Modification of Pomegranate Waste With Iron Ions A
Modification of Pomegranate Waste With Iron Ions A
Modification of Pomegranate Waste With Iron Ions A
Abstract
Pomegranate waste modified with Fe2+ and Fe3+ ions followed with carbonization were used as an adsorbent to
remove the Pb2+ ions from aqueous solution. To optimum the highest adsorption efficiency, adsorption experiments
were conducted on iron modified carbons by batch technique. The characteristic of composite was studied by scan-
ning electron microscope (SEM) and Fourier transform infrared spectrometer (FT-IR). The best pH for control of chemi-
cal adsorption was selected within pH of 6.0–6.5. It was observed that the contact time of 90 min, initial concentration
50.0 ppm, and adsorbent dose, 1.0 g/100 ml solution was found to be optimum conditions. On this condition, the
maximum adsorption capacity was obtained 27.5 and 22.5 mg/g for Fe2+ and Fe3+ impregnated pomegranate peel
carbons (PPC), respectively. The value of Cid, 1.584 for Fe2+-PPC and 0.552 for Fe3+-PPC, indicates that the effect of
the boundary layer is more important in adsorption of Pb2+ by Fe2+-PPC and the pore diffusion is the rate limiting
mechanism after 30 min. Thermodynamic parameters of Gibbs free energy, enthalpy, and entropy of P b2+ adsorp-
tion on iron-modified carbons suggest that the adsorption process is favorable and spontaneous under the optimum
condition.
Keywords: Iron modified carbon, Pomegranate peels, Composite, Thermodynamic, Kinetic
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of peanut shell (Wilson et al. 2006), pistachio shell, and and Fe2+ solutions for 12 h, separately. The impregnated
apricot stone (Kazemipour et al. 2008), have been exam- granules were dried and then carbonized at 400 °C for
ined for removing of P b2+ ions from aqueous solutions. 3 h into a programmable furnace in the absence of air.
Pomegranate wastes as a by-product of juice, jams, The residual was washed 3 times with distilled water to
syrup, and sauce manufacturing industries, which pro- eject excess ions from the modified carbons. Eventually,
duced in large amounts in Iran. The peels include about the iron modified carbons were heated at 105 °C, named
45–50% of the total weight of fruit. The fruit peels have Fe2+-PPC and Fe3+-PPC and maintain for further uses.
a strong affinity and high selection towards heavy metals
because of the various functional groups on the surface Calibration
of it. Hence, the idea to change the by-product of pome- The ranges of the calibration curves (0–50 ppm) for P b2+
granate fruit to iron impregnation carbon for cleaning of the samples were selected for calibration of AAS. For
the environment and removing of heavy metal is valu- this purpose, the absorbance of standard solutions was
able. Abedi et al. impregnated of Fe2+ and Fe3+ ions to constructed versus concentration at a maximum wave-
the PPC were studied to remove Cd(II) ions (Abedi et al. length of 283.3 nm. Detection and quantification limits
2016). were defined as the lowest concentrations of a compo-
Considering the above descriptions, we used as an nent that produces a signal equal to three and ten times
adsorbent the iron modification of PPCs for removing of the standard deviation for a series of the blank solu-
of Pb2+ from aqueous solution by one factor at a time tion. The following equations were used for calculation of
methodology. The main objective of this work is to obtain the detection (DL) and quantification (QL) limit:
the adsorption kinetic and thermodynamic parameters
3.3 ∗ σ A
for the adsorption reaction of Pb2+ ions with prepared D.L. = (1)
composite. m
The adsorption process depends on many factors
10 ∗ σ A
including pH, temperature, adsorbent mass, concentra- Q.L. = (2)
tion of pollutant, adsorbent type, contact time and agita- m
tion time. In the present study, the effect of initial lead DL and QL are the detection and quantification limit, σA
concentration, adsorbent dose, and temperature was is the standard deviation of the intercept, and m is the
screened for removing of Pb2+ ions by Fe2+ and Fe3+ slope of the calibration of linear equation.
impregnated into PPC adsorbents. The experiments were
performed in batch technique and adsorption capacity Experiments
was calculated in the each step. Then, the plot of adsorp- To obtain optimal conditions, the effect of contact time,
tion capacity via parameter changes was used to choose initial Pb2+ concentration, and adsorbent dose were
the optimum amount of each factor. determined at laboratory temperature (27 °C) based on
the following experiments:
Materials and methods The effect of initial P b2+ concentration was studied
Reagents using 0.2 g of adsorbents and 50 ml of different concen-
All of the chemicals used in this work were of analytical trations of Pb2+ solution in the range of 10, 25, 50, 75 and
grade. The 100 ppm stock solution of P b2+ was prepared 100 ppm in the screw-capped containers. The influence
by dissolving of Pb(NO3)2 in distilled water. The FeCl3 of composite dose on P b2+ adsorption was examined by
and FeCl2 solutions were used for modification of pome- taking 50 ml of 50 ppm of Pb2+ solutions and shaking
granate peels. Five standard solutions of 0.0, 5.0, 10.0, with varying amounts of adsorbents in ranging from 0.1
25.0, 50.0 ppm were made from a solution of 100 ppm to 1.5 g. The similar solutions without adsorbents as con-
by dilution with 1% (v/v) HNO3 for calibration of atomic trol samples were examined in parallel. All of the batch
absorption spectrometer (AAS). The working solutions experiments were performed at solution pH of 6.5 in the
with desired P b2+ concentration were daily made by dilu- 150 ml closed containers and constant shaker 180 RPM
tion of the stock solution. using a shaker equipped with an electrical heater. At the
end of all the experiments, the suspension was filtered
Preparation of composites and the concentration of P b2+ in the filtered solution
Pomegranate wastes were collected from Agro Indus- was measured by AAS that it was calibrated, previously.
tries Co in Fars province, Iran. They were dried at labo- According to the obtained data, the adsorption capacity
ratory temperature in the absence of sunlight and sized (q) of adsorbents (mg/g) was determined by the differ-
in mesh 40–100 by standard sieves. To modify them, ence of initial and equilibrium concentration using the
10 g of the granules were mixed with 10 ml of 0.1 M Fe3+ mass balance equation, as follows:
Fig. 1 SEM images of adsorbents prepared for adsorption of Pb. SEMs were recorded in the acceleration voltage 15.00 kV and magnitude ×100.00
for focusing on surface porous. a SEM image of pomegranate peel carbon and b iron modified pomegranate peel carbon. There was a significant
difference of porous between two image corresponding modifications
Thermodynamic
The equilibrium constant, adsorption free energy,
enthalpy, and entropy changes of reaction were estimated
by Eqs. 6 and 7. The corresponding values of thermody-
namic functions are summarized in Table 4.
Fig. 4 The effect of initial concentration on adsorption capacity. The
change of adsorption capacity in removal of Pb2+ vs initial concen- Discussion
tration of Pb2+ for Fe2+-PPC is depicted in red and for Fe3+-PPC is Comparison of two images in Fig. 1 revealed that the PPC
depicted in blue
had low porosity and regular surfaces, whereas iron mod-
ified composite showed the development in their poros-
ity and hence an increasing of the number of sites on the
to 20.6 mg/g for Fe2+-PPC and 3.1 to 19.4 mg/g for surface, consequently the modification with iron have
3+
Fe -PPC until 50 ppm, but it had a little increasing to been enhanced the active surface of composite.
27.5 and 22.5 mg/g by increasing duplicate of the initial The functional groups on the surface adsorbent are
concentration of Pb2+ from 50 to 100 ppm. important for understanding of the adsorption process.
The Fig. 2 shows a broadband about 3400 and 2900/cm
Effect of dose which denote the presence of hydrogen-bonded OH
The influence of the adsorbent dose on the adsorption groups on the surface of adsorbent, originally bonded
process at a constant initial concentration of Pb2+ was to an organic polymeric structure. The IR spectra indi-
examined to obtain the right adsorbent mass. Figure 5 cates a strong peaks about 1600/cm band is related to
(10)
(11)
2+
Fig. 6 Diffusion kinetic models for Pb adsorption. The Morris Weber pH = 7−8 2HO− + Pb2+ = Pb(OH)2(aq.) (12)
model kinetic were don’t in various times. This model for Fe2+-PPC is
depicted in blue. The Morris Weber model in the range of 0–30 min
for Fe3+-PPC is depicted in red and in the range of 30–60 min is pH > 8 2HO− + Pb2+ = Pb(OH)2(s) and then
depicted in green
HO− + Pb(OH)2(s) = Pb(OH)−
3 (aq) (13)
Based on the above equations, dissolved Pb species
Table 3 The intraparticle diffusion kinetic data for adsorp-
which are present in the solution, depend on pH and
tion of Pb2+ ions on iron modified pomegranate peel car-
bons are in different forms such as Pb2+, PbOH+, Pb(OH)2,
and Pb(OH)3−. The Eqs. 9 and 10 indicate that P b2+
Adsorbent Parameters ions are the predominant species to pH of 6.5, and are
Kid Cid R2 responsible for maximum adsorption. Another pH con-
ditions for the formation lead hydroxide species like
Up to 30 min
PbOH+, Pb(OH)2, and Pb(OH)− 3 occur after pH of 6.5,
Fe2+ PPC 0.228 1.584 0.998
which causes a decrease in the adsorption yield. It is
Total of time
clear that precipitation of Pb2+ in the form of Pb(OH)2
Fe3+ PPC 0.299 0.552 0.986
at pH > 7 can be decreased the adsorption of Pb2+ ions,
which cause a decrease in the adsorption yield. The
precipitation did not occur at the pH lower than 6.5,
the vibration of –C=O group stretching from aldehydes, but the adsorption yield of metal ions may be very low
ketones, and carboxylic acids (Palin et al. 2016). The at acidic pH values. This situation is explained based
peaks of 500–900/cm regions indicate the loading of Fe2+ on electrostatic repulsion forces between surface posi-
ions into functional groups of granola surface. tive charges and Pb species. The Pb2+ ions adsorption
The pH value not only has an impact on the charge of occurred on the adsorbent surface by exchange with
the adsorbent surface, but also the ionization degree of H+ at pH of 6.5.
particles and the existence of adsorbate species in solu- Regards to the above, it is concluded that the pH for
tion (Zhan and Zhao 2003). In the case of P b2+ ions, adsorbents must be selected higher than the pHzpc
the relative hydrolysis and precipitation of Pb species of adsorbate that it was obtained for F e2+-PPC (4.3)
3+
at different pH, have an effect on the adsorption pro- and Fe -PPC (6.0) in our previous work (Abedi et al.
cess with changing of the form and number of Pb ion 2016). In this state, most of the sorption sites on the two
Table 4 Thermodynamic parameters for Pb(II) adsorption on iron modified pomegranate peel carbons (Fe2+-PPC
and Fe3+-PPC)
Temp (°C) Fe2+-PPC Fe3+-PPC
ΔG* ΔH* ΔS* ΔG* ΔH* ΔS*
25 − 0.17 50.0
55 − 3.87 40. 6 0.136 − 2.51 27.5 0.092
85 − 8.35 − 5.45
* kJ/mol
composites are negatively charged in the solution. In are governed by the adsorption mechanism (Weber and
contrast, the pH for formation of Pb2+ must be selected Morris 1963). Figure 6 is not linear at all times, but have
lower than pH of 6.5. According to the above description, two regions linear. The first stage (until 30 min) indicates
it is concluded that the adsorption process for Pb2+ ions intraparticle diffusion or pore diffusion and the second
will be electrically favorable at pH of 6.0–6.5. So, this pH region (up to 30 min) related to the adsorption on the
was selected for other adsorption experiments. Under interior of the adsorbent. It also indicates that the pore
this condition, biosorption of P b2+ on the F
e2+-PPC and diffusion is not only the rate limiting mechanism and
3+
Fe -PPC was expected to be favorable by electrostatic other mechanisms are involved in the adsorption of P b2+
2+
forces. by Fe -PPC. Similar results were obtained in the study
The effect of time data was studied to investigate the of (Jiménez-Cedillo et al. 2013). In addition, The result
adsorption mechanism of P b2+ ions on the iron-modified shows that the linearity q t vs t 1/2 plots for a total of con-
carbons. A time required for the adsorbate concentration tact time between the Pb2+ ions and F e3+-PPC did not
to reach a constant value during the adsorption process pass through the origin. This show that the intraparticle
was defined as adsorption equilibrium time. Figure 3 diffusion was only the rate-controlling step, but also the
shows the rate of Pb2+ adsorption was fast in the initial one portion linearity of the plot for Fe3+-PPC shows that
times proportional to the enough available surface area the one stage is involved in adsorption mechanism and
on the adsorbent. Until time increased, more amount of the boundary layer effect on the adsorption is limiting
Pb2+ adsorbed on the active sites on the adsorbent sur- control of mechanism. According to Table 3, The value
face by attraction forces and caused a decrease in avail- of Cid gives information about the boundary layer, so the
able surface areas on adsorbent (Onundi et al. 2011). value of C e2+-PPC and 0.552 for F
id, 1.584 for F e3+-PPC,
According to Fig. 4, the two states of adsorption of indicates that the effect of the boundary layer is more
Pb2+ indicated that from 0 to 50 ppm the adsorption important in adsorption of Pb2+ by Fe2+-PPC after
capacity increased proportional to the existence of unoc- 30 min. These deviations from the origin may be due
cupied adsorption sites on both biosorbents, but from to the difference in the initial and the final rate of mass
50 to 100 ppm the adsorption sites gradually saturated transfer.
and the additional concentration of Pb2+ remained in Thermodynamic studies are used to predict the possi-
the solution, therefore the adsorption capacity remained bility of doing reaction in a better way and performed by
nearly constant. changing temperature against the yield of P b2+ adsorp-
The Fig. 5 showed, at a constant concentration of Pb2+, tion (Huang et al. 2007). Adsorption of Pb2+ ions on
the adsorption capacity F e2+-PPC and F e3+-PPC to the two composites increased by rising of the tempera-
2+
adsorb of Pb ions increased by increasing of the adsor- ture from 25 to 85 °C. It is clear, increasing temperature
bent dose. It is related to the presence of more sites on the enhances the chemical affinity and mobility of the Pb
surface of biosorbents at higher doses and the fact that cations toward the active sites on the biosorbent surface
certain adsorption sites are unsaturated during the batch leading to the occurrence of chemical interaction during
adsorption process (Mehrasbi et al. 2009). The adsorption the adsorption process. The same conclusion reported by
capacity of Fe2+-PPC and Fe3+-PPC was about marginal Garcia-Rosales and Colin- Cruz in adsorption of Pb(II)
to 25 mg/g for two studied adsorbents when adsorbent and Cd(II) on the stalk sponge of Zea mays (García-
dose increased from 0.1 to 1.0% w/v. This fall in the P b2+ Rosales and Colín-Cruz 2010).
adsorbed amount per unit mass of biosorbent is a usual The positive value of enthalpy changes (40.6 and
manner which has also been reported by Acharya et al. 27.5 kJ/mol) indicates the endothermic nature of adsorp-
(2009). Hence, other experiments were conducted at the tion of P b2+ on Fe-PPC. A possible interpretation is that
2+
optimum value of 1.0% w/v of adsorbent dose. the Pb ions are hydrated in the solution. This reaction
Obtaining of the kinetic data is necessary to extend requires high energy, is endothermic, and supersedes the
an equation for designing of the rate system and under- exothermic attraction of Pb ions toward active sites on
standing the process mechanism that evaluated by the composite surface. The similar observation has been
matching the experimental data to kinetic models. Vari- previously found in the removal of lead onto prepared
ous kinetic models are used for evaluation of the rate activated carbon from coconut shell (Sekar et al. 2004).
adsorption process. The intraparticle diffusion model is The positive value of entropy changes (136 and 92.0 J/
an equation to survey the rate and mechanism of adsorp- mol) also indicates the affinity of Pb2+ ions toward active
tion process (Srihari and Das 2008). According to them, sites of adsorbents and suggests an increasing degree of
If the line of qt via t1/2 goes through the origin, then the freedom during the metal ions adsorption on an adsor-
limiting rate of reaction is intraparticle diffusion; as well bent (Arshadi, et al. 2014). The negative values of Gibbs
as, if the plot forms multi-linearity, more than one stage free energy changing (ΔG), except for adsorption in the
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