244 (2017) 478–488.
[22] Q. Feng, D. Wu, Y. Zhao, A. Wei, Q. Wei, H. Fong, J. Hazard. Mater. 344 (2018)
819–828.
[23] U. Habiba, T.A. Siddique, S. Talebian, J.J.L. Lee, A. Salleh, B.C. Ang, A.M. Afifi,
Carbohydr. Polym. 177 (2017) 32–39.
[24] H. Homayoni, S.A.H. Ravandi, M. Valizadeh, Carbohydr. Polym. 77 (2009) 656–661.
[25] M.Z. Elsabee, H.F. Naguib, R.E. Morsi, Mater. Sci. Eng. C 32 (2012) 1711–1726.
[26] M.I. Shariful, S.B. Sharif, J.J.L. Lee, U. Habiba, B.C. Ang, M.A. Amalina, Carbohydr.
Polym. 157 (2017) 57–64.
[27] L.L. Min, L.B. Zhong, Y.M. Zheng, Q. Liu, Z.H. Yuan, L.M. Yang, Sci. Rep. 6 (2016)
32480.
[28] G.L. Dotto, V.C. Souza, J.M. Moura, C.M. Moura, L.A.A. Pinto, Dry. Technol. 29 (2011)
1784–1791.
[29] J.M. Moura, B.S. Farias, D.A.S. Rodrigues, C.M. Moura, G.L. Dotto, L.A.A. Pinto, J. Polym.
Environ. 23 (2015) 470–477.
[30] G.L. Dotto, J.M. Moura, T.R.S. Cadaval, L.A.A. Pinto, Chem. Eng. J. 214 (2013) 8–16.
[31] J.I. Goldstein, D.E. Newbury, P. Echlin, D.C. Joy, A.D. Romig Jr., C.E. Lyman, C. Fiori, E.
Lifshin, Scanning Electron Microscopy and X-ray Microanalysis, third ed. Springer
US, New York, 2003.
[32] ASTM D7426–08, Standard test method for assignment of the DSC procedure for de-
termining Tg of a polymer or an elastomeric compound, ASTM International, http://
www.astm.org/cgi-bin/resolver.cgi?D7426 2008 (accessed 10 December 2017).
[33] ASTM D3850–12, Standard test method for rapid thermal degradation of solid elec-
trical insulating materials by thermogravimetric method (TGA), http://www.astm.
org/cgi-bin/resolver.cgi?D3850 2012 (accessed 10 December 2017).
[34] R.M. Silverstein, F.X. Webster, D.J. Kiemle, Spectrometric Identification of Organic
Compounds, seventh ed. John Wiley& Sons, New Jersey, 2005.
[35] D.F. Swinehart, J. Chem. Educ. 39 (1962) 333–335.
[36] S. Azizian, J. Colloid Interface Sci. 276 (2004) 47–52.
[37] F.C. Wu, R.L. Tseng, R.S. Juang, Chem. Eng. J. 150 (2009) 366–373.
[38] A.L. Yarin, W. Kataphinan, D.H. Reneker, J. Appl. Phys. 98 (2005) 064501.
[39] M. Pakravan, M.C. Heuzey, A. Ajji, Biomacromolecules 13 (2012) 412–421.
[40] S. Zivanovic, J. Li, P.M. Davidson, K. Kit, Biomacromolecules 8 (2007) 1505–1510.
[41] G.Z. Kyzas, D.N. Bikiaris, Mar. Drugs 13 (2015) 312–337.