south african journal of chemical engineering 23 (2017) 42e49

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South African Journal of Chemical Engineering

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Adsorption of protein on activated carbon used in

the filtration of mucilage derived from Pereskia
aculeata Miller

Karen Cristina Guedes Silva, Tatiana Nunes Amaral,

Luciana Affonso Junqueira, Nata
lia de Oliveira Leite,
*
Jaime Vilela de Resende
Laboratory of Food Refrigeration, Department of Food Science, Federal University of Lavras, P.O. Box 3037,
37200-000, Lavras, Minas Gerais, Brazil

article info abstract

Article history: Mucilage is derived from Pereskia aculeata Miller via precursors obtained by an extraction
Received 9 October 2015 process. However, this process produces dark liquor whose coloring is not desirable in the
Received in revised form final food additives. Therefore, a fixed-bed filtration system with activated carbon was used
4 January 2017 for pigment elimination and clarification of the final product. Color parameters and protein
Accepted 25 January 2017 contents were evaluated by comparing the extract and the filtrate. At the same time, an
experimental study was conducted that monitored changes in pH and in the adsorption
Keywords: kinetics of proteins on the activated carbon using reactor tanks at various temperatures
Filtration and residence times. When using a filtration column, the results showed an increase in
Adsorption parameters L*, b* and Hue angle, thereby indicating that the filtrate was closer to the yellow
Fixed-bed column color when compared with the liquor feed. The results obtained using reactor tanks
Activated carbon showed that the protein contents and the pH were dependent on the contact time of the
Kinetic models substrate with the activated carbon and on the temperature. The experimental time
necessary to reach equilibrium was of 15.15 h for treatments at 30
C, 19.70 h at 45
C, and
26.06 h at 60
C. In these equilibrium conditions, the experimental adsorbed quantities of
protein (qe) were 223.03 mg/g, 232.02 mg/g and 332.02 mg/g respectively. The pH value
increased linearly as a function of temperature and residence time in the reactor. Reaction-
based kinetic models were expressed by the pseudo-first order, pseudo-second order,
WebereMorris and Elovich models. Specifically, sorption kinetics follows the pseudo-
second order mechanism for protein adsorption. Scanning electron microscopy analyses
proved that the non-diffusive is the sorption mechanism of protein on activated carbon
surface.
© 2017 The Authors. Published by Elsevier B.V. on behalf of Institution of Chemical Engi-
neers. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction for controlling the growth of ice and sugar crystals. Several
studies (Lin and Lai, 2009; Lai and Liang, 2012; Yapo, 2009) have
Vegetable gums have been widely used by the food industry as shown that the part of the plant being processed and the
thickening and gelling agents, emulsifiers and stabilizers and extraction conditions significantly affect the production and

* Corresponding author. Fax: þ55 35 3829 1401.

E-mail address: jvresende@dca.ufla.br (J.V. de Resende).
http://dx.doi.org/10.1016/j.sajce.2017.01.003
1026-9185/© 2017 The Authors. Published by Elsevier B.V. on behalf of Institution of Chemical Engineers. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 south african journal of chemical engineering 23 (2017) 42e49
physico-chemical characteristics of the resulting gums.
Characteristics such as the chemical composition (including
the neutral sugar, ash and protein content, and the degree of
esterification, methoxylation and acetylation) and molecular
weight distribution affect the rheological characteristics and
the function of these gums as emulsifying agents (by influ-
encing the emulsification capacity and stability) and as gelling
and thickening agents. The chemical structure of these hy-
drocolloids varies depending on the type of extraction and the
source material, and they can have one or more physical
properties that are useful commercially.
In Brazil, the Pereskia aculeata Miller plant is popularly
known as ora-pro-no
bis (OPN). It belongs to the cactaceae
family and is used as a nutritional supplement due to its
protein, fiber, iron and calcium content. This non-
conventional vegetable has succulent leaves, is edible, and
can be used in various preparations (Takeiti et al., 2009). Ac-
cording to Merce ^ et al. (2001), the leaves of OPN, contain
approximately 25% protein, which is a higher percentage than
is found in staple foods such as cabbage (1.6%), lettuce (1.3%),
corn (7.6e10%) and beans (18e20%). Lysine is an essential
amino acid, and in OPN, it is responsible for 5.4% of the protein
content present in the leaf. OPN has a carbohydrate compo-
sition based on structural polysaccharides belonging to the
arabinogalactan family.
OPN leaves are highly mucilaginous and a recent study
showed that the extraction of gum from them is feasible (Lima
Junior et al., 2013). OPN-derived gum presents a solution vis-
cosity and an emulsifying capacity and this has led to an
increased interest in studying OPN-based precursors and their
composition. When gums are used as food additives, certain
requirements must be met. These hydrocolloids must not alter
the color of the original product; they must present a neutral
taste, be easily dispersed, thermostable, and free of pathogens
and microorganisms and have low cost. To meet these char-
acteristics for the commercial application of gum OPN, a
filtration system was developed for pigment removal and final
product clarification. The conventional extraction process
gives rise to dark liquor whose coloring is not appropriate for
application as an additive in foods. In extraction process that
produces gum from P. aculeata Miller, the total protein contents
were reduced after passage through the fixed-bed column and
the reduction was related to the residence time of the extract
into the column (Lima Junior et al., 2013).
Colorings, suspended solids, organic matter, oils and odors
can be removed by adsorption (Juang et al., 2002; Andersson and
Eriksson, 2011; Ahmedna et al., 2000). Many industrial wastes
and agricultural by-products have been used as adsorbents for
the removal of organic compounds, dyes, color, and surfactants
from wastewaters (Mittal et al., 2009a, 2009b, 2010a, 2010b;
Gupta and Nayak, 2012; Gupta et al., 2011, 2012; Saleh and
Gupta, 2014, 2012). Activated carbon has been used in many
applications, such as air and water purification, removal of toxic
pollutants, heavy metals from industrial wastewater and in
catalysis (Saleh and Gupta, 2012; Turov et al., 2008; Juang et al.,
2001; Kuhn and Maugeri Filho, 2010; McKay et al., 1980; Aun Ng
et al., 2006; Vigneswaran et al., 2007; Yang and Al-Duri, 2005;
Gupta et al., 1997; Dizge and Tansel, 2011; El-Sheikh et al., 2004;
Derylo-Marczewska et al., 2005; Zhu et al., 2008; Rao et al., 2010;
Al-Asheh and Banat, 2001; Hasar et al., 2003). Activated carbon
has an important role in the adsorption of molecules that cause
taste, color and undesirable odors and is widely used for the
purification and separation of various materials. Separation by
solid/liquid adsorption is the process of selective removal of a
43
component or impurity from a solution by fluid contact with a
solid surface. This technique is effective for the removal of non-
biodegradable compounds and dyes that exhibit high molecular
stability (Juang et al., 2001). Studies with adsorbed protein on
the surfaces of activated carbon were performed by Garke et al.
(1999) and Dizge and Tansel (2011). The adsorption capacity of
activated carbon is determined not only by the total surface area
but also by the internal pore structure, by the presence of
functional groups on the pore surfaces and also by its electrical
charge that can generate attraction or repulsion (Kuhn and
Maugeri Filho, 2010).
Samples submitted to reactor tanks are usually stirred
according to a procedure designed to promote a reduction in
the resistance of the peripheral layer that surrounds the
adsorbent particle. In addition, stirring is used to increase the
mobility of the system, causing an increase in the rate of
adsorption (Kuhn and Maugeri Filho, 2010; McKay et al., 1980;
Aun Ng et al., 2006). Additionally, the adsorption rate depends
on the driving force per unit area. When the initial concen-
tration of the solution and the other system variables remain
constant, increasing the adsorbent mass increases the surface
area for adsorption and the adsorption rate. The adsorption
rate increases with time until it reaches a constant value,
beyond which no further adsorption takes place. The time
required to achieve this equilibrium state reflects the
maximum capacity of sorbent adsorption under these oper-
ating conditions (Aun Ng et al., 2006; Vigneswaran et al., 2007;
€
Ozacar and Sengil, 2003). Temperature is one of the most
important factors in adsorption systems because many pro-
cess rates are affected by temperature changes. An increase in
temperature causes an increase in kinetic energy and molec-
ular mobility, thereby enhancing adsorption. Moreover, tem-
perature can affect the solubility and the chemical potential of
the adsorbent, which are also factors that control the
adsorption process. However, very high temperatures may
favor the desorption process (Yang and Al-Duri, 2005).
The present study aims to determine the experimental
conditions that achieve a better yield of OPN mucilage with
high protein content at the end of the filtration process. To
determine the best operating conditions in the OPN extract/
activated carbon adsorption system, a study of this system for
different contact times and at various temperatures is
required. Therefore, in this work, we developed a filtering
system based on activated carbon and optimized its operating
parameters for the production of OPN gum by filtration of the
OPN extract. The main purpose was to optimize the system for
the adsorption of the molecules that cause dark pigmentation
in the OPN extract. Another objective was to evaluate the
extract's colorimetric parameters before and after filtration on
activated carbon in the fixed-bed column. A third goal was to
evaluate the adsorption of activated carbon in reactor tanks
under different residence times and temperature conditions
and to determine the influence of experimental parameters on
the pH and on the protein content of the filtrate, and, evalu-
ation of kinetics and sorption mechanism using scanning
electron microscopy (SEM).
2. Materials and methods
2.1. Materials
The P. aculeata Miller raw material was harvested in the
municipal district of Itutinga, Minas Gerais, Brazil. All of the
samples were harvested at the same place to reduce
44 south african journal of chemical engineering 23 (2017) 42e49
Fig. 1 e Flow chart of operations for the filtration of the
extract derived from OPN leaves.
interference due to alterations in species composition that
can be caused by the variability of available nutrients in the
soil and by climatic differences. After harvesting, the leaves
were taken to the laboratory. They were washed with running
water, manually selected and placed in polyethylene bags that
were sealed, labeled and stored in a freezer until the experi-
ments were performed. The processing of the OPN leaves and
the filtration of the OPN extract on activated carbon in the
fixed-bed column followed the operations shown in the
flowchart in Fig. 1.
2.2. Extraction process for the leaf hydrocolloids of P.
aculeata Miller
The various steps of the process of obtaining the OPN gum
were optimized as previously described in Lima Junior et al.
(2013). The conditions that provided the highest pH value for
Filtrate 1 and the highest hue (lighter product), highest vis-
cosity and lowest flow index values for Filtrate 2 were water to
raw material ratio of 2.46e3.70 L/kg and an extraction tem-
perature in the range of 54.6e80
C. The samples were pro-
duced using 2.5 L of water/kg of raw material and processed at
75
C, which was the optimal process temperature determined
by optimization tests.
2.3. Filtration on activated carbon in a fixed-bed column
Filtrate 1 was placed in the fixed-bed column to remove
pigments and insoluble solids. The columns were built
with cylindrical tubes of polyvinyl chloride with 1.00 m in
height and 0.11 m in diameter. The bed in the column,
0.80 m in length, was composed of activated carbon (Sci-
entific Exodus, Sa~ o Paulo, Brazil) with a 1e2 mm particle
size. Filtration with activated carbon is a process that de-
mands an extended period of time, which can result in the
proliferation of microorganisms in the separation envi-
ronment. To avoid their growth, the filtration process in
the fixed-bed column was conducted entirely in an inert
atmosphere using compressed nitrogen gas at a pressure of
1.2 atm.
Table 1 e Results of instrumental color analysis for
Filtrate 1 and Filtrate 2.
L* a* b* Hue Chroma DE*
Filtrate 1 17.43 6.15 0.5 4.64 6.17 75.19
Filtrate 2 34.93 5.64 14.13 68.24 15.21 59.34
Fig. 2 e Variation of pH values as a function of time in
reactor tanks with OPN gum operating at different
temperatures.
2.4. Characterization of filtrates 1 and 2
The pH of the filtrates was determined using a digital poten-
tiometer (Micronal, model 320, Sa ~ o Paulo, Brazil) (IAL Instituto
Adolfo Lutz, 2008). The instrumental analysis of color was
conducted in a Minolta CR 200 colorimeter following the
guidelines of the International Commission on Illumination
system. The L* value expresses the brightness such that a
value closer to 100 indicates a lighter product. The a* value
indicates a tendency towards coloration from green () to red
(þ); the b* value indicates a tendency of coloration from blue
() towards yellow (þ). The hue angle, which indicates the
chromatic shade (the attribute determining where the color is
perceived), was evaluated in each assay using Eq. (1) (McGuire,
1992):
H* ¼ tan1 ðb*=a*Þ: (1)
2.5. Adsorption kinetics in reactor tanks with stirring
To determine the adsorption kinetics, adsorption experiments
on activated carbon were conducted in reactor tanks with
agitation at a fixed temperature until the equilibrium point
was reached. Each experiment used 5 g of activated carbon
and 0.1 L of solution containing the Filtrate 1. Sample aliquots
were taken periodically, filtered and subjected to analysis.
The amount of adsorbed compound per mass of adsorbent
can be calculated according to Eq. (3) (Dizge and Tansel, 2011):
ðC0  Ct ÞVsol
qt ¼ ; (2)
ma
where qt is the quantity of adsorbed compound at equilibrium,
C0 is the concentration of compound in the initial solution, Ct
is the concentration of compound in solution at time t, Vsol is
Table 2 e Statistical parameters for the linear variation of
pH with time.
Temperature (
C) A B R2
30 6.62 0.01 0.99
45 6.72 0.10 0.88
60 6.48 0.01 0.98
 south african journal of chemical engineering 23 (2017) 42e49 45

The pseudo-second order model is represented by Eq. (4).

Table 3 e Proximate composition of Filtrate 1.
Component Composition (g/100 g) Standard deviation t 1 t
¼ þ (4)
qt k2 q2e qe
Protein 29.93 ±0.18
Carbohydrate 44.97 ±1.76 where k2 is the second-order adsorption constant (g mg1 h1),
Mineral 24.13 ±2.07 qe and qt are adsorbed quantities (mg g1) in equilibrium and at
Dry material 0.97 ±0.02
time t (h), respectively.
pH 5.45 ±0.01
Another mathematical model tested was the
WebereMorris intra-particle diffusion (Eq. (5)) with the pur-
the volume of the solution and ma is the mass of adsorbent. pose of to identify a possible intra-particle diffusion mecha-
The proximate composition was evaluated considering the nism as limiting step.
protein contents analyzed according to the following meth-
qt ¼ kp t1=2 þ C (5)
odologies. The protein fraction was obtained by determining
the total nitrogen percentage in the sample using the Kjeldahl where kp is intra-particle diffusion rate constant (mg g1 h1/2),
method as described by AOAC (2006). In this method, we used C is a constant related to the diffusion resistance (mg g1) and
6.25 as the conversion factor from total nitrogen to total pro- qt is the adsorbed quantity (mg g1) at time t (h).
tein. All chemical analyses were performed in triplicate and The Elovich equation (Eq. (6)) is suitable for systems whose
the results expressed as mean values. adsorption surfaces are heterogeneous.

qt ¼ bðIn abÞ þ bðIn tÞ (6)

2.5.1. Variation of pH
1
The pH of the filtrates was determined using a digital poten- where b is the desorption constant (g mg ), a is initial rate of
~ o Paulo, Brazil) (AOAC, 2006).
tiometer (Micronal, model 320, Sa adsorption (mg g1 h1) and qt is the adsorbed quantity
(mg g1) at time t (h).
2.5.2. Effect of contact time
The effect of adsorbate/adsorbent contact time was evaluated
keeping OPN gums in contact with activated carbon for 2.5, 2.7. Scanning electron microscopy (SEM)
5.0, 10.0, 20.0 and 30.0 h.
The activated carbon that was kept in contact with OPN gums
2.5.3. Effect of temperature for 2.5, 5.0 and 10.0 h at 30
C, 45
C and 60
C were separated
The effect of temperature on the adsorption characteristics by filtration. Samples of activated carbon fixed in modified
was evaluated by conducting tests at 30
C, 45
C and 60
C. Karnovsky were transferred to 30% glycerol for 30 min and
then cross sectioned in liquid nitrogen in about 2 mm frag-
ments. These were rinsed in distilled water and post-fixed in
2.6. Kinetic models
1% osmium tetroxide aqueous solution for 1e2 h and then
dehydrated in an increasing series of acetone solution (25, 50,
With the purpose of establishing an equilibrium time for the
70 and 90% for 10 min, and three times for 10 min at 100%).
maximum adsorption, different mathematical models were
Afterward, the samples were transferred to a Balzers CPD 030
used to explain the sorption kinetics of protein on activated
critical point dryer (Balzers, Liechtenstein, Germany) to com-
carbon. The pseudo-first order model, also known as Equation
plete the drying process with carbon dioxide as a transition
of Lagergren, is represented by Eq. (3) (Dizge and Tansel, 2011).
fluid. The specimens obtained were mounted on aluminum

stubs with double-stick carbon tape on aluminum foil coated
In qe  qt ¼ In qe  kt1 (3)
with gold using a Balzers SCD 050 sputter and kept in a
where k1 is the adsorption constant of first order (h1), qe and desiccator with silica gel until observation. SEM analyses were
qt are adsorbed quantities (mg g1) in equilibrium and at the conducted using a Leo EVO 40 microscope (Leo Electron Mi-
time t (h), respectively. croscopy, Cambridge, UK), and the images generated at
various magnifications were digitally recorded.

3. Results and discussion

3.1. The instrumental analysis of color

The main objective of the filtration in the fixed-bed activated

Fig. 3 e Effect of contact time on sorption capacity for
protein onto activated carbon.
carbon column is the clarification of the product. Product
coloring was significantly improved after filtrate 1 was passed
through the column. It can observed that there was an in-
crease in the parameters associated with less coloration,
namely, L* (which expresses the brightness such that a value
closer to 100 indicates a lighter product), b* (which indicates a
tendency of coloration from blue () towards yellow (þ)),
chroma and hue, which were all increased when comparing
Filtrate 2 to Filtrate 1, as shown in Table 1. Additionally, a
decrease in the parameter a* can be observed, which indicates
a tendency towards coloration from green () to red (þ). These
parameter values indicate how much closer to neutral colors
46 south african journal of chemical engineering 23 (2017) 42e49

Table 4 e Reaction-based parameters for OPN protein sorption on the activated carbon.
Temperature (
C) Pseudo-first order Pseudo-second order
qe (mg g1) k1 (h1) R2 qe (mg g1) K2 (g mg1 h1) R2
30 139.97 0.256 0.927 221.24 2.75  103 0.999
45 159.87 0.213 0.962 251.89 1.81  103 0.995
60 246.10 0.186 0.905 369.00 9.12  104 0.993

(white, gray or black) the analyzed Filtrate 2 extract is. The
increase in the hue angle parameter should be interpreted by
considering that values close to 0
are related to colors close to
red, while values close to 90
are related to colors close to
yellow (pure red has a hue angle of 0
, and pure yellow has hue
angle of 90
). When passing Filtrate 1 through the fixed-bed
column, all the coloration metrics tested showed values
indicating a color closer to yellow in the resulting Filtrate 2.
Therefore, the column was efficient at removing pigments
from Filtrate 1.
produced by hydrocolloids depends on the type of hydrocol-
loid used and on the physical-chemical conditions of the
medium, i.e., the pH, presence of ions and temperature. These
parameters affect each type of gum differently and can
determine the texture of the final product. Fig. 2 shows that
extract neutralization occurred at temperatures of 30
C and
45
C, leading to final pH values of 7.06 and 7.07, respectively.
The treatment at 60
C resulted in a lower pH value in the OPN
gum.
The variation of pH as a function of residence time can be
represented by Eq. (7):

3.2. Variation of pH Y ¼ Y0 þ Bt (7)

where Y0 is the initial pH value, Y is the pH value at time t, t is

The adsorption process is influenced by both the adsorbent
surface charge and the degree of ionization of the adsorbed
substance. The latter is influenced by the pH of the extract.
Saha and Bhattacharya (2010) assert that the thickening effect
the time and B is the angular coefficient of the equation. The
coefficients for each temperature tested are shown in Table 2.
The variation in pH values show that these gums behave
like polyelectrolytes in contact with activated carbon (Medina-
Torres et al., 2000). These gums contain a large number of

Fig. 4 e Adequacy of the (a) pseudo-first order and (b) Fig. 5 e Adequacy of the (a) WebereMorris intra-particle
pseudo-second order kinetic models for protein sorption. diffusion and (b) Elovich models for protein sorption.
 south african journal of chemical engineering 23 (2017) 42e49 47

Table 5 e Diffusion-based parameters for OPN protein sorption on the activated carbon.
Temperature (
C) WebereMorris Elovich
kp (mg g1 h1/2) C (mg g1) R2 b (g mg1) a (mg g1 h1) R2
30 35.500 50.27 0.736 31.477 1.042 0.894
45 41.844 44.637 0.779 46.443 0.153 0.812
60 61.091 51.500 0.820 101.032 0.021 0.837

carboxyl and hydroxyl groups, which are characteristic of
polysaccharides, and the OPN gum also has a high protein
content, whose functionality depends on the isoelectric point.
Changes in pH values certainly result from the changes in
ionization states of these structural groups.
3.3. Adsorption kinetics
The adsorption equilibrium point was determined as function
of time for each temperature in reactors. For comparison of
the adsorption levels under different treatments, samples of
the extract obtained from Filtrate 1 were analyzed considering
the parameters of interest. Table 3 presents the chemical
composition of Filtrate 1 on a dry basis as used in the fixed-bed
column feed.

3.3.1. Effect of the temperature on the adsorption of proteins

The experiments were carried out with the initial protein
concentration of 29.93 g/100 g at temperatures of 30, 45 and
60
C and contact times of 2.5, 5.0, 10.0, 20.0 and 30.0 h. Fig. 3
displays the amount of protein adsorbed on activated carbon
as function of time. The experimental time necessary to reach
equilibrium was of 15.15 h for treatments at 30
C, 19.70 h at
45
C, and 26.06 h at 60
C. In these equilibrium conditions, the
adsorbed quantities of protein (qe) were 223.03 mg/g,
232.02 mg/g and 332.02 mg/g respectively. The contact time
necessary to reach equilibrium and the adsorbed quantities
showed direct correlation with the temperature.
The results showed that activated carbon presented better
affinity for protein adsorption with temperatures of 60
C,
45
C and 30
C, respectively. Fig. 3 shows that the higher
temperatures yielded higher protein adsorption and also that
longer contact times were more effective in the removal of
this component. Fig. 3 indicates that 30
C is the optimal
process temperature because lower temperatures resulted in
less adsorbed protein.

3.3.2. Reaction-based kinetic models

Fig. 6 e Scanning electron microscopy of the activated
carbon surfaces with adsorbed OPN extracts after
treatments in tank reactor at (a) 30
C, (b) 45
C and, (c)
60
C.
The mechanisms of protein sorption on activated carbon and
sorption rates were investigated using the Lagergren pseudo-
first order (Eq. (3)) and the pseudo-second order (Eq. (4)) kinetic
models. Table 4 presents the parameters defined as constant
rates (k1) estimated from the linear form of Lagergren pseudo-
first order model. For the pseudo-second order kinetic model
the sorption constant rates (k2) and sorption capacities (qe)
were calculated graphically from the linear model (i.e., from
the graphs of t/qt as function of t). The graphics of the pseudo-
first order and pseudo-second order at temperatures of 30, 45
and 60
C are showed in Fig. 4. The estimated kinetic constants
(qe, k2) for the linear form of the pseudo-second order model at
different temperatures also are presented in Table 4.
Fig. 4 and Table 4 shows that the best correlations were ob-
tained from pseudo-second order model which presented higher
values of R2 (greater than 0.99) and confirm that the sorption
kinetics have followed this mechanism for protein adsorption.
Adsorption process that follows the pseudo-second order is
controlled by chemisorption as limiting step. A comparison of
the difference between the calculated and experimental values
of qe showed that the results of pseudo-second order model were
similar to the experimental observations with errors of 0.80,
7.89 and 10.02% for treatments at 30, 45 and 60
C, respectively.
48 south african journal of chemical engineering 23 (2017) 42e49
3.3.3. Diffusion-based kinetics models
The Graphics of the WebereMorris and Elovich models at
temperatures of 30, 45 and 60
C are displayed in Fig. 5 and the
parameters calculated from the diffusion-based models are
presented in Table 5. The values of WebereMorris intra-
particle diffusion rates increase from 35.500 to
61.091 mg g1 h1/2 for protein with the increase in tempera-
tures from 30 to 60
C. If the two models are compared, the
Elovich model (intra-particle diffusion model) showed the
highest coefficient of correlation R2 (greater than 0.81).
Considering Elovich model, Table 5 shows that desorption
constants increased and initial adsorption rates decreased
with increase of temperature which indicated that the process
is endothermic. R2 values are high for all the conditions tested.
These results indicate that protein adsorption by the activated
carbon is intra-particle diffusion controlled.
3.4. Microstructure using scanning electron microscopy
Analysis of the activated carbon surfaces with adsorbed OPN
extract was performed at the three-dimensional level by SEM,
and representative electron micrographs are presented in
Fig. 6. Fig. 6a shows the activated carbon structures with
adsorbed OPN extract treated at 30
C after 10 h in the reactor
tank. It can observe its high porosity and adherence of smaller
particles on the exterior surfaces of larger particles.
One image of the microstructure of an activated carbon
with adsorbed OPN extract treated at 45
C after 10 h in the
reactor tank is presented in Fig. 6b, and, at 60
C after 10 h in
the reactor tank is presented in Fig. 6c. These images
demonstrate that the gel particles were larger and of size more
uniform and were more strongly adherent onto exterior sur-
faces compared with Fig. 6a. In comparing Fig. 6a and c, it can
be observe that the increases of temperature caused strong
interactions inter-particles. Larger agglomerates with stron-
ger interactions and inter-particle adherence to exterior sur-
face were observed in Fig. 6c. Notably, Fig. 6c shows that there
was a higher level of porosity, differences in the particle sizes,
and a higher frequency of particles adhered to exterior
surfaces.
Activated carbon has a porous structure with high specific
surface (area/unit weight); however, the utilization of surface
depends on the activation characteristics, roughness, and
accessibility of the interior surfaces (El-Sheikh et al., 2004).
The compounds with smaller molecular size can diffuse into
the porous structure of carbon particles; hence, exhibit a multi
layered sorption profile. On the other hand, larger molecules
have limited ability to diffuse into the porous matrix; hence,
can be adsorbed primarily on the exterior surfaces. The
analysis by SEM demonstrates that the mechanism of non-
diffusive sorption is involved in adsorbed protein of OPN
extract on the porous matrix of activated carbon.
4. Conclusions
The process developed in this study for the filtration and
clarification of precursors presented satisfactory results
confirmed by the color analysis. Studies on the adsorption
kinetics demonstrated that at 30
C the protein adsorption
was lowest. Taking into account that protein is an essential
component of OPN hydrocolloids and that at this temperature
exhibited lower loss levels, it is recommended that the pro-
cess be performed under lower temperature conditions.
According to reaction-based kinetic models, the best cor-
relation was obtained for the pseudo-second order model
which presented higher values of R2 (greater than 0.99) and
confirm that the protein sorption kinetics of OPN extract have
followed this mechanism for protein adsorption. The results
of pseudo-second order model were similar to the experi-
mental observations with errors of 0.80, 7.89 and 10.02% for
treatments at 30, 45 and 60
C, respectively. Elovich model
showed that desorption constant increases and initial
adsorption rate decreases with increase of temperature which
indicated that the process is endothermic, and that the pro-
tein adsorption by the activated carbon is intra-particle
diffusion controlled. SEM demonstrated that the mechanism
of non-diffusive sorption is involved in adsorbed protein of
OPN extract on the porous matrix of activated carbon.
Acknowledgments
The authors wish to thank the Fundaça ~ o de Amparo a  Pes-
quisa do Estado de Minas Gerais (FAPEMIG-Brazil), the Con-
selho Nacional de Desenvolvimento Cientı́fico e Tecnolo
gico
(CNPq e Brazil) and the Coordenaça~ o de Aperfeiçoamento de
Pessoal de Nı́vel Superior (CAPES e Brazil) for their financial
support of this research.
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