Hindawi

International Journal of Polymer Science

Volume 2020, Article ID 1239267, 15 pages
https://doi.org/10.1155/2020/1239267

Research Article
Removal of Cadmium (II), Chromium (III), and Lead (II) Heavy
Metal Ions from Water by Graft Copolymerization of
Acrylonitrile onto Date Palm Fiber Using H2O2/Fe++ as
an Initiator

1,2
Faraj Ahmad Abuilaiwi
1
Department of Chemistry, College of Science, University of Hafr Al Batin, P.O. Box 1803, Hafr Al Batin 31991, Saudi Arabia
2
Affiliated Colleges at Hafr Al Batin, King Fahd University of Petroleum and Minerals, P.O. Box 1803,
Hafr Al Batin 31991, Saudi Arabia

Correspondence should be addressed to Faraj Ahmad Abuilaiwi; [email protected]

Received 28 June 2020; Revised 30 September 2020; Accepted 4 October 2020; Published 21 October 2020

Academic Editor: Mehdi Salami-Kalajahi

Copyright © 2020 Faraj Ahmad Abuilaiwi. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

The study is aimed at assessing how the date palm wood fibers (DPWF) can be used for the removal of heavy metals from water.
The study involved examination of the radical polymerization and graft polymerization parameters such as reaction period,
reaction time, monomer volume, amount of the catalyst, and concentration of initiator to obtain the maximum yield of graft
polymerization. Fiber and copolymer were characterized using SEM and FT-IR spectroscopy to ensure the completion of
polymerization. Hydroxylamine hydrochloride was used for treating the grafted copolymers for the preparation of
polyamidoxime chelating resin, which was then examined for removing the heavy metal ions. Different resin dosages, contact
time, and initial concentrations were used, and the batch technique experiment was utilized. The study also applied the
Langmuir and Freundlich isotherm model, and Langmuir was found to be better. The absorption ability was found to be better
for polyamidoxime resin for metal ions of cadmium (II), chromium (III), and lead (II).

1. Introduction In order to address this issue, researchers are focusing on

the use of natural and bio-based materials [6]. Various kinds
Discharge of heavy metals in the industrial effluents has of biobased materials have been introduced, which may be
increased the problem of water pollution [1]. Previous studies based on cellular fibers, wood, or protein and help in reduc-
have revealed that nonbiodegradable heavy metals tend to ing the harmful effects caused by nonbiodegradable elements
accumulate in the bodies of living organisms and, for the same
[7]. Similarly, for the removal of heavy metals from aqueous
reason, they are more hazardous as compared to other water
solution, different methods, including precipitation and
pollutants [2]. Copper, silver, zinc, selenium, cadmium, mer-
cury, lead, nickel, chromium, tin, iron, arsenic, gold, molybde- membrane processes: reverse osmosis, ion exchange, ultrafil-
num, cobalt, manganese, aluminum, etc. are some commonly tration, and more, are being used [8]. The use of precipitation
found heavy metals [3], which are proved to be harmful for after coagulation is limited on account of high sludge volume.
humans and other living organisms [1]. Fu and Wang [4] Studies have identified membrane filtration as a cost-effective
stated that regular deposition of heavy metal subsequently way of ensuring the removal of metal ions; however, its cost is
causes severe damage to the central nervous system, skin, kid- a major impediment in its implementation [9, 10].
neys, teeth, liver, or lungs and could also lead to death. Addi- Kanamarlapudi et al. [10] found absorption as an effi-
tionally, the removal of heavy metals is also challenging on cient, simple, and effective approach in the removal of heavy
account of their nonbiodegradability [5]. metals from the wastewater; however, its high cost is also
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2 International Journal of Polymer Science

major challenge in its implementation. These challenges 1.1. Modified Date Palm as Adsorbent of Heavy Metals. In 30
instigated scholars and researchers to find or develop cost- countries, approximately 120 million date palm trees are cul-
effective, eco-friendly, and nonconventional absorbents [9]. tivated covering an area of 800,000 hectares [22, 23]. The
Recently, the interest in the use of plant-based fiber has investigation of the regional distribution shows that approx-
increased, which is commercially in the production of poly- imately 60 million date palm trees are located in Iran, Iraq,
mer composites [1]. These composites can be used for Oman, Pakistan, Saudi Arabia, Yemen, Bahrain, and Turk-
removing the heavy metal ions from water especially when menistan, and almost 32.5 million date palm trees are located
conventional methods are proved ineffective [11]. In order in Africa. El-Hendawy [24] investigated the adsorption
to satisfy and solve the above-mentioned problems, some capacities of date pit-activated carbons with respect to Pb2+
natural materials such as cellulose, chitosan, chitin, and their and Cd2+. Data were compatible with the Langmuir model,
derivatives have been specified as good and inexpensive which substantially contributed to the increase in adsorption
options because of their economic efficiency, absorbent prop- capacity in comparison with raw date pits and subsequently
erties, safety, and biodegradability. led to the increase in the adsorption of lead. The consump-
Ion exchange is a reaction in which free mobile ions of a tion was higher than cadmium due to its suitable pH for
solid are exchanged with different ions of identical charge in complexation or deposition and lower solubility. el Nemr
a solution. The exchanger contains an open network structure, et al. [25] assessed the removal of toxic chromium (VI) from
either organic or inorganic, which carries the ions and let ions different aqueous solutions with the help of an adsorbent
to pass through it. Ion exchangers may be organic or inorganic containing activated carbon obtained date palm seed. The
and are natural or synthetic materials such as synthetic resins optimum pH for absorption was 1.0, and the increase in
which function as ion exchangers based on three-dimensional pH decreased the adsorption percentage. 120.48 mg/g was
organic networks bearing charged or potentially charged the maximum adsorption capacity for chromium (VI), and
groups [12]. Past research has shown increased interest in the equilibrium was obtained in 180 min due to the fast
the use of date palm as a biodegradable material [13]. adsorption process. Studies have shown that the use of date
Recently, many studies have focused on exploring an stone and palm tree waste increases the Cu2+ adsorption,
alternative metal adsorbent and grafted polymers. Grafting is where equilibrium was obtained within 120 min [26, 27].
the method in which functional monomers are covalently Hilal et al. [28] stated that maximum absorption capacity of
bonded to the backbone polymer chain [14–17]. Graft polymer- activated date pits was at a pH of 5:8 ± 0:5, which was five
ization is significant as it permits implementing different func- times greater than that of the raw date pits.
tions of the grafted monomer on the parent polymer while Abdulkarim and Al-Rub [29] studied the removal of lead
retaining the mechanical features of the parent polymer. (II) onto activated carbons, and 8-hydroxyquinoline modi-
Radiation-induced grafting technique is dominant over all other fied activated carbons from date pits. The adsorption capac-
approaches implemented to initiate graft copolymerization ity was high in both the carbons; however, no significant
such as ultraviolet light, decomposition of chemical initiators, improvement was found in adsorption after modification.
oxidation of polymers, plasma treatment, and ionizing radiation Removal of Pb (II) ions using activated carbons was
because of its extensive penetration into the polymer matrix and increased with an increase in pH. This process followed
its rapid and homogeneous development of radicals [18, 19]. pseudo-second-order kinetics. The Langmuir and Freundlich
Date palm (“Phoenix dactylifera”) is abundantly grown models showed good agreement from the equilibrium data
throughout Saudi Arabia, and its global production rate is for the adsorption of lead (II) ions. Yadav et al. [30] showed
42%. It is an edible fruit with a papery skin and a single, long, that date palm fibers can remove 99.955 chromate anions
narrow, hard seed. There are many uses of date palm wood; (Cr6+) from a 100 mg L-1 solution with the use of a small
for instance, it is used as posts and rafters for huts because it absorbent dosage, i.e., 1.2 g L-1.
is lighter than coconut. It is also used in the construction of Tunisian date stones activated via phosphoric acid were
aqueducts, bridges, and parts of boats and dhows. Moreover, used for the removal of copper (II) from aqueous solutions.
the tree residues are used as fuel [20]. Date palm contains three The best-activated carbon for the removal process was
major components: cellulose, lignin, hemicellulose, and other obtained with 60% phosphoric acid and an impregnation
minor constituents such as protein and oil [21]. ratio of 1.75 at 450°C. Dubinin–Kaganer–Radushkevich and
The focus of this is on date palm on account of its abun- Langmuir adsorption isotherm models were enough to
dance, cost-effectiveness, and renewability in the Kingdom of explain the adsorption of copper (II) onto activated carbon
Saudi Arabia. Its fiber produces biodegradable materials (q°) which was found to be 31.25 mg/g. Bouhamed et al.
when treated with certain monomers and can be obtained [26] suggested a chemisorption process from kinetic data
at low costs in comparison with the costly plastic materials that were compatible with the pseudo-second-order kinetic
which are commonly used for removing metal ions from model.
water. The limitations associated with heavy metals have el-Shafey and al-Kindy [31] modified leaflets of date palm
led to extensive researches for the production of cost- using the sulphuric acid method at 170°C. They suggested
effective alternatives which should be excessively available that the hot sulphuric acid dehydrates and induces reduction
as waste materials. In the current study, the effectiveness of property in carbon. This carbon was used to remove copper
date palm fibers as low-cost bioabsorbent of heavy metals and silver from aqueous solution using various parameters
has been studied, with a focus on the impacts of the different such as contact time, pH, temperature, and metal concentra-
reaction parameters that influence the adsorption efficiency. tion. Adsorption of copper was greater as compared to the
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International Journal of Polymer Science 3

adsorption of silver as the equilibrium was reached within times with the methanolic solution. The resin was neutral-
∼2 h and ∼60 h, respectively. The adsorption of copper was ized by treating it with 0.1 M HCl solution for 15 min;
carried out through the diffusion-controlled ion exchange afterwards, it was again filtered, washed several times with
process; however, the value of activation energy of silver indi- the methanolic solution, and then dried in an oven at a
cated chemisorption of silver ions into carbon. constant weight at 60°C.
The adsorption capacities of raw date pits and CO2 acti-
vated date pits were compared with respect to the adsorption 2.5. Sorption of Lead Cadmium and Chromium Ions Using the
of copper and zinc ions. Banat et al. [32] found adsorption of Batch Technique. The lead, cadmium, and chromium ion
both copper and zinc onto raw date pits higher than adsorp- adsorption capacities of the resin were measured over the
tion onto activated date pit carbon. This attributed to the dif- pH range of 1–6. Thus, ca. 0.1 g of dried resin was placed in
ference in the surface functional groups of date pits and a series of 100 ml polyethylene bottles and equilibrated with
activated date pits. The heating during the activation process 20 ml of distilled water. After adding 20 ml of 0.1 M sodium
may have destroyed the functional groups that facilitate acetate buffer solution in each bottle, 10 ml of 0.1 M lead-
binding of zinc and copper. The removal of copper was better ions solution was added. The resulting mixture was shaken
in comparison with the removal of zinc with respect to both for 24 h by a rotary shaker, and afterwards, 5 ml of the super-
the materials on account of its small ionic radius that facili- natant was collected for the determination of metal-ions. An
tates an easy movement into porous surface. The best result AGBC-903 atomic absorption spectrometer was used to
was obtained at pH = 5 and temperature at 25°C. determine the initial and final amounts of metal ions present
in the solutions.
2. Methodology Blank experiments were performed, and the same exper-
imental procedure was conducted for checking the adsorp-
2.1. Materials and Reagents. A nonwoven polyethylene fabric tion level by the membrane filters and glass flasks for all
was used as a trunk polymer for graft polymerization; the adsorption tests. The kinetic samples were conducted in
material was obtained from Kurashiki MFG Co. Monomer 1000 ml batch reactors at 20.0 in deionized water. The flasks
acrylonitrile (BDH, England) was used for grafting onto a were vigorously and magnetically stirred for 1.5 h for hydrat-
trunk polymer. Sodium carbonate, methanol, acetone, and ing the beet pulp to naturally maintain the pH at 5.5.
sulphuric acid were obtained from Merck, Germany, and
hydroxyl amine hydrochloride was obtained from Sigma- 2.6. Graft Copolymerization. To prepare the fiber/PAN
Aldrich, USA. Cadmium (II), lead (II) acetate trihydrate copolymer, 1.00 g DPW fiber was placed in 250 ml three-
(Merck, Germany), and chromium (III) (Techno Pharm- necked flasks equipped with a stirrer and condenser and
chem, India) were used for a metal adsorption study. Date immersed into a thermostatic water bath. The DPW suspen-
palm fiber was obtained from a local market, and the size of sion was obtained by adding 100 ml distilled water and 0.1 g
the fiber was less than 200 μm. The fiber was washed two ferrous ammonium sulphate with continuous stirring. Nitro-
times with hot distilled water and acetone. The acetone was gen purged through the DPW fiber slurry to remove oxygen
removed by heating the fiber in an oven at 60°C. during the reaction. After 30 min, the required volume of
2.0 M H2O2 was added and the mixture was mixed for
2.2. FTIR Spectroscopy. Infrared (IR) spectra of the DPW, 5 min; afterwards, the required amounts of monomer (AN)
grafted DPW, and the poly (amidoxime) ion-exchange were added into the mixture. The reaction mixture was stir-
resin samples were recorded on a Fourier transform–IR red under nitrogen at the chosen temperature and for the
spectrometer (Perkin–Elmer 1725, Norwalk, CT) using a predetermined reaction period. Immediately after the reac-
KBr disk pellet. tion, the reaction flask was cooled by placing it under run-
ning tap water, and the product was filtered. The crude
2.3. Scanning Electron Microscopy (SEM). The SEM photo- product was washed thoroughly with distilled water and
graphs of the fiber surfaces of grafted PAN onto DPW and oven-dried at 60°C at a constant weight.
ungrafted DPW fiber were captured using a scanning electron
microscope model SEM JEOL 6400 (JEOL, Peabody, MA). 2.7. Removal of Polyacrylonitrile and Determination of Graft
Level. The crude product was purified with N,N-dimethylfor-
2.4. Preparation of a Chelating Resin Containing mamide using a Soxhlet extractor for 48 h to remove the
Polyamidoxime Groups. Hydroxylamine hydrochloride polyacrylonitrile (PAN). The pure grafted copolymers were
(NH2OH.HCl) solution was prepared by dissolving 20 g then dried at 65°C at a constant weight. The following for-
(0.288 mol) of hydroxylamine hydrochloride in 300 ml of a mula determined the percentage of grafting (Pg):
methanolic aqueous solution (methanol/water ratio = 80).
The hydrochloride content of NH2OH.HCl was neutralized
by the addition of NaOH solution, and the precipitated NaCl W2 − W1
Pg = × 100, ð1Þ
was removed by filtration. The grafted product was placed in W1
a two-necked flask equipped with a condenser; the flask was
placed in a thermostatic water bath, and the hydroxylamine
solution was poured in it. The mixture was allowed to react where W 1 is the weight of the original DPW fibers in grams
at 70°C with continuous stirring for 180 min. After comple- and W 2 is the weight of the grafted product after copolymer-
tion of the reaction, the resin was filtered and washed several ization and extraction [33].
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4 International Journal of Polymer Science

Fe2+ + H2O2 Fe3+ + HO– + HO

Initiation
HO
H2O
Fiber + Fiber· +
Fe3+ Fe2+

Propagation C N C N
+ n H2C CH Fiber CH2 CH
M

C N C N C N C N

Fiber CH2 CH + H2C CH Fiber CH2 CH CH2 CH

n–1

C N C N C N C N
Fiber CH2 CH CH2 CH + HC CH2 CH CH2 Fiber
n m

N C N C C N C N
Fiber CH2 CH CH2 CH CH CH2 CH CH2 Fiber
m+n
Grafted copolymer

Fiber + M M Fiber M M
n n
Grafted copolymer

M M + M M M M M
n n 2n
Homopolymer

Figure 1: Mechanism of graft copolymerization of acrylonitrile onto DPWF.

2.8. Graft Copolymerization. Date palm wood fiber (DPWF) 2.9.1. Effect of Temperature. A wide range of temperatures
was treated with a mixed solution of hydrogen peroxide was used to obtain the best yield of the grafted copolymer.
and ferrous ammonium sulfate to initiate a free radical Figure 2 illustrates the effect of temperature that increase in
in the backbone of the fiber and provide cellulose macro- temperature from 30°C up to 75°C increases the % yield of
radical. Graft copolymerization occurred after adding acry- grafting. This increase could be attributed to the increase of
lonitrile (AN) monomer to the mixture during which the monomer diffusion into the active sites on the backbone of
cellulose macroradical broke the double bond in AN and the substrate. If temperature goes above 75°C, the monomer
a covalent bond between monomer and cellulose was starts to evaporate, and hydrogen peroxide decomposes. This
formed, the chain initiated with continues creation of free condition leads to creation of a huge number of free radicals,
radical on the AN. Chain grafting onto the cellulose was the yield of a homopolymer will increase, and % of the
possible by adding AN monomer subsequently. The reac- grafted copolymer in pg will decrease [36, 37].
tion was ultimately terminated either by the formation of
a copolymer on account of the reaction of two macroradi- 2.9.2. Effect of the Concentration of Initiator. The yield of
cal or formation of poly(methacrylate) by the reaction of grafted polymer is clearly affected by the concentration of
two monomer radicals. Figure 1 explains the whole pro- the initiator. As shown in Figure 3, the % of grafting
cess [34, 35]. increased with the increase in the concentration of the hydro-
gen peroxide as it increases the production of free radicals in
2.9. Optimization of Grafted Polymerization Parameters. the active sites of the fiber. At 0.03 M concentration, 81%
Effects of various parameters on the yield of grafted copoly- grafting was obtained. However, the grafting percentage
merization were studied. These parameters included temper- decreased with further increase in the percentage of hydro-
ature, reaction time, monomer volume, cocatalyst amount, gen peroxide because of the reaction between cellulose radi-
and concentration of initiator. All these parameters were cals before addition of monomers, and this reaction is the
studied separately to investigate the best conditions and to termination step. Moreover, at higher concentrations, the
obtain the best yield. yield of homopolymer increases [34].
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International Journal of Polymer Science 5

90

80

70

60

% of grafting (pg)
50

40

30

20

10

0
30 40 50 60 70 80 90

Temperature ( C)

Figure 2: Effect of reaction temperature on the % of grafting in pg. Reaction time: 60 min, AN: 8 ml, H2O2: 0.03 M, Fe+2: 0.3 mmol, and (Δ): %
of grafting.

90
80
70
60
% of grafting

50
40
30
20
10
0
0.01 0.02 0.03 0.04
Concentration of initiator (M)

Figure 3: Effect of the amount of initiator H2O2 on the % of grafting. Reaction time: 60 min, AN: 8 ml, temperature: 75°C, Fe+2: 0.3 mmol, and
(Δ): % of grafting.

2.9.3. Effect of the Amount of Monomer. The percentage of found to be enough for the best yield of a product
grafting increased with the increasing volume of the (AN) (Figure 6), where 0.306 mmol of catalyst gave 81% of grafting
monomer on account of the availability of a large number product. This yield decreased with the increase in the amount
of monomer molecules reaching the active sites in the back- of the catalyst on account of a large number of radicals pro-
bone of the fiber. However, as shown in Figure 4, increase duced by the decomposition of hydrogen per oxide. The reac-
in volume over 8 ml decreased the percentage of grafting on tion finally terminates due to the reaction between radicals
account of the increased possibility of homopolymerization and yield will decrease [33, 40].
[37, 38].
2.10. Preparation of Polyamidoxime Resin. The AN-DPWF
2.9.4. Effect of Reaction Period. The percentage of grafting grafted copolymer containing nitrile group was treated with
was found directly proportional to the increase in the reac- hydroxylamine hydrochloride at pH 11 to change the nitrile
tion time, and it increases the time available to all monomer group into amidoxime. This reaction was performed for 3
molecules to reach the active sites on the backbone; however, hours at 75°C, and the ratio between grafted copolymer and
the maximum grafting yield was obtained with the reaction hydroxylamine in methanolic solution was 1 : 1. The mecha-
time of 60 minutes. Afterwards, all active sites were covered, nism of this conversion is shown in Figure 7.
and the concentration of all reaction species decreased and
this accounted for the low yield of grafting which almost 2.11. Characterization of AN-DPWF Grafted Copolymer and
remains constant with increasing time [39]. This explanation Resin. FT-IR spectra were obtained for DPWF, grafted copol-
is in line with the results shown in Figure 5. ymer, and amidoxime resin to confirm the completion of
polymerization and conversion of grafted copolymer into
2.9.5. Effect of the Amount of Catalyst. Small amount of the chelating resin. In Figure 8, the same characteristic
ammonium ferrous sulphate [(NH4)2SO4·FeSO4·6H2O] was adsorption bands for DPWF, such as broad absorption band
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6 International Journal of Polymer Science

140

120

100

% of grafting
80

60

40

20

0
2 4 6 8 10
Volume of monomer (ml)

Figure 4: Effect of the amount of monomer (AN) on the % of grafting. Reaction time: 60 min, H2O2: 0.03 M, temperature: 75°C, Fe+2:
0.3 mmol, and (Δ): % of grafting.

100
90
80
% of grafting

70
60
50
40
30
20
30 45 60 75 90 105 120

Time (min)

Figure 5: Effect of reaction period on the % of grafting and efficiency. AN: 8 ml, H2O2: 0.03 M, temperature: 75°C, Fe+2: 0.3 mmol, and (Δ): %
of grafting.

90

80

70
% of grafting

60

50

40

30
0.15 0.35 0.55 0.75 0.95 1.15
Amount of catalyst Fe+2 (mmol)

Figure 6: Effect of the amount of catalyst Fe+2on the % of grafting. AN: 8 ml, H2O2: 0.03 M, temperature: 75°C, time: 60 min, and (Δ): % of
grafting.

between 3000 and 3500 cm-1 were assigned to O-H stretching teristic adsorption at 2240 cm-1 for C≡N stretching modes
vibration and bands that appeared at 2900 and 1020 cm-1 for confirms the presence of acrylonitrile onto the backbone of
C-H stretching and bending modes, respectively. The charac- DPWF and grafting reaction completely [41].
 9484, 2020, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2020/1239267 by Nat Prov Indonesia, Wiley Online Library on [24/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
International Journal of Polymer Science 7

Polymer +
NH2
C + H2N – OH
Polymer OH
N N–

NH
NH
Polymer OH
Polymer OH
NH
NH

NH2
P C N + H2NOH NaOH P C
N OH

Figure 7: Reaction mechanism of preparation of polyamidoxime resin.

110

105
Transmittance (%)

100

95

90

85
4000 3500 3000 2500 2000 1500 1000 500
Wave length (cm−1)
AN polymer
Fiber
Resin

Figure 8: FTIR DPWF fiber (─), AN-g-DPWF fiber (- -), and resin containing amidoxime groups (···).

This band disappeared completely after conversion to counter ions on the resin, ability of ionization, and solubility
amidoxime resin, and new adsorption band formed at of adsorbates depend on pH [43]. A wide range of pH (1.0 to
1650 cm-1 associated with C=N vibration of the amidoxime 6.0) was investigated to get the optimum pH for a fixed con-
group. Another adsorption band observed at 941 cm–1 may centration of metals and dosage of resin at 25°C. The adsorp-
be assigned to the N–O bond of the oxime group [42]. Scan- tion of lead (II), Cr (III), and Cd (II) was maximum at the
ning electron microscope (SEM) images were taken for pH = 5:0 as shown in Figure 11. At low pH (<3.0), the com-
DPWF before and after polymerization to investigate the petition between H+ ions for the resin sites increased and the
changes in the morphology of the fiber surface. Figures 9 resin’s chelating ability was greatly reduced. At pH 5, the
and 10 show the surface of the fiber before and after grafted competition of H+ ions for the resin sites decreases and the
polymerization, respectively. As can be seen in Figure 10, chelating ability of the metal ion increases [44]. Equation
all pours on the DPWF surface were covered with polyacry- (2) is used to calculate the percentage of the removal of metal
lonitrile (PAN) via the chemical bond and this covering ions using this resin [39, 45, 46].
yielded a homogeneous surface with less porosity.
C0 − Ce
%of removal = × 100: ð2Þ
2.12. Effect of Initial pH. The pH solution is a substantial C0
parameter used in the study of the removal of heavy metal
ions from aqueous solution or water on account of many rea- 2.13. Effect of Contact Time and Initial Concentration. The
sons such as its effects on the concentration of counter ions contact time is one of the important parameters to study as
placed in adsorbent functional clusters, the level of ionization it affects the adsorption of heavy metals onto chelating resin.
of the adsorbate during the reaction, and the solubility of From Figure 12, it can be observed that the adsorption of
metal ions. Batch technique was conducted to find out the heavy metals increases with the increase in the contact time.
optimum pH level required for the removal of heavy metals Also, the adsorption was fast in the beginning until it reaches
using amidoxime chelating resin. The concentration of the equilibrium at 35 min, and afterwards, the value of qt (mg/g)
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8 International Journal of Polymer Science

Figure 9: Scanning electron micrographs of DPWF before grafting, SEM MAG (1.36 KX).

Figure 10: Scanning electron micrographs of DPWF after grafting, SEM MAG (1.47 KX).

120

100

80
% of removal

60

40

20

0
1 2 3 4 5 6
pH
% of removal Pb
% of removal Cd

Figure 11: Effect of pH on the adsorption of (Pb+2), (Cr+3), and (Cd+2) ions; dosage of chelating resin: 1 g; ion concentration: 50 mg/L; time:
60 min; and temperature: 25°C.
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International Journal of Polymer Science 9

25 20 20

20
15 15

qt (mg/g)
15
qt (mg/g)

qt (mg/g)
10 10
10
5 5
5

0 0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60

Time (min) Time (min) Time (min)

70 mg/L 70 mg/L 70 mg/L

50 mg/L 50 mg/L 50 mg/L
30 mg/L 30 mg/L 30 mg/L

(a) (b) (c)

Figure 12: Effect of contact time on (a) lead (II), (b) Cr (III), and (c) Cd (II) adsorption at different initial feed concentration; solution: pH 5;
and temperature: 25°C.

100

80
Removal (%)

60

40

20

0
0.5 1 1.5 2
Resin dosage (g/L)
Pb (II)
Cr (III)
Cd (II)

Figure 13: Effect of adsorbent dosage on adsorption of lead (II), Cr (III), and Cd (II); initial concentrations: 50 mg/L; time: 60 min; solution:
pH 5; and temperature: 25°C.

remains constant. This can be attributed to the availability of 2.14. Effect of Adsorbent Dosage. The efficiency of the ami-
active sites on the surface of chelating resin in the beginning doxime chelating resin dosage was investigated on the basis
of reaction [47]. Initial concentration of metals under study: of its initial concentrations. Adsorption of lead (II), Cr (III),
lead (II), Cr (III), and Cd (II), influenced the removal of these and Cd (II) was studied with different dosages of resin and
metals. The amount of metal ions, qt (milligrams per gram) 50 mg/l as the initial concentration of metals at 25°C and
adsorbed, is calculated by increasing the initial concentra- pH = 5. According to Figure 13, when the resin dosage was
tions. The following equation is used to calculate metal ion increased from 0.05 g/l to 2 g/l, the percentage of removal
adsorption at certain time, t (qt mg/g): from 61.1% to 87.84% for lead (II), from 49.94 to 71.50%
for chromium (III), and from 50.26 to 67.48 for cadmium
ν (II) was observed. This increase in the removal percentage
qt = ðc0 − ct Þ × : ð3Þ can be attributed to the availability of huge surface area and
m number of active sites on account of increase in the dosage
of resin at constant concentration of metal ions.
This can be illustrated by the ratio between available sur-
face and initial metal ion concentration. On higher concen- 2.15. Adsorption Kinetics. To investigate the adsorption
tration, this ratio was low and it increased with the lower mechanism and reaction pathways, some adsorption kinetic
concentration and the initial concentration also affects the studies were conducted. Various kinetic models were applied
removal of heavy metals [48]. to analyse the adsorption process of lead (II), Cr (III), and Cd
 9484, 2020, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2020/1239267 by Nat Prov Indonesia, Wiley Online Library on [24/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
10 International Journal of Polymer Science

1.2 1.4
1.3
1.0 1.2
1.1
1.0
0.8 0.9
0.8
0.6 0.7
0.6
0.5 0.4
0.4
0.3 0.2
0.2 0.1 0.0
0.0 –0.1 -0.2
5 10 15 20 25 30 35 40 5 10 15 20 25 30 35 40 5 10 15 20 25 30 35 40
Time (min) Time (min) Time (min)
70 mg/L 70 mg/L 70 mg/L
50 mg/L 50 mg/L 50 mg/L
30 mg/L 30 mg/L 30 mg/L

(a) (b) (c)

Figure 14: Lagergren first-order plot for adsorption of (a) Pb (II), (b) Cr (III), and (c) Cd (II) on amidoxime chelating resin for different initial
feed concentrations at pH 5 and temperature at 25°C.

(II) onto chelating resin. These models include pseudo-first- Equation (6) can be expressed as
order, pseudo-second-order, and intraparticle diffusion.
Models with high correlation coefficients (R2 ) may describe t 1 t
= + : ð7Þ
the adsorption of metal onto chelating resin. qt k2 qe2 qe
2.15.1. The Pseudo-First-Order Model. The pseudo-first-
The initial adsorption rate, h (milligrams per gram per
order kinetic model illustrates the adsorption mechanisms
minute), is given as
in solid-liquid systems, which is generally expressed as

k1 t h = k2 qe2 : ð8Þ
Logðqe − qt Þ = Logqe − , ð4Þ
2:303
Equation (7) also can be written as
where k1 is the rate constant of pseudo-first-order adsorption
(per minute) and qt and qe are the quantities of metal ions t 1 t
= + : ð9Þ
adsorbed (milligrams per gram) at time t and equilibrium, qt h qe
respectively [39, 49]. The plots of log (qe − qt ) versus t dem-
onstrated in Figure 14 give the value rate constant k1 and The plots of t/qt versus t from Equation (9) at different
adsorption density qe from the slope and intercept, respec- concentrations of lead (II), Cr (III), and Cd (II) are shown
tively. Bad linearity was obtained for this model, and it was in Figure 15. From slope and intercept, adsorption parame-
clear from the values of correlation coefficients (R2 ) which ters qe (Cal.) and k2 were calculated, respectively (Table 1).
was low for different concentrations. Moreover, no agree- The high linearity of the plots was indicated by values of cor-
ment was observed between the experimentally observed relation coefficients (R2 ) (≥0.99), which means that the
equilibrium adsorption (qe , exp) and that derived theoreti- adsorption kinetics between amidoxime chelating resin and
cally (qe , cal), which means that the adsorption of metal ions heavy metals can be described using a pseudo-second-order
onto chelating resin kinetic data was not compatible with the adsorption kinetic model. Moreover, the good agreement
pseudo-first-order kinetic model. between (qe , Cal.) and (qe , Exp.) gives evidence for the com-
patibility of the adsorption data. This shows that the adsorp-
2.15.2. The Pseudo-Second-Order Equation. The pseudo- tion of heavy metals onto amidoxime chelating resin occurs
second-order adsorption kinetic rate is expressed as through the chemical interaction between the adsorbent
and adsorbate [50–52].
dqt
= k2 ðqe − qt Þ2 , ð5Þ
dt 2.15.3. The Intraparticle Diffusion Model. Adsorption mech-
anism and intraparticle diffusion rate determined steps of
where k2 is the rate constant of the pseudo-second-order lead (II). Cr (III) and Cd (II) onto chelating resin were iden-
sorption (g/mg·min), qe and qt are the sorption capacities at tified using the Weber and Morris model. The rate constant
equilibrium and time t (mg/g), respectively. For the bound- for intraparticle (kid) can be expressed as
ary conditions t = 0 to t = t and qt = 0 to qt = qt , the inte-
grated form of Equation (5) will be as qt = kid t 1/2 + C: ð10Þ

1 1 Figure 16 shows the plots of qt versus t 1/2 . It is clear that

= + k2 t: ð6Þ
qe − q t qe all lines for different concentrations do not pass through the
 9484, 2020, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2020/1239267 by Nat Prov Indonesia, Wiley Online Library on [24/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
International Journal of Polymer Science 11

6 7
5
5 6
4 5
4
3 4
3
3
2
2
2
1 1 1
0 0 0
10 15 20 25 30 35 40 45 50 55 60 10 15 20 25 30 35 40 45 50 55 60 10 15 20 25 30 35 40 45 50 55 60

Time (min) Time (min) Time (min)

70 mg/L 70 mg/L 70 mg/L
50 mg/L 50 mg/L 50 mg/L
30 mg/L 30 mg/L 30 mg/L

(a) (b) (c)

Figure 15: Pseudo-second-order kinetic plot for adsorption of (a) Pb (II), (b) Cr (III), and (c) Cd (II) on amidoxime chelating resin for
different initial feed concentrations at pH 5 and temperature at 25°C.

Table 1: Kinetic constant parameters obtained for heavy metal adsorption on polyamidoxime resin.

Pseudo-first order Pseudo-second order Intraparticle diffusion model

Metal Ci qe exp K 1 (10-3) qe cal 2 K 2 (10-2) qe cal h K id C
R R2 R2
(mg/L) (mg/g) (min-1) (mg/g) (g/mg·min) (mg/g) (g/min) (mg/g·min) (mg/g)
70 22.40 41.22 518.8 0.976 0.30 17.95 0.97 0.996 2.262 5.397 0.992
Lead (II) 50 23.90 32.7 226.01 0.976 0.40 27.03 2.91 0.992 1.733 10.521 0.990
30 13.81 53.19 363.09 0.981 0.24 27.85 1.82 0.990 1.567 2.112 0.979
70 19.58 62.87 1659.7 0.880 0.08 32.79 0.898 0.974 2.929 1.631 0.965
Chromium (III) 50 16.39 33.85 111.88 0.994 0.93 17.64 2.89 0.995 0.856 9.645 0.986
30 10.72 29.48 43.58 0.974 0.31 14.47 0.64 0.970 1.259 1.08 0.988
70 16.24 45.14 832.6 0.937 0.399 36.49 0.53 0.947 2.745 3.999 0.983
Cadmium (II) 50 15.54 53.19 19.13 0.921 1.1 16.86 3.14 0.998 0.808 9.54 0.977
30 8.92 51.82 72.31 0.924 0.503 11.48 0.66 0.986 0.977 1.662 0.967

point of origin indicating the difficulty of predicting the where C e is the equilibrium concentration (mg/l) of metals in
mechanism of the overall process, and it seems to be very solution; qe is the amount of metal ions adsorbed (mg/g) at
complex [46, 53]. equilibrium; K L is the Langmuir equilibrium constant
(l/mg), and it is related to the affinity of adsorption sites;
2.16. Adsorption Isotherm Models. The adsorption efficiency and qm gives the maximum theoretical monolayer adsorption
of polyamidoxime chelating resin towards heavy metals was capacity (mg/g). The values of qm and K L (Table 2) were
tested using some isotherm models. It describes the partition obtained from the slope and intercept, respectively, of plots
of adsorbate molecules between liquid and solid phases at of Ce /qe versus Ce , which are shown in Figure 17. The linear-
equilibrium. Langmuir and Freundlich adsorption isotherm
ity and high values of correlation coefficients (R2 ) indicate
models were used to determine the adsorption capacity of
that the Langmuir model describes the adsorption process
amidoxime chelating resin towards lead (II), Cr (III), and
very well, confirming the formation of monolayer. Weber
Cd (II).
and Chakravorti [55] defined the separation factor (RL ) as a
2.16.1. The Langmuir Isotherm Model. The Langmuir model characteristic dimensionless equilibrium parameter for the
assumes that the monolayer adsorption process takes place Langmuir model, and it is expressed as
between the adsorbate and adsorbent, and the surface is
homogenous with a finite number of active sites when sites 1
are filled with adsorbate molecules. There is no chance of fur- RL = : ð12Þ
1 + K L Co
ther adsorption on this site, and the saturation point is
accomplished [54]. The linear equation is expressed as
The values of RL for each initial concentration was less
than unity and greater than zero indicating the favourable
Ce 1 C
= + e, ð11Þ adsorption of lead (II), Cr (III), and Cd (II) on polyamidox-
qe K L qm qm ime chelating resin [53].
 9484, 2020, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2020/1239267 by Nat Prov Indonesia, Wiley Online Library on [24/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
12 International Journal of Polymer Science

25 25 20

20 20
15
15 15
10
10 10

5 5 5

0 0 0
3 4 5 6 7 8 3 4 5 6 7 8 3 4 5 6 7 8

70 mg/L 70 mg/L 70 mg/L

50 mg/L 50 mg/L 50 mg/L
30 mg/L 30 mg/L 30 mg/L

(a) (b) (c)

Figure 16: Intraparticle diffusion kinetic plot for adsorption of (a) Pb (II), (b) Cr (III), and (c) Cd (II) on amidoxime chelating resin for
different initial feed concentrations at pH 5 and temperature at 25°C.

Table 2: Langmuir and Freundlich isotherm constants for lead (II), Cr (III), and Cd (II) adsorption on amidoxime chelating resin.

Langmuir isotherm constants Freundlich isotherm constants

Compounds T (k)
qm (mg/g) K L (L/mg) RL R2 1/n n KF R2
Lead (II) 298.16 43.86 9.12 0.002 0.999 0.04 23.15 48.62 0.8638
Chromium (III) 298.16 42.74 5.32 0.004 0.999 0.06 15.43 49.74 0.9701
Cadmium (II) 298.16 32.47 1.54 0.012 0.993 0.10 10.04 48.07 0.7647

0.3 1.0 1.0

0.8 0.8
0.2
0.5 0.5

0.1
0.3 0.3

0.0 0.0 0.0

0.0 2.0 4.0 6.0 8.0 10.0 12.0 9.0 11.0 13.0 15.0 17.0 19.0 21.0 23.0 12.0 14.0 16.0 18.0 20.0 22.0

(a) (b) (c)

Figure 17: Langmuir adsorption isotherms for adsorption of (a) Pb (II), (b) Cr (III), and (c) Cd (II) on amidoxime chelating resin, pH 5, and
temperature at 25°C.

2.16.2. The Freundlich Isotherm Model. The Freundlich Values of n more than the unit mean favourable adsorption
model is always used to describe the adsorption on heteroge- condition, and lead (II), Cr (III), and Cd (II) are favourably
neous surface of adsorbent [56]. Different initial concentra- adsorbed via amidoxime resin [53].
tions of heavy metals were used with fixed dosage of
amidoxime resin to obtain the equilibrium data. The Freun-
dlich isotherm model is expressed as follows: 3. Conclusion
This study used the grafted copolymerization of date palm
1
ln qe = ln k f + ln C e , ð13Þ wood fiber using hydrogen peroxide as an initiator and
n ammonium ferrous sulphate as a catalyst. It studied the
grafting parameters for obtaining the best grafting percent-
where K f (mg/g) and n (g/L) are the Freundlich adsorption age. The grafting percentage depends upon the parameters
constants. The plots of ln qe against ln C e shown in such as the reaction period, reaction temperature, amount
Figure 18 give straight lines. From the slope and intercept of the catalyst, concentration of the initiator, and mono-
of those lines, the values of n and K f can be calculated. Bad mer volume. The best grafting percent was obtained using
linearity and low values of correlation coefficient (R2 ) indi- acrylonitrile monomer under following conditions: 8 ml
cate disagreement between equilibrium data and this model. monomer, 0.03 M solution of hydrogen peroxide, and
 9484, 2020, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1155/2020/1239267 by Nat Prov Indonesia, Wiley Online Library on [24/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
International Journal of Polymer Science 13

3.7
4.0 3.8
3.7 3.6
3.9
3.6
3.8 3.5 3.5

3.4
3.7 3.4
3.3
3.6 3.2 3.3
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 2.2 2.4 2.6 2.8 3.0 3.2 2.5 2.6 2.7 2.8 2.9 3.0 3.1

(a) (b) (c)

Figure 18: Freundlich adsorption isotherms for adsorption of (a) Pb (II), (b) Cr (III), and (c) Cd (II) on amidoxime chelating resin, pH 5, and
temperature at 25°C.

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by King Abdulaziz City for Science and Technology and chromium (VI) ions from aqueous solution using clay,”
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