Research Article

Journal of Elastomers & Plastics

117
New efficient chelating The Author(s) 2016
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DOI: 10.1177/0095244316673134

plastic waste for jep.sagepub.com

removal of toxic heavy

metal pollutants
Noha Elhalawany1, Rasha Abdel Baseer1,
Abdallah Bakr Mostafa1 and Abdel Gawad Rabei2

Abstract
New efficient chelating polymers (CPs) based on waste polystyrene functionalized by
itaconic acid moieties in absence and presence of montmorillonite clay have been pre-
pared using high shearing effect homogenizer. The obtained CPs have been characterized
using spectrophotometric and thermal analyses. The prepared CPs have been used as
potential adsorbents for removal of different toxic metal ions from their aqueous
solutions. The adsorption performance of the obtained CPs was found to match well
with Langmuir adsorption isotherms. The highest sorption affinity of the obtained CPs
toward different metal ions was for copper and lead.

Keywords
Chelating polymers, copper ion uptake, sorption kinetics, sorption affinity

Introduction
Nowadays heavy metal pollution has come to be one of the most serious threats for
environment. Exposure to a trace of heavy metals is considered a risk for human
beings.1,2 Efficient removal of toxic heavy metals from water systems is still very
important and interesting task for environmental engineers. Many technologies such as
chemical precipitation, ion exchange, adsorption, and membrane filtration have been
adopted to remove poisonous metal ions from water.35

1
Department of Polymers and Pigments, National Research Centre, Cairo, Egypt
2
Department of Chemistry, Ain Shams University, Cairo, Egypt

Corresponding author:
Noha Elhalawany, Department of Polymers and Pigments, National Research Centre, Elbhoos St, Dokki, Cairo
12622, Egypt.
Emails: nr.ibrahim@nrc.sci.eg; elhalawany1933@gmail.com
2 Journal of Elastomers & Plastics

Recently, numerous approaches have been discovered to develop low-priced and

more effective technologies for water purification. Adsorption has proven to be cost-
effective and competent for removing heavy metals, organic pollutants, and dyes from
water systems.6
Adsorbents attracted vast attention due to accessibility of various adsorbent types,
environmental friendly, cost viability, and their high effectiveness in removal of organic
and inorganic pollutants. There are several important standards governing the selection
and design adsorbents such as fast removal, ion selectivity, and reusability.7,8
Recently, adsorbents built on nanomaterials gained great attention due to their
extraordinary performance to adsorb pollutants from aqueous environments such as
carbon nanotubes, titania, silica, and clay polymer composites.9,10 Ionic polymer clay
nanocomposites11 showed effectiveness for removal of inorganic and organic pollu-
tants.12,13 The sorption capacity of polymerclay composites was affected by preparation
process, type of polymerclay composites, and application technique such as membrane,
nanofilters, and so on.1416
The use of (inorganicorganic) nanomaterials such as polymer clay composites as an
adsorbent is regarded as one of the most effective methods for removal of heavy metal
ions from aqueous phase.17 On other hand, structural flexibility, mechanical perfor-
mance, and prospective applications in harsh environmental conditions are some of the
major merits of these hybrid polymeric materials. Research is working on synthesizing
and testing the possibilities to apply these hybrid polymeric adsorbents for removal of
toxic metal ions from aqueous solutions.1820
Considering the merits of the aforementioned polymerclay composites as adsor-
bents, in present study, we have used a new facile synthesis type route to prepare effi-
cient and low-cost chelating polymers (CPs) based on cheap waste polymeric materials
functionalized by itaconic acid (IA) moieties and montmorillonite (MMT) clay for
removal of some toxic heavy metal ions from their aqueous solutions.

Experimental work
Materials
Copper acetate (CH3COO)2Cu4H2O, cobalt acetate Co(Ac)24H2O, nickel acetate
Ni(Ac)24H2O, CrCl36H2O, cadmium acetate Cd(Ac)22H2O, lead acetate Pb(Ac)2.OH,
Cu(Ac)2H2O, butyl acrylate (BA), and IA are purchased from Sigma-Aldrich (St Louis,
Missouri, USA). All other chemicals used were chemically pure and are obtained from
BDH Prolabo chemical company (England).

Characterization techniques
Infrared spectra. Infrared (IR) analyses of the prepared CPs have been measured using
Jasco 6100 plus Fourier transform infrared (FTIR) spectrometer (Japan).

Differential scanning calorimetric analysis and thermogravimetric analysis. Thermal analysis,

thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) for the
Elhalawany et al. 3

tested samples have been measured using a PerkinElmer thermogravimetric analyzer

(Waltham, Massachusetts, USA) under nitrogen conditions. The heating rate was 10 C
min1 from 50 C to 500 C.

Scanning electron microscope/EDX). Morphological studies as well as element constitution

of the tested samples have been measured using scanning electron microscope (SEM)/
energy-dispersive X-ray (EDX; JEOL JXA- 840 A Electron PROBE, Japan), micro-
analyzer microscope, Japan.

UV-Vis spectrophotometer. Spectrophotometric measurements were carried out using

ultravioletvisible (UV-Vis; JASCO V-630, Japan) spectrophotometer.

Synthesis of CPs
In presence of MMT clay. The synthesis reaction was done according to previous work14
and it is detailed as follows:
First, 6 g WPst (yoghurt cups) and 0.2 g MMT were soaked in 25 mL dioxane, then
homogenized using Greaves homogenizer X120 (Germany) at 6000 r min1 for 10 min.
The previous homogenized solution was charged into 100 mL two-necked flask fitted
with a reflux condenser followed by the addition of 0.2 g benzoyl peroxide PBO dis-
solved in 5 mL dioxane and 9.6  103 moles BA drop wisely under continuous stirring
at 750 r min1 at 75 C. The reaction was left for 2 h to form the seed polymer. Finally,
3.8  103 moles of IA were added to the reaction media. The polymerization reaction
was left for further 2 h. The resultants CP have been purified by washing with water/
methanol mixture of ratio (3:1) several times to remove the unreacted water-soluble
monomers followed by Soxhlet extraction from diethyl ether to remove the excess
initiator and the unreacted BA monomer.

In absence of clay. The reaction was done as the aforementioned procedure.

Metal ion uptake measurements

Preparation of Cu (II) solution. Stock solution of copper ion of initial concentration (Ci;
7.852  103 mg/L) have been prepared by dissolving 1.963  103 mg (CH3COO)2Cu in
250 mL distilled water.

Copper ion uptake experiments. A 0.3 g of the obtained CPs was placed into separating
funnel with sintered glass filter system containing 30 mL of (CH3COO)2Cu solution of
well-known Ci at room temperature for a definite time. The residual concentration (Cr) of
the copper ion under investigation was determined using UV-Vis spectrophotometer via
different absorption/concentration standard curves. The copper ion uptake (CIU) was
determined by equation (1):
V Ci  Cr
qe 1
m
4 Journal of Elastomers & Plastics

Figure 1. Conceptual structure of the prepared CP in presence of MMT clay14. CP: chelating
polymer; MMT: montmorillonite.

where Ci and Cr are the initial and final metal ion concentration (mg/L), respectively;
V is the volume of solution (L); and m is the mass of the dried CPs (g).

Effect of pH on the uptake of copper ion. Uptake experiments under controlled pH were
carried out following the above procedure for uptake experiments. The pH was adjusted
using the suitable buffer.

Competitive removal of metal ions from aqueous solution. A mixture solution containing
(Cr3, Co2, Ni 2, Cu2, Cd2, and Pb2) ions of concentrations 1281, 1057, 1051,
197.5, 592.7, and 331.4 mg L1, respectively, was added to 0.05 g of dry CP at
room temperature and left for 2 h. The percentage of adsorbate ions onto the CP was
determined by EDX (JEOL JXA-840 A Electron PROBE, Japan) microanalyzer
microscope.

Results and discussion

The resultant CP in presence of MMT is supposed to have the following conceptual
structure and it is represented in Figure 1.
The proposed mechanism for the interaction of the prepared CPs with the studied
copper ions is illustrated in Figure 2.

Characterization of the prepared CPs

FTIR spectra. The FTIR spectra of CPs with and without clay are represented in Figure 3.
The adsorption bands at 3438 and 1452 cm1 are attributed to the stretching and bending
of OH group of IA. The adsorption bands at 1733 and 1168 cm1 are attributed to CO
and CO stretching of ester group of BA. The band near 755 cm1 is characteristic for
CH bending of monosubstituted benzene derivative of polystyrene.

Thermogravimetric analysis. Thermogravimetric analyses for the prepared CPs are shown
in Figure 4. It is clearly seen from the figure that the weight losses of CP with and
Elhalawany et al. 5

Figure 2. The interaction of the prepared CPs with the tested copperion.14 CP: chelating
polymer.

755
1648
1168
1452
3438
T%

1733 b

1643 756
3439 1453 1160
1734
4000 3500 3000 2500 2000 1500 1000 500
Wave number (cm1)

Figure 3. FTIR spectra of the prepared CPs (a) without clay and (b) with clay. FTIR: Fourier
transform infrared; CP: chelating polymer.

without clay are 10.08% and 15.94% at temperatures 390.69 C and 376.45 C,
respectively. The CP containing clay showed higher thermal stability. In general, it
can be concluded that the presence of slight amount of MMT clay enhances the
thermal stability.

Differential scanning calorimetry. Figure 5 shows DSC thermograms of the prepared CPs in
absence and presence of MMT clay. In both thermograms, two glass transition tem-
peratures (Tgs) are clearly observed, which reveals the existence of two separated
6 Journal of Elastomers & Plastics

(a) CP without clay

100
(b) CP with clay

80
a b
Weight (%)

60

40

20

0 100 200 300 400 500 600

Temperature (C)

Figure 4. TGA of the prepared CPs (a) without clay and (b) with clay. TGA: thermogravimetric
analysis; CP: chelating polymer.

a
4

Tg
2
Tc
Heat flow (W/g)

Tm
0 b
Tg
Tc
2 Tm

8
0 100 200 300 400 500 600
Temperature (C)

Figure 5. DSC curves for the prepared CPs (a) without clay and (b) with clay. DSC: differential
scanning calorimetric; CP: chelating polymer.

polymeric microdomains within the same sample.21 The high-temperature transitions at

95.44 and 104.75 C for CP without and with clay, respectively, are corresponding to the
polystyrene waste forming the core. On the other hand, the low-temperature transitions at
63.83 and 71.71 C for CP without and with clay, respectively, are corresponding to the
Tg of the BA and IA copolymer forming the shell. In addition, the endothermic crys-
talline transitions for CP without and with clay appear at 396.65 C and 405.06 C,
Elhalawany et al. 7

Figure 6. SEM for the surface morphology of CPs (a) without clay and (b) with clay. SEM: scanning
electron microscope; CP: chelating polymer.
respectively, while the endothermic melting transitions for CP without and with clay
appear at 429.52 C and 438.33 C, respectively.

Scanning electron microscope. SEM analysis for the prepared CPs in presence and absence
of MMT clay is shown in Figure 6. Figure 6 showed that the CP without MMT displayed
a rough surface, while the CP with clay has a smooth surface indicating a well-dispersed
MMT nanoparticles through the polymer matrix and this morphological situation is
believed to be responsible for enhanced sorption capacity.

Sorption kinetics
Effect of contact time. The CIU by the prepared CPs (0.3 g) at natural (pH 5.8) and at
different time intervals is shown in Figure 7. It is clearly seen from the figure that if fast
CIU is observed nearly at the first 5 min, then enhanced increase in the uptake with
increasing time has taken place. The CP containing MMT clay showed noticeable
increase in CIU. It is clearly seen from the data that the maximum sorption capacities for
Cu2 ions were 123.36 and 110.36 mg g1 for CP with and without clay, respectively.

Kinetics of Cu(II) sorption. The kinetics of Cu 2 ion sorption can be demonstrated using
two basic kinetic models including pseudo-first and pseudo-second order. The pseudo-
first-order model is expressed as22:
k1 t
Log qe  qt log qe  2
2:3
where k1 is the pseudo-first-order rate constant (min1) of adsorption and qe and qt
(mmol g1) are the amounts of metal ion adsorbed at equilibrium and time t (min),
respectively. On the other hand, the pseudo-second-order model is expressed as23:
t 1 t
3
qt k 2 qe q
8 Journal of Elastomers & Plastics

(a) CP without clay

130 (b) CP with clay

120
qe (mg g1)

b
110
a
100

90
0 20 40 60 80
Time (min)

Figure 7. Sorption of Cu2 ions by the prepared CPs (a) without clay and (b) with clay at different
time intervals. Cu: copper; CP: chelating polymer.

where k2 is the pseudo-second-order rate constant of adsorption. The abovementioned

two models basically considering external film diffusion, intraparticle diffusion, and
interaction step for adsorption process. The rate determining step of adsorption reaction
may be one of the above three steps.24
The kinetic parameters for the pseudo-first and pseudo-second models were determined
from the linear plots of log (qe  qt) versus t and (t/qt) versus t, respectively, as shown in
Figures 8 and 9 and Table 1. The validity of each model could be checked by the fitness of
the straight lines according to the values of correlation coefficients (R2 values).
It is clearly seen from the figures and correlation coefficient values that the sorption of
Cu2 ions by the prepared CP in presence and absence of clay fit well the pseudo-first-
order model and pseudo-second-order model, respectively. This indicated that the
sorption of Cu2 ions by the CP free of clay depends on both the concentration of Cu2
ions and adsorbent, while in case of CP containing clay, the sorption depends only on the
textural type of the adsorbent.

Adsorption isotherms. Equilibrium data, commonly known as adsorption isotherms, are

crucial necessities for the design of adsorption systems. These data give information on
the capacity of the adsorbent or the amount necessary to eliminate a unit mass of pol-
lutant under the system conditions.25,26
In order to adjust the design of a sorption system to remove pollutants from effluents,
it is important to set up the most proper correlation for the equilibrium curve. Two
isotherm equations have been tested in the current study, namely, Langmuir and
Freundlich. This modeling allows us to define the maximum capacity of removal. The
quality of the isotherm to fit the experimental data is normally verified according to the
value of the correlation coefficient (R2), that is, the isotherm giving R2 value closest to
unity is considered to provide the best fit.
Langmuir isotherm. The Langmuir adsorption model assumes that the molecules are
adsorbed at fixed number of definite sites, each of which can only hold one molecule and
Elhalawany et al. 9

4.56
4.54 a
ln (qe qt )

4.52
4.50
4.48
4.46
4.44
0 10 20 30 40 50 60
t
4.50
4.45 b
ln (qe qt )

4.40
4.35
4.30
4.25
0 10 20 30 40 50 60
t

Figure 8. The first-order plots for (a) CP without clay and (b) with clay. CP: chelating polymer.

0 .6
0 .5
0 .4
t/qt

0 .3 a
0 .2
0 .1
0 .0
0 20 40 60 80 100
t
0 .5
0 .4
0 .3 b
t/qt

0 .2
0 .1
0 .0
0 20 40 60 80 100
t

Figure 9. The second-order plots for (a) CP without clay and (b) with clay. CP: chelating polymer.
10 Journal of Elastomers & Plastics

Table 1. The kinetic parameters for pseudo-first-order and pseudo-second-order models.

First order Second order

Sample k1 R2 k2 R2

CP without clay 0.00131 0.72639 4.119  104 0.89688

CP with clay 0.00363 0.99902 4.377  104 0.92776

CP: chelating polymer.

Table 2. Different adsorption models parameters and coefficients for Cu2 ions sorption.

Langmuir Freundlich

Sample Qmax K R2 Kf N R2

CP without clay 55.804 0.00235 0.99982 51.712  103 0.912 0.996

CP with clay 66.934 0.00297 0.99908 11.857  103 0.694 0.988

Cu: copper; CP: chelating polymer.

no transfer of adsorbate in plane of the surface. These sites are also supposed to be
energetically equivalent and far away from each other, so that there are no interactions
between the molecules adsorbed to neighboring sites. The linear form of the Langmuir
isotherm is represented by the following equation27:
Ce Ce 1
4
qe Qmax Qmax K
Where qe is the amount of metal ion sorbed per unit weight of adsorbent (mg g1), Ce
is the equilibrium concentration of the metal ion in the equilibrium solution (mg L1),
Qmax (mg g1) is the monolayer adsorption capacity, and K (L mg1) is Langmuir
constant, which is related to the adsorption heat energy. The results obtained from the
Langmuir model for CIU by the prepared CPs are shown in Table 2 and Figure 10. The
values of maximum monolayer capacity Qmax obtained from Langmuir isotherm indicate
that the CP with clay has higher sorption capacity than that of clay free.

Freundlich isotherm. Freundlich isotherm is an empirical equation that involves the

heterogeneity, the exponential distribution of sites, and their energies. The sorption
data have been analyzed using the logarithmic form of the Freundlich isotherm as
shown below28:
Log qe N log Ce log Kf 5

Where Kf (mg L1) and N are Freundlich constants related to adsorption capacity and
adsorption intensity, respectively. The value of term N in the Freundlich isotherm model
shows the nature of isotherm to be unfavorable (N > 1), favorable (0 < N < 1), or
Elhalawany et al. 11

10.0 a
9.5
Ce /qe(gL1)

9.0
8.5
8.0
7.5
860 880 900 920 940 960
Ce (mg L1)
9.0
b
8.5
8.0
Ce /qe(gL1)

7.5
7.0
6.5
6.0
5.5
720 740 760 780 800 820 840 860 880 900 920
Ce (mg L1)

Figure 10. The Langmuir isotherm plots for (a) CP without clay and (b) CP with clay. CP: chelating
polymer.

irreversible (N 0). The results obtained from the Freundlich model for CIU by the
prepared CPs are shown in Table 2 and Figure 11. The correlation coefficients values
deduced from Freundlich equation showed that the Freundlich model is comparable to
the Langmuir model. The N values reported in Table 2 are lower than 1 indicating that
Cu2 ions sorption by the prepared CPs is favorable.
The correlation coefficients values listed in Table 2 indicated that the Cu2 ions
sorption process match more with Langmuir adsorption model than that of Freundlich.

Effect of pH. Figure 12 shows the uptake of Cu2 ions by the obtained CPs at different pH
values. It is shown from the figure that the metal ion uptake (MIU) increases as the pH
increases. At lower pH value (1 and 3), the dissociation of the carboxylic acid groups is
limited and hence reduces the chelation with different metal ions, but at higher pH value
(8.5 and 10), ionization of carboxylic acid groups takes place, which causes these
polymers to undergo a transition from a compact form to an extended form upon the
ionization of the primary carboxyl group29 and hence an increase in the MIU occurs. It is
clearly seen from the figures that CP with clay has much better sorption capacities than
CP free form clay. The maximum sorption capacities for Cu2 ions at the highest pH
value (pH 10) were 194 and 179.75 mg g1 for CP with and without clay, respectively.

Selectivity measurements. Since various metal ion pollutants may present in drinking water
as well as wastewater, it is essential to investigate the competitive binding affinity of
12 Journal of Elastomers & Plastics

2.05
2.04 a
2.03
log qe

2.02
2.01
2.00
2.98 2.97 2.96 2.95 2.94 2.93
log Ce

2.07 b
2.06
log qe

2.05
2.04
2.03
2.95 2.94 2.93 2.92 2.91 2.90 2.89
log Ce

Figure 11. The Freundlich isotherm plots for (a) CP without clay and (b) CP with clay.
CP: chelating polymer.

(a) CP without clay

(b) CP with clay
200
180
160
qe (mg g1)

140
120
100
80
60
0 2 4 6 8 10 12
pH

Figure 12. Uptake of Cu2 by CP without clay and CP with clay as a function of pH. Cu: copper;
CP: chelating polymer.

these ions toward the prepared CPs. The elements constitutions of the tested CPs were
detected by the EDX using a standard less qualitative (EDX) analytical technique. The
peak heights in the EDX spectra are proportional to the metallic elements concentration
which is chemisorbed. The EDX spectrum for Cr3, Co2, Ni2, Cu2, Cd2, and Pb2
ions is illustrated in Figure 13. It could be seen that all previously mentioned metal ions
Elhalawany et al. 13

Figure 13. EDX spectrum of grafted waste under adsorbed (a) without clay and (b) with clay.
EDX: energy-dispersive X-ray.

Table 3. Elemental constitutions (%) by EDX analyses.

Metal ions weight %

CPs Cr Co Ni Cu Cd Pb

Without clay 2.19 1.17 0.48 4.19 0.41 3.00

With clay 0.43 0.05 0.01 0.85 0.13 0.61

CP: chelating polymer; Cr: chromium; Co: cobalt; Ni: nickel; Cu: copper; Cd: cadmium; Pb: lead.

became one element of solid sample in this spectrum and that can be explained as those
ions may be chemisorbed on the surface of the CPs. Elemental constitution is illustrated
in Table 3, where it can be concluded that the percentage of adsorbed ions in absence of
clay is much higher than that of CP with clay. This may be attributed to the presence of
clay that enhances the Physisorption leading to weakness of the chemisorption on the
surface of CP containing clay.30 The sorption capacities of the tested metal ions are in the
order Cu2 > Pb2 > Cr3 > Cd2 > Co2 > Ni2 for CP with clay and in the order
Cu2 > Pb2 > Cr3 > Co2 > Cd 2 > Ni2 for CP free of clay, as shown in Figure 14
and Table 3.
Finally, we can conclude that the prepared CPs in this study have given promising
results compared to those reported by the traditional chelating resins. The maximum
sorption capacity reported in our study for Cu2 ions is much higher than that reported by
Coskun et al.,31 Turkmen et al.,32 Wang et al,33 Ji et al.,34 and Yoo and Kwak,35 as shown
from Table 4. In addition, the maximum sorption capacity for the studied metal ion is
highly increased at elevated pH values.
14 Journal of Elastomers & Plastics

Figure 14. The competitive binding affinity of the tested metal ions toward the prepared CPs.
CP: chelating polymer.

Table 4. Sorption capacity of different chelating resins.

Sorption
CPs capacity References

CP without clay 110 mg g1 Present study

CP with clay 123.36 mg g1 Present study
Methacrylic acid/acrylamide monomer mixture grafted 31.25 mg g1 Coskun et al.31
poly(ethylene terephthalate) fiber
Poly(hydroxyethyl methacrylate) 58 mg g1 Turkmen et al.32
Hyper-cross-linked polystyrene 75 mg g1 Wang et al33
Cellulose acetate/zeolite composite fiber 28.57 mg g1 Ji et al.34
Hyperbranchedpoly(amidoamine)-graftedpoly 14.2 mg L1 Yoo and Kwak35
(tetrafluoroethylene)

CP: chelating polymer.

Conclusion
In this study, a new easily prepared, low-cost, and efficient CPs based on waste poly-
styrene plastics have been used as potential adsorbents for removal of toxic heavy metal
pollutants from water system. The adsorption of Cu2 ions was found to be time
dependent. Adsorption isotherms have been studied in terms of Langmuir and Freundlich
isotherms models. The values of correlation coefficients deduced from the aforemen-
tioned two models confirmed that Cu2 ions sorption followed Langmuir adsorption
Elhalawany et al. 15

model. The selectivity measurements for different toxic heavy metal ions have been
investigated and it was found that the competitive binding affinity of the tested metal
ions is in the order Cu2 > Pb2 > Cr3 > Cd2 > Co2 > Ni2 for CP with clay and in
the order Cu2 > Pb2 > Cr3 > Co2 > Cd2 > Ni2 for CP free of clay. The MIU
increases with increasing pH values due to complete ionization of the COOH groups
occurred at higher pH values. Finally, we can conclude that these commercial, easily
prepared CPs have double positive features in which it helps to get rid of the organic
plastic wastes as well as toxic heavy metal pollutants.

Declaration of Conflicting Interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship,
and/or publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publication of this
article.

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