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PII: S2213-3437(17)30127-6
DOI: http://dx.doi.org/doi:10.1016/j.jece.2017.03.035
Reference: JECE 1541
To appear in:
Please cite this article as: Arvind Kumar, Hara Mohan Jena, Adsorption of Cr(VI)
from aqueous solution by prepared high surface area activated carbon from Fox
nutshell by chemical activation with H3PO4, Journal of Environmental Chemical
Engineeringhttp://dx.doi.org/10.1016/j.jece.2017.03.035
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Adsorption of Cr(VI) from aqueous solution by prepared high surface area activated
Highlights
Cr(VI) adsorption study onto prepared activated carbon with H3PO4 activator.
The maximum adsorption capacity of Cr(VI) is 74.95 mg/g.
The adsorption process is endothermic and spontaneous one.
A maximum removal of 71.86% is achieved in the column study.
Abstract
Adsorption studies of Cr(VI) onto activated carbon, FNAC-700-1.5 (BET surface area of 2636
m2/g and total pore volumeof 1.53 cm3/g), prepared from Fox nutshell by chemical activation
with H3PO4 at an impregnation ratio of 1.5 and activation temperature of 700 oC under N2
atmosphere were carried out in the present work. In batch adsorption experiments the effect of
agitation speed, pH, temperature, adsorbent dosage, initial concentration of Cr(VI), and contact
time were studied. Also adsorption kinetics, equilibrium, and thermodynamics of Cr(VI)
adsorption were studied. The adsorption was found to follow the pseudo second order model.
A maximum adsorption of 74.95 mg/g was obtained at the operating condition of 35 mg/L of
Thermodynamic parameters such as ΔGo, ΔHo and ΔSo were calculated by using Van´t hoff
equation. The adsorption process was endothermic and spontaneous one. In column
experiments, the effects of the bed height of the packing material and flow rate of Cr(VI)
1
solution on adsorption characteristics were studied. A maximum removal of 71.86% was
achieved in the column study for 10 mg/L initial Cr(VI) concentration at 4 cm bed height, and
Column study.
1. Introduction
Primary sources of wastes containing heavy metals are the industrial activities (e.g.
mining, painting, car manufacturing, metal plating, and tanneries) and agricultural activities
(when fertilizers and fungicidal sprays are intensively used) [1]. Heavy metals are considered
one of the most hazardous contaminants in wastewater. Cadmium, chromium, copper, lead,
mercury, and nickel are most toxic metals according to the WHO, 2004 and WHO, 2006 [1].
metabolism, amino, and nucleic acid synthesis). When chromium accumulated at high levels,
generate serious problems (nausea, skin ulcerations, lung cancer) and, when the concentration
reaches 0.1 mg/g body weight, it becomes lethal [2]. Chromium is considered as an important
toxic material as it does not undergo biodegradation [3]. Chromium as pollutant is introduced
into natural waters by a variety of industrial wastewaters coming out from industries such as;
electroplating, and metal finishing ones [3-5]. Chromium occurs as both trivalent [Cr(III)] and
hexavalent [Cr(VI)] states in the aquatic environment. Cr(VI) is primarily present in the form
of chromate (CrO4−) and dichromate (Cr2O7−). Cr(VI) possesses significantly higher levels of
toxicity than the other valency states [4-5]. Cr(VI) tolerance limit for discharge into inland
2
surface waters is 0.1 mg/L and in potable water is 0.05 mg/L [6]. Thus removal of Cr(VI) from
Among the various removal techniques, the adsorption by using activated carbon is
effective than other adsorbents (clay material, natural and synthetic polymers and their
composites) due to its high specific surface area, adequate pore size distribution, variable
characteristics of surface chemistry [7-9]. The activated carbons are most widely used in many
applications such as wastewater treatment, removal of harmful gasses, solvent recovery, colour
removal, and as electrode materials in electrochemical devices and processes [9-10]. In the
adsorption process, the high cost of adsorbents is the main barrier in industrial use. The
adsorbent cost can be reduced if prepared from some waste materials such as; agricultural
waste, biomass, and various solid waste substances [11] and if appropriate regeneration is done
[12]. So there is a need to develop low-cost and easily available adsorbent for removal of
In the present work adsorptive removal of Cr(VI) from aqueous solution was carried
out by previously prepared high surface area activated carbon from Fox nutshell (FNAC-700-
1.5) by activation with H3PO4 [13]. Among the various dehydrating agents used for chemical
activation, phosphoric acid (H3PO4) is preferred recently due to environmental and economic
concerns. Phosphoric acid allows the development of both micropores and mesopores in the
resulting activated carbon [14]. Polyphosphoric acids are formed by condensation of two or
more H3PO4 molecules with the elimination of water as a complex mixture of linear molecules
of various chain lengths. At high temperatures, the reactions with carbon matrix increases and
develop more pores and release P4, CO2, H2O and other volatile materials [15]. To the best of
our knowledge, no study was reported on the removal of hexavalent chromium from aqueous
solution by FNAC-700-1.5. Fox nutshell, a low ash (5%) content and high volatile matter
(70.1%), is a good precursor for the production of an effective activated carbon due to its
3
abundance and availability. The adsorption kinetics, equilibrium, and thermodynamics of
Cr(VI) adsorption on the prepared activated carbon were studied. In the batch adsorption study
the influence of operating parameters, such as agitation speed, pH, temperature, contact time
and initial concentration of Cr(VI) on adsorption characteristics were investigated. Linear least
square method and non-linear method of three widely used isotherms, Langmuir, Freundlich,
and Tempkin, was examined to experiment Cr(VI) adsorption onto FNAC-700-1.5. A trial and
error procedure was used for non-linear method by using the solver add-in with Microsoft’s
spreadsheet, Microsoft Excel. In the column study effect of bed height of carbon and flow rate
on breakthrough and saturation times, adsorption capacity and percentage removal were
studied.
2. Experimental
2.1. Materials
The chemicals used in the present study, such as; ZnCl2, K2Cr2O7, NaOH and HCl were
of AR grade of brand Merck, India. Stock solution of 1000 mg/L of Cr(VI) was prepared by
dissolving 2.8269 g K2Cr2O7 in 1000 mL distilled water. Standard working solutions of Cr(VI)
ions of various concentrations ranging from 10 to 35 mg/L were obtained by dilution of the
stock solution.
The effect of pH on the amount of Cr(VI) removal was analyzed over the pH range
from 2 to 7 by using 0.1 N NaOH and 0.1 N HCl solutions for the pH adjusting. In this study,
100 mL of Cr(VI) solution of 10 mg/L was agitated with 0.02 g of FNAC-700-1.5 using orbital
shaker at 30 °C temperature. Agitation was made for 3 h that is more than sufficient to reach
equilibrium at a constant agitation speed of 150 rpm. The samples were then centrifuged, and
the left out concentrations in the supernatant solution were analyzed by a spectrophotometer.
4
The PZC was measured as follows: 20 mL of NaCl solution (0.1 N) was placed in an
Erlenmeyer flask including 0.1 g of AC. The initial pH was adjusted between 2 and 12 by the
addition of 0.1 N NaOH and 0.1 N HCl. After a contact time of 24 h under magnetic agitation,
flasks containing 100 mL of Cr(VI) (10, 15, 20, 25, 30 and 35 mg/L) solution with
predetermined amount of adsorbent (in the range of 0.01g 0.07 g). The flasks were agitated in
an isothermal orbital shaker at 150 rpm and temperature range of 25-45 °C for 3 h. The pH was
maintained by the addition of 0.1 N NaOH and 0.1 N HCl as required and was recorded by
using pH meter (361 model, Systronic). The following relations were used to determine the
(𝐶0 − 𝐶𝑒 )𝑉
𝑞𝑒 = , (1)
𝑚𝑠
𝐶0 − 𝐶𝑒
𝑅(%) = 100 , (2)
𝐶0
Kinetic studies were also performed according to the method as described above.
Kinetic study provides the information of uptake rate and controls the equilibrium time [16].
As per literature the most appropriate pseudo first and pseudo second order model were used
different contact time t (min) was determined using the following equation:
(𝐶0 − 𝐶𝑡 )𝑉
𝑞𝑡 = , (3)
𝑚𝑠
where C0, Ce, and Ctwere the initial, equilibrium, and at time t (min) of Cr(VI) concentrations
(mg/L) respectively, V the volume of solution (L) and ms was the dry weight of the adsorbent
(g) added.
5
2.4. Fixed-bed column adsorption studies
A Perspex glass cylindrical tube having 2.5 cm internal diameter and 20 cm height was
used to construct the adsorption column. The schematic of the experimental arrangement and
photographic view of the adsorption column is shown in Fig.1. The column was packed with
calculated amount of FNAC-700-1.5 to obtain a desired bed height of 4 cm. For this amount
of activated carbon used was 6.0 g. The bed was held in place between two plugs of cotton.
The glass beads supported the cotton in the lower and upper part of the column. The volumetric
flow rate of Cr(VI) solution was adjusted to 5, 10 and 15 mL/min in the experiments at various
flow rates in the range 5-15 mL/min. The adsorbate solutions were fed continuously to the
column in an upward flow mode using the peristaltic pump (Rivtek, India) at room temperature
of 30 °C. To study the effect of bed height, sample collection ports were provided at each 1 cm
interval. Effluent samples were collected from the samplecollecting sites of the column at
different time intervals, and the concentration of Cr(VI) was determined colorimetrically.
The loading behavior of Cr(VI) in its dynamic adsorption from the solution by FNAC-
700-1.5 was shown in the form of breakthrough (BT) curves. The BT curve is usually expressed
in terms of normalized concentration, as the ratio of outlet adsorbate concentration to the inlet
adsorbate concentration (Ct/C0) for a given bed height. The total adsorbed quantity of
adsorbate, qtot (mg) was estimated as area under the BT curve which was obtained by
integrating the plot as per the Eq. (4) [17-18] shown below.
𝑡=𝑡𝑡𝑜𝑡
𝑄
𝑞𝑡𝑜𝑡 = ∫ 𝐶𝑎𝑑 𝑑𝑡, (4)
1000 𝑡=0
where Q (mL/min) is the volumetric flow rate, Cad (mg/L) is the difference between the initial
and final concentrations of adsorbates at the end of the total flow time till exhaustion, ttot (min).
Equilibrium adsorbates uptake in the column or maximum capacity of the column (bed
6
𝑞𝑡𝑜𝑡
𝑞𝑏𝑒𝑑 = , (5)
𝑊
where W is the amount of prepared activated carbon FNAC-700-1.5. The quantity of Cr(VI)
𝐶0 𝑄𝑡𝑡𝑜𝑡
𝑚𝑡𝑜𝑡 = , (6)
1000
𝑞𝑡𝑜𝑡
%𝑟𝑒𝑚 = 100, (7)
𝑚𝑡𝑜𝑡
Aliquot of adsorbate was withdrawn from the suspension at pre-set time intervals and
centrifuged (2 mL) at 10,000 rpm for 5 min to remove the adsorbent particles before analytical
measurements were made. The concentrations of Cr(VI) after adsorption was carried out
Figure 2 shows the effect of agitation speed on % removal of Cr(VI) adsorption onto
FNAC-700-1.5. From Fig.2, the results show that the removal efficiency of Cr(VI) increases
with increase in agitation speed and maximum removal by FNAC-700-1.5 are achieved at 150
rpm, and above 150 rpm, the % removal is almost constant. Thus, the agitation speed was fixed
at 150 rpm for Cr(VI) adsorption for the further experiments. These results indicate that an
effective transport of Cr(VI) ions towards the adsorbent surfaces occurred, due to less
resistance to diffusion at higher agitation speed. Some studies also report similar variation in
Cr(VI) adsorption and speed of 150 rpm as sufficient to break all diffusion resistances [21-24].
3.1.2. Effect of pH
7
The solution pH is one of the important parameter having considerable influence on the
heavy metal ions adsorption from aqueous solution, because the pH affects surface charge
density of the adsorbent and the charge of the metallic species present [25-26]. To study the
effect of pH on adsorption, pH was varied from 2-7 at 10 mg/L of initial Cr(VI) concentration
with carbon dose of 0.02 mg/100 mL adsorbate solution and 30 °C temperature. pH below 2
was not experimented as per the published reports, which says “Cr(VI) could be reduced to
Cr(III) in the presence of activated carbon under highly acidic conditions (pH < 2)” [12]. Figure
Fig. 3, the removal of Cr(VI) from aqueous solution is greatly dependent on the pH values, and
Hexavalent chromium exists in different forms in varying pH of aqueous solution and the
stability of these forms, such as HCrO4−,CrO42−, or Cr2O72− [12]. In the pH ranging from 2.0 to
6.0, HCrO4− and Cr2O72− ions mainly exist in equilibrium; HCrO4− is the dominant form of
Cr(VI) at pH 2 and the predominant form shifts to chromate ion (CrO42−) as pH increases. A
chromate ion (CrO42−) needs two active sites due to its two negative charges, whereas an
HCrO4− ion only needs one active site. It is well known that an increase in the adsorption
capacity of Cr(VI) is observed due to more HCrO4− ions formed at the expense of CrO42−ions
with decreasing the pH value. So that HCrO4− is adsorbed preferentially on carbon [24]. The
behavior for better adsorption at low pH by activated carbon may be attributed to the large
number of H+ ions present which in turn neutralize the negatively charged adsorbent surface,
thereby reducing hindrance to the diffusion of chromate ions [12]. At higher pH, decreasing
the adsorption capacity may be due to the competitive adsorption of chromate and hydroxyl
ions [24].
8
The pH at point zero charge (PZC) was found to be 2.7. At pH < pHPZC, the carbon
surface takes up more H+, increasing Cr(VI) ions bind on the adsorbent surface. At pH > pHPZC,
the adsorbent surface is negatively charged, the increasing electrostatic repulsion between
negative adsorbate species and adsorbent particles would lead to decrease adsorption capacity
of Cr(VI) ions. From Fig. 3, the adsorption was high as 46.32 mg/g at pH value of 2 that was
below PZC of the FNAC-700-1.5. However, the adsorption was decreasing at pH of solution
more than the PZC. This is in agreement with our experimental observations showing
To access the effect of temperature on Cr(VI) adsorption, the temperature of the system
was varied from 20-45 °C at pH of 2, initial concentration of 10 mg/L, carbon dose of 0.02
g/100 mL and shaken in the orbital shaker for 3 h at agitation speed of 150 rpm. Figure 4 shows
the effect of temperature on % removal of Cr(VI). The figure indicates an increase in removal
of the adsorbate with temperature that indicates the adsorption process is endothermic in nature.
At this particular condition, % removal increased from 55.88 to 60.02% for an increase in
mg/L at 45 °C temperature and pH 2 while the amount of adsorbent added was varied to
evaluate the effect of carbon dose on removal of Cr(VI) and the result is presented in Fig. 5.
Activated carbon dosage were ranged from 0.01 to 0.07 g/100 mL of chromium solution and
equilibrated for 3 h. The percentage removal of Cr(VI) is found to increases with increase in
adsorbent dose up to 0.04 g significantly and after that remained unchanged. Thus, to get the
better Cr(VI) removal, 0.04 g was chosen as an optimal mass of the adsorbent in further
9
experiments. With increasing adsorbent dose, there is increase in adsorbent surface area and
To see the effect of contact time and initial concentration of Cr(VI) percentage removal
from the solution and the uptake of FNAC-700-1.5, experiments were conducted at different
initial concentrations (10, 15, 20, 25, 30 and 35 mg/L) by varying the time till 3 h., at 45 ºC
and pH 2. It can be readily observed from Fig. 10(a) that the uptake capacity of FNAC-700-1.5
to Cr(VI) drastically increased during the initial stage because of high available surface area
and vacant site of AC and then marginal increase with raising the time and reach equilibrium.
The growing trend stopped when a state of equilibrium was reached. FNAC-700-1.5 removed
a larger amount of Cr(VI) in the first 20 min of contact time, and the equilibrium was
established in 60 min for all different adsorbate concentration studied (Fig 6(a)). A large
number of vacant sites with active functional groups were available on FNAC-700-1.5 at an
early stage of adsorption for the Cr(VI). The equilibrium adsorption increased from 24.92 mg/g
to 74.95 mg/g (Fig 6(a)), which may be due to the availability of more number of Cr(VI) ions
in solution for adsorption [27]. Furthermore, higher initial adsorbate concentration provided
higher driving force to overcome all mass transfer resistances, resulting in high adsorption of
Cr(VI) [27-29]. The percentage removal of Cr(VI) was observed in reverse behaviour, as
decreased from 99.67% to 86.85% with initial concentration increased from 10 mg/L to 35
into the reaction pathways and the mechanism of the reactions. Any adsorption process is
normally controlled by the three diffusion steps: (i) transport of the solute from bulk solution
to the film surrounding the adsorbent, (ii) from the film to the adsorbent surface, (iii) from the
10
surface to the internal sites followed by binding of the metal ions to the active sites. The slowest
steps determine the overall rate of the adsorption process, and usually, it is thought that the step
(ii) leads to surface adsorption, and the step (iii) leads to intra-particle adsorption [12]. The
pseudo first and pseudo second order models were used to fit the experimental data of Cr(VI)
adsorption by using nonlinear regression method. To evaluate the goodness of fitting and
suitability of the model, the Coefficient of Determination (R2) and normalized standard
deviation ∆q (%) were used in the kinetic model study. A higher value of R2 and lower value
of ∆q denoted better model fitting. The standard deviation ∆q (%) was calculated as follows:
where, qexp and qcal (mg/g) are the experimental adsorption capacity and calculated adsorption
Nonlinear and linear forms of pseudo first order equations are given in Eqs. (9) and
(10), respectively.
−𝑘1 𝑡
𝑞𝑡 = 𝑞𝑒 (1 − 𝑒𝑥𝑝𝑒 ), (9)
Nonlinear and linear forms of pseudo second order are given in Eqs. (11) and (12),
respectively.
𝑘2 𝑞𝑒2 𝑡
𝑞= , (11)
1 + 𝑘2 𝑞𝑒 𝑡
𝑡 1 1
= 2
+ ( )𝑡 , (12)
𝑞𝑡 𝑘2 𝑞𝑒 𝑞𝑒
where qe and qt (mg/g) are the adsorbed Cr(VI) amounts onto FNAC-700-1.5 at the equilibrium
and any time t (min), respectively and k1 (min−1) and k2 (g/min/mg) are the rate constant of the
11
The study of adsorption kinetics describes the solute uptake rate, and evidently, this
rate controls the residence time of adsorbate at the solid–solution interface. The adsorption
kinetics of pseudo first order and pseudo second order for Cr(VI) onto FNAC-700-1.5 is shown
in Figs. 7 (a) and (b). The derived kinetic parameters of pseudo first and pseudo second order
model was estimated by nonlinear regression method and tabulated in Table 1. As observed,
the experimental kinetic data are better fitted by the pseudo second order model (R2 = 1 for all
Cr(VI) concentrations). Also, the calculated value (qcal) that was derived from the pseudo
second order equation is quite similar to those obtained experimentally, which indicates that
the pseudo second order model is suitable for the observed kinetics than pseudo first order
model. Moreover, all the calculated normalized standard deviation Δq (%) of pseudo first and
pseudo second order model are shown in Table 1. The resulted Δq (%) values are relatively
lower for the pseudo second order than the pseudo first order model.
At equilibrium state, the adsorption isotherm is very useful to describe how the
adsorbed molecules distribute between the liquid phase and the solid phase. The Langmuir,
Freundlich, and Temkin isotherm models were used for the adsorption isotherm. The results of
the fitting done for used models of Cr(VI) adsorption are listed in Table 2.
The Langmuir isotherm is valid for monolayer and homogeneous sites within the
adsorbent surface with a uniform distribution of energy level. The model assumes uniform
adsorption and no transmigration in the plane of the adsorbent surface [30]. The nonlinear and
𝑞𝑚 𝑘𝐿 𝐶𝑒
𝑞𝑒 = , (13)
1 + 𝑘𝐿 𝐶𝑒
𝐶𝑒 1 𝐶𝑒
= + , (14)
𝑞𝑒 𝑘𝐿 𝑞𝑚 𝑞𝑚
12
where qm (mg/g) represents the maximum adsorption capacity of the solid phase loading and
kL (L/mg) is the Langmuir constant. Figure 8(a) shows a linear relationship of C e/qe vs. Ce
using experimental data obtained for Cr(VI) adsorption. The qm and kL values are obtained
from slope and intercept of the plot and are tabulated in Table 2. Figure 8 shows experimental
data and the predicted equilibrium curve using non-linear method for the three-equilibrium
isotherms Freundlich, Langmuir and Temkin at 45 oC. The obtained isotherm parameters are
listed in Table 2.
1
𝑅𝐿 = , (15)
(1 + 𝑘𝐿 𝐶𝑜 )
where kL is the Langmuir constant and Co is the highest Cr(VI) concentration (mg/L). The RL
value indicates the isotherm typeto be either unfavourable (RL> 1), linear (RL = 1), favourable
(0 < RL<1) or irreversible (RL = 0). The value of RL was found to be 0.0069 for Cr(VI)
adsorption, and it confirms that the Langmuir isotherm is favorable for Cr(VI) adsorption on
where kF ((mg/g)(L/mg)1/n) is the Freundlich constant related to adsorption capacity and 1/n is
1
ln 𝑞𝑒 = ln 𝑘𝐹 + ln 𝐶𝑒 , (17)
𝑛
The plot of ln qe vs. ln Ce confirms the validity of the Freundlich model and is shown in Fig.
8(b). The value of 1/n (0.213 by linear regression and 0.305 by nonlinear regression) < 1
13
Temkin and Pyzhev have suggested that the heat of adsorption should decrease linearly
with the surface coverage because of the existence of adsorbate-adsorbate interactions [33].
The nonlinear and linear form of the Temkin and Pyzhev equation is represented as follows:
where B=RT/b is related to the heat of adsorption (L/g), and A is the dimensionless Temkin
The Coefficient of Determination (R2) values of these isotherm models are shown in Table 2.
For linear regression analysis, the Langmuir model is best fitted for Cr(VI) adsorption onto
FNAC-700-1.5. Thus, from Table 2, the comparison of tested models for the description of
Freundlich > Temkin. From Table 2, it is observed that, the isotherm parameters estimated for
different isotherms by linear and non-linear methods are entirely different. R2 values suggest
that the Freundlich isotherm was best-fitted model with the larger value of coefficient of
determination (Table 2). For nonlinear regression analysis, the comparison of tested models for
To justify the viability of the prepared activated carbon as effective adsorbents for
Cr(VI) removal, the adsorption capacity of FNAC on Cr(VI) were compared to the efficiency
of other low-cost adsorbents found in literature with similar batch studies. Table 3 shows a
summary of Cr(VI) removal capacity (mg/g), at optimum pH, and maximum concentration of
Cr(VI) used (mg/L) for various adsorbents in the present study and previously studied. The
adsorption capacity of Olive bagasse activated carbon (136.63 mg/g) [12] is larger than FNAC-
14
700-1.5 activated carbon (74.95 mg/g). Hence, Fox nutshell activated carbon can be considered
in the reaction. The thermodynamic parameters such as; Gibbs free energy (∆Go) for
adsorption, change in enthalpy (∆Ho) i.e. heat of adsorption of Cr(VI) onto FNAC-700-1.5 and
change in entropy (∆So) were determined by using the following equations [16,44-45]:
∆𝐺 𝑜 = −𝑅𝑇 𝑙𝑛 𝐾𝐶 , (20)
∆S 𝑜 −∆H 𝑜
ln 𝐾𝐶 = + , (21)
𝑅 𝑅𝑇
where R (8.314 J/mol.K) is the universal gas constant, T (K) is the solution temperature, and
KL (L/g) is the adsorption affinity (Langmuir equilibrium constant) and is calculated as the ratio
between adsorption capacity (qe, mg/g) and equilibrium concentration (Ce, mg/L) [42-43]. KC
is the thermodynamic equilibrium constant (dimensionless) [44-45]. The values of ΔHo and
ΔSo were determined from the slope and intercept of the Van´t hoff plot of ln KC vs. 1/T (Fig.
9). The calculated thermodynamic parameter values are tabulated in Table 4. Generally, a value
of ΔGo in between 0 and -20 kJ/mol indicates physical adsorption i.e., electrostatic interaction
between adsorption sites and the adsorbing ion while a more negative ΔGo value ranging from
-80 to -400 kJ/mol indicates that the adsorption involves charge sharing or transferring from
the adsorbent surface to the adsorbing ion to form a coordinate bond (chemisorption) [46-47].
From Table 4, the negative Gibbs free energy of the experimental value indicates the adsorption
process to be spontaneous. The positive value of the enthalpy change (ΔHo = 10.29 kJ/mol)
shows that the Cr(VI) adsorption process onto FNAC-700-1.5 is endothermic in nature. The
positive value of ΔSo indicates the increased randomness at the solid-solution interface during
The operating variables such as volumetric flow rate (Q), and length of the bed (L) have
a great influence on breakthrough and saturation times, and on the dynamics of the column. In
this study, the effect of these variables on the breakthrough curves of Cr(VI) onto FNAC-700-
Fig. 10(a) shows the Breakthrough (BT) curves obtained for Cr(VI) adsorption onto
prepared activated carbon at bed heights of 2, 3 and 4 cm, and a constant flow rate of 5 mL/min
and initial adsorbate concentration of 10 mg/L. The figure shows that both the BT and
exhaustion times increase as bed height is increased. The increase in the breakthrough time
could be ascribed to the longer distance it takes the mass transfer zone to move from the
entrance of the bed to the exit when the bed height is increased. Furthermore, higher uptake of
Cr(VI) by FNAC-700-1.5 was observed at higher bed height, which could be attributed to rising
in the surface area of the adsorbent, which provide more fixation binding sites for adsorbate to
adsorb. From Table 5, it can be noticed that the breakthrough time and exhaustion time
increased, uptake capacity decreased from 17.16-29.10 mg/g and percentage removal of Cr(VI)
from the solution increased from 58.18-71.86% as the bed height increased from 2-4 cm.
The effect of flow rate on Cr(VI) removal by prepared FNAC-700-1.5 was studied by
varying the flow rate in the range of 5, 10 and 15 mL/min, while the bed height of 4 cm and
initial Cr(VI) concentration of 10 mg/L held constant. The breakthrough curves of both
activated carbons obtained by plotting effluent Cr(VI) concentration versus time at different
flow rates are represented in Fig. 10(b). As the flow rate is increased, the breakthrough curves
became steeper, and the slope of the breakthrough curve increased. The residence time of the
Cr(VI) in the column decreases due to flow rate increases, which leads to the early exit of the
16
Cr(VI) solution from the column. From Table 5, it can be noticed that the breakthrough time,
exhaustion time, % removal decreased and uptake capacity is increased as the flow rate is
increased. From Table 5, it can be noticed that the breakthrough time and exhaustion time
decreased. The uptake capacity increased from 29.10-36.17 mg/g and percentage removal of
Cr(VI) from the solution decreased from 71.86-58.82% as the flow rate increased from 5-15
mL/min.
4. Conclusions
In the present study, activated carbon with a well-developed pore structure of high
surface area was prepared from Fox nutshell by chemical activation with phosphoric acid and
studied for Cr(VI) adsorption from the synthetic waste water. Under the prevailing
thermodynamic parameters as ∆Go, ∆So and ∆Ho conforms that the adsorption was feasible,
spontaneous and endothermic in nature. The results indicate that the FNAC-700-1.5 could be
used to adsorb Cr(VI) effectively from aqueous solutions. The highest bed capacity of 36.17
mg/g was obtained using 10 mg/L initial Cr(VI) concentration at 4 cm bed height, and 15
mL/min flow rate. FNAC-700-1.5 activated carbon proved to be an effective adsorbent for
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Figure Caption
22
Figure captions:
Figure 2. Effect of agitation speed on the Cr(VI) removal (C0 = 10 mg/L, temperature = 30 oC,
Figure 3. Effect of pH on the Cr(VI) removal (C0 = 10 mg/L, temperature = 30 oC, FNAC-700-
Figure 5. Effect of FNAC-700-1.5 dosage on the Cr(VI) removal (C0 = 10 mg/L, pH = 2.0,
Figure 6. Effects of contact time on the adsorption capacity at different initial concentrations
Figure 7. (a) Pseudo first and (b) Pseudo second order plot for the Cr(VI) adsorption by FNAC-
Figure 8. (a) Langmuir and (b) Freundlich isotherms for the adsorption of Cr(VI) onto FNAC-
Figure 10. Breakthrough curves for Cr(VI) adsorption on FNAC-700-1.5 at different bed
23
Fig.1
1. Peristaltic pump
2. Wastewater reservoir
3. Packed column (glass beads +cotton +activated carbon +cotton +glass beads)
4./5./6. Sample storing vial (at each 1 cm height of filled activated carbon)
Fig. 2
24
Fig. 3
Fig. 4
25
Fig. 5
26
Fig. 6
27
Fig. 7
28
Fig. 8
29
Fig. 9
30
Fig. 10
31
Table captions
Table 1 Kinetic constants obtained by nonlinear regression for the adsorption of Cr(VI) onto
FNAC-700-1.5
Parameters ACPA-700-1.5
Cr(VI), C0 (mg/L)
10 15 20 25 30 35
qe,exp (mg/g) 24.92 35.82 46.47 56.31 65.83 74.95
R2 1 1 1 1 1 1
32
Table 2 Langmuir, Freundlich, and Temkin parameters for Cr(VI) adsorption onto the FNAC-
700-1.5
33
Table 5 Column data parameters obtained at different bed heights and flow rates
Adsorbents Bed Flow rate Breakthrough exhaustion Bed %
height (mL/min) time (min) time (min) capacity, qeq Removal
(cm) (mg/g)
FNAC-700- 2 5 420 3060 17.16 58.18
1.5 3 5 1680 3660 22.70 66.77
4 5 2520 4500 29.10 71.86
4 10 1380 3020 35.61 64.75
4 15 780 2220 36.17 58.82
34