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Journal of Environmental Chemical Engineering 6 (2018) 2137–2147

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Journal of Environmental Chemical Engineering


journal homepage: www.elsevier.com/locate/jece

Grafting polymerization of acrylic acid onto chitosan-cellulose hybrid and T


application of the graft as highly efficient ligand for elimination of water
hardness: Adsorption isotherms, kinetic modeling and regeneration

Xiaojian Zhoua, Hisham A. Essawyb, , Magdy F. Mohamedc, Hanan S. Ibrahimd, Nabila S. Ammard
a
Yunnan Provincial Key Laboratory of Wood Adhesives and Glued Products, Southwest Forestry University, Kunming, China
b
Department of Polymers and Pigments, National Research Centre, Dokki 12622, Cairo, Egypt
c
Delta Agrochemicals Company, Giza, Egypt
d
Department of Water Pollution, National Research Centre, Dokki 12622, Cairo, Egypt

A R T I C LE I N FO A B S T R A C T

Keywords: Grafting copolymerization of acrylic acid from chitosan-cellulose hybrid ((CTS/Cell)-g-PAA) was conducted and
Chitosan-cellulose the grafting efficiency and crosslinking level were optimized at 86.5% and 2.5%, respectively. Investigation
Acrylic acid grafting using scanning electron microscopy (SEM) indicated a mechanically robust material with a porous surface which
Water hardness allows diffusion. This property along with the high water absorption under wide range of pH values qualified the
Removal
material for application as adsorbent/ligand to metal ions from aqueous solutions. This was additionally sig-
nified using fourier transform infrared (FTIR) spectra collected for the graft before and after chelation to metal
ions that cause water hardness, which confirmed that the oxygenated and nitrogenated groups are the main sites
for binding metal ions in high capacity with removal efficiency above 90% in most cases. Application of
Langmuir and Freundlich adsorption isotherm models for the metal ions on the graft copolymer indicated that
the adsorption data are better fitted by Freundlich model for all metal ions while a chemisorption nature of
adsorption was deduced by a kinetic modeling study. Further, the adsorption was highly favoured in case of Ca
(II) and Mg(II) while to a much lesser extent in case of Na(I). The polymeric ligand showed also outstanding
performance during competitive removal of a mixture of metal ions from aqueous solution with a selectivity
order Ca(II) > Mg(II) > > Na(I), such selective removal activity of the ligand was almost not influenced after
induced desorption and reuse for additional four succeeding cycles.

1. Introduction carbohydrate polymers and considered as the most abundant biopo-


lymer, present mostly in wood, cotton and other sources [23]. Super-
Polymeric superabsorbents are characterized by high absorption absorbents made from chitosan lonely exhibit weak mechanical
levels of water in short time [1,2]. This makes them largely liable for strength therefore limited possibility of reusability is encountered. This
utilization in various fields [3–5]. Graft polymerization is considered as induced other researchers for blending it with cellulose or other re-
one of the most important methods devoted for preparation of super- inforcing materials such as attapulgite, hydroxypropyl cellulose, mus-
absorbents by polymerizing vinyl monomers onto natural bio-based covite or pillared clay, before grafting [24–29]. However, this route was
materials such as starch [6,7], chitosan [8–11], sodium alginate [12], associated by a drop in water absorption and mass transfer. In addition,
carrageenan [13], and cellulose [14,15]. This gives rise to unique the chemical activity was not that high as for superabsorbents con-
characteristics including low toxicity, antibacterial, enhanced chemical structed from chitosan and its blends with analogous structures.
activity and reduced cost [16–21]. The need for fresh water in some areas of the world exceeded the
Chitosan is a natural polysaccharide containing free amino and natural capacity in particular that the fast population growth and
hydroxyl groups which entitles it for crosslinking and chelation reac- growing spending of per capita caused further limitations of the world’s
tions. Chitosan was utilized as backbone for grafting polymerization of resources of fresh water which imposes an extreme need in few years to
acrylic acid and yielded materials that exhibited superabsorbency [22], get fresh water from conversion of sea water via desalination. However,
while cellulose is another material belonging to natural linear this will be far too expensive and impractical for wide use. Thus, it is


Corresponding author.
E-mail address: ha.el-fatah@nrc.sci.eg (H.A. Essawy).

https://doi.org/10.1016/j.jece.2018.03.022
Received 25 November 2017; Received in revised form 9 March 2018; Accepted 10 March 2018
Available online 11 March 2018
2213-3437/ © 2018 Elsevier Ltd. All rights reserved.
X. Zhou et al. Journal of Environmental Chemical Engineering 6 (2018) 2137–2147

Fig. 1. A simplified scheme for cellulose–chitosan combination via chemical crosslinking using thiourea formaldehyde and use of their hybrid as precursor for preparation of a polymeric
ligand ((CTS/Cell)-g-PAA) via graft copolymerization of acrylic acid in presence of MBA as a crosslinker.

necessary to make maximum avail of the present resources of natural pressure, anemia, weakness in fingers and wrists, etc.
water. Unfortunately, dissolved salts of different concentrations are Various techniques have been broadly employed for softening of
usually included in natural waters. Additionally, industry produces water from existing divalent ions such as Ca(II) and Mg(II) [30–40].
water contaminated with salts, which renders it unsuitable for drinking. Two major methods are typically applied to remove hardness form
Consequently, reducing salts content in water is an essential issue to water, namely using lime soda and ion exchange. The main dis-
avoid serious health problems associated with their accumulation in advantages of the lime soda method are the production of a high sludge
human organs, e.g., disorder of the nervous system, high blood volume which requires post-treatment, too much use of chemicals and

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Fig. 2. SEM micrographs of a) CTS-g-PAA, b) (CTS/Cell)-g-PAA, and c) swelling behavior of (CTS/Cell)-g-PAA as a function of pH.

Fig. 3. FTIR of (CTS/Cell)-g-PAA and (CTS/Cell)-g-PAA…M(II).

addition of acids for pH adjustment, which increases operation costs using polymeric adsorbents considering the cost point of view and lack
[41,42]. To date, adsorption proved to be the most simple and pro- of sludge formation.
mising alternative for purification of water especially if to be performed Polymeric network structures are widely utilized as adsorbents for

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Fig. 4. Effect of contact time on separate removal of 20 mg/L from each metal ion using 0.5 g/L of the polymeric ligand at pH 7.5–8.

Fig. 5. Effect of polymeric ligand dosage on separate removal of 20 mg/L from each metal ion after 5 min contact time.

Fig. 6. Effect of initial metal ion concentration on separate removal of the ions using 0.5 g/L of the polymeric ligand in case of Ca(II) and Na(I) whereas 1 g/L in case of Mg(II).

metal ions from aqueous solutions because of their active functional poor mechanical properties and weak acid resistance of chitosan based
groups such as carboxylic, amine and hydroxyl, which can interact ef- graft copolymers through chemical modification of chitosan with cel-
ficiently with the ions [43]. The present report attempts to modify the lulose fibers using thiourea-formaldehyde as a binder in presence of

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Table 1 2.5 wt.% thiourea, 2.2 g formaldehyde solution, and 2.5 wt.% sulfuric
Effect of pH on adsorption of different metal ions onto 0.5 gm/L of polymeric ligand at acid solution dissolved in 100 mL of ethanol-water mixture (1:1) at
20 mg/L initial concentration and 2 h contact time.
room temperature for 2 h. The film was exposed to several washing
pHinitial pHfinal Ce (mg/L) Removal, % cycles with distilled water before dried at room temperature for 48 h.
The film was subjected to grinding and sieved to a size of 75 μm or less.
Ca++
2 6.3 1.3 93.5
2.3. Preparation of the graft copolymer ((CTS/Cell)-g-PAA)
4 7.5 0.5 97.5
6 7.5 0.42 97.9
7.5 7.5 0.4 98 The polymeric graft was synthesized following a general procedure
Mg++ detailed in previous reports from our group and others [45–48]: 1 g of
2 6.18 10 50 crosslinked CTS/Cell hybrid particles was suspended in 30 mL distilled
4 7.6 4.84 75.8
water under stirring in a three-neck flask equipped with a reflux con-
6 7.6 5.3 73.5
7.7 7.6 4.47 77.65 denser, funnel, and nitrogen line. Nitrogen was purged with for 30 min.
Na+ Subsequently, 0.1 g of APS was added to produce radicals onto the
2 6.8 11 45 surface of CTS/Cell hybrid. After 15 min, a mixture containing 3.60 g
4 7.8 10 50
acrylic acid and 0.1 g N,N'-methylenebisacrylamide as crosslinker was
6 8.0 9.8 51
8 8.0 9.6 52 added to the solution. The temperature was kept at 70 °C and agitation
continued for 3 h to ensure end of polymerization. The product was
cooled down to room temperature and the pH was neutralized using
sulfuric acid as a catalyst. Such reaction leads to combination of both 1 mol L−1 KOH solution. The material was washed with a large volume
carbohydrates into an integrated stable hybrid. The chemical reaction of distilled water to take away any residual reactants then oven dried at
between chitosan and cellulose involves crosslinking, which improves 70 °C. The product was milled to a particle size of 400–840 μm.
not only the mechanical integrity of the produced hybrid and resistance
to acidic mediums but also its liability for grafting copolymerization of 2.4. Characterizations of the graft copolymer
acrylic acid. As a result, formation of a robust chemically active su-
perabsorbent composite is expected. This strategy warrants obtaining a FTIR spectra of the samples were recorded using FTIR spectro-
package of advantages such as high water absorbency and excellent photometer (Jasco, Model 6100, Japan) in the range 500–4000 cm−1 at
chemical activity in the sense of chitosan existence and simultaneous a resolution of 4 cm−1. The dried samples were blended with KBr and
high grafting ratio of acrylic acid and cheaper price in presence of bio- pressed into discs before acquisition. The morphological features of the
based waste such as cellulose. samples were examined using SEM-EDS (JSM-5500LV, JEOL, Ltd.),
The prepared superabsorbent graft copolymer, with its exceptional operated at a vacuum mode, after being gold coated with a sputter
structural characteristics, rich function groups and reduced cost, is Coater (SPI-Module). Zeta potential measurements of the hybrid par-
expected to perform promisingly in environment protection applica- ticles were conducted on NICOMP 380 ZLS dynamic light scattering
tions as polymeric ligand/adsorbent, namely for removal of water (DLS) instrument (Santa Barbara, CA, USA) using 632 nm line of HeNe
hardness. laser as the incident light with angle 90° and zeta potential with ex-
ternal angle 18.9°. The dispersions were diluted with distilled water
adjusted to a predetermined pH values before the measurements. The
2. Experimental
zeta potentials were taken as average values of three readings.
2.1. Materials
2.5. Metal ions removal using the graft copolymer as ligand/ion exchanger
Acrylic acid (AA) and ammonium persulfate (APS) were purchased
A batch sorption method was employed for investigating the effi-
from Sigma-Aldrich, USA. Chitosan (CTS, with deacetylation above
cacy of the polymeric graft as ligand for metal ions. A mechanical
85%) was purchased from Euromedex, France. Cellulose pure powder
shaker operated at 120 rpm was used for homogenization of the metal
(Cell) and potassium hydroxide were supplied from Sd. fine Chem.,
ions solution with the graft copolymer. The concentrations of the metal
India. N,N'-methylenebisacrylamide (MBA) was ordered from Merck,
ions were estimated after filtration with Whatman® filter papers (No.
Germany. Calcium chloride (CaCl2), magnesium sulfate (MgSO4) and
44). Control samples were also prepared without the polymeric ligand
sodium chloride (NaCl) of analytical grade from Merck, were used in
and used for comparison. All experiments were carried out in triplicates
the preparation of stock standard solutions (1000 mg/L). The different
and the removal efficacy of metal ions by the polymeric ligand was
concentrations of metal ion solutions were then prepared by diluting
assessed for all samples using inductive coupled plasma optical emis-
the stock standard solutions. All other chemicals were of analytical
sion spectrometry (Agilent ICP-OES 5100, Australia) according to
grade.
standard methods dedicated for examination of water/wastewater [49].
The loaded polymeric ligand with the mixture of metal ions was re-
2.2. Preparation of chitosan-cellulose hybrid (CTS/Cell) generated by washing 0.1 g of it in100 mL of different eluting media
such as brine solution (0.5 g KOH and 5% KCl), 0.1 M HCl and 0.1 M
Chanachai et al. [44] suggested a simple procedure for comprising HNO3 under stirring for 5 min at room temperature to extract the metal
chitosan and cellulose in one crosslinked structure. Thus, 1.2 g of ions. After filtration, the ligand was washed with deionized water until
chitosan was dissolved in 100 mL of 2 wt.% aqueous solution of acetic reaching pH 7 then dried in a vacuum oven at 50 °C till reaching con-
acid. In parallel, a diluted cellulose suspension in water was prepared stant weight before use. The same procedure was repeated in the same
by dispersing 1.2 g of its powder in 100 mL distilled water under vig- sequence for additional three times.
orous stirring at ambient temperature. The chitosan solution was fil-
tered and both solutions were mixed together and stirring was per- 3. Results and discussion
formed at room temperature for another one day. The mixture was
poured into a glass plate and dried at room temperature for 4 days. The 3.1. Characterization of the graft copolymer
blend was removed out from the plate in the form of a film. The film
was crosslinked by immersion in a homogenized solution containing Structures containing chitosan units are considered promising

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Fig. 7. Langmuir and Freundlich adsorption isotherms for Ca(II) (a,b); Mg(II) (c,d); and Na(I) (e,f) on the polymeric ligand.

Table 2 materials due to their high absorption capacity of water which allows
Parameters resulting from the application of Langmuir and Freundlich isotherm models for high mass transfer. Additionally, they possess the aptitude for re-
for Ca, Mg and Na ions adsorption on the polymeric ligand under optimum operating
generation and consequently several cycles of reuse after metal ad-
conditions.
sorption are warranted [50,51]. However, broadening of their appli-
Metal ion Langmuir model Freundlich model cation is restricted because of their poor mechanical strength and weak
resistance to acidic mediums [52]. Rigorous efforts were exerted to
KL qmax R2 Kf n R2 overcome these drawbacks via chemical modification of chitosan by
Ca (II) 0.75 90.78 0.858 41.896 5.716 0.984
combination with cellulosic materials. Cellulose was chosen specifically
Mg (II) 2.08 34.63 0.941 21.720 9.544 0.952 due to its large abundance, good mechanical properties and analogous
Na (I) 0.53 12.11 0.822 8.859 15.91 0.983 chemical structure, which provides a good possibility for obtaining a

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Table 3
Kinetic parameters obtained by applying pseudo-first- order and pseudo-second- order models for the individual removal of 20 mg/L of Ca(II), Mg(II), and Na(I) using 0.5 g/L of the
chelating polymer.

M(II) Pseudo-first-order kinetics Pseudo-second-order kinetics

qe (exp) (meq/g) qe (meq/g) k1 (min−1) R2 qe (meq/g) k2 (g mg−1 min−1) R2

Ca(II) 1.93 0.93 0.8655 0.9745 2.0 1.48 0.999


Mg(II) 2.44 2.72 1.44 0.908 2.475 2.523 0.999
Na(I) 0.906 0.93 0.7664 0.958 0.903 2.51 0.991

Table 4 which allows diffusion of existing metal ions in water (Fig. 2b). Inter-
Effect of time on competitive removal of 20 mg/L of each metal ion from combined estingly, no free cellulose particles could be detected to exist liberally
mixture using 1 gm/L of the polymeric ligand at pH 7.9.
on the surface of the hybrid which supports the chemical hybridization
Time, min Ce (mg Ca2+/ % Ce (mg Mg2+/ % Ce (mg Na+/ % of chitosan and cellulose before grafting. Fig. 2c shows the swelling
L) L) L) profile of the polymeric ligand as a function of pH. The profile dictates
that the swelling increases with the pH from 2 to 6.5 then became al-
5 2.6 87 3.8 81 18.7 6.5 most stable. For more understanding of the swelling behavior of (CTS/
10 2.6 87 3.8 81 18.9 5.5
30 2.57 87.15 3.8 81 18.7 6.5
Cell)-g-PAA, the zeta potential measurements were undertaken on their
60 2.46 87.7 3.7 81.5 18.8 6.0 dispersions at different pH values. The acquired potentials were 426 mV
90 2.6 87 3.8 81 18.9 5.5 at pH 2, −2.3 mV at pH 4, −4.3 mV at pH 6 and −2.5 mV at pH 8.5.
120 2.69 86.55 3.78 81.1 19.2 4.0 This reveals that at low pH value, the high concentration of H+ pro-
tonates most of the carboxylate groups thus electrostatic repulsion be-
tween the carboxylate anions becomes limited. Conversely, protonation
cheap homogeneous structure combining unique properties such as
of eNH2 groups takes place at the same pH range which improves the
higher water absorption and enhanced chemical activity [53]. Different
electrostatic repulsion. Starting from pH 6–7, the amino groups are free
reports proposed chemical crosslinking of chitosan and cellulose by
while the carboxyl groups convert to COO− thus anion–anion repulsion
employing crosslinking agents such as glutaraldehyde, ethylene glycol
becomes higher which maintains the swelling capacity at a high level.
diglycidyl ether, epichlorohydrine, etc [54]. The current work uses
Overall, this shows from one side the suitability of the prepared ma-
thiourea formaldehyde resin (TUF) as a crosslinker [16] to fabricate a
terial for facile diffusion of the metal ions into the network structure
chemically active superabsorbent composite based on this hybrid via
while from another side that the proposed interaction between metal
grafting polymerization of acrylic acid.
ions with this polymeric ligand is dominated mainly by electrostatic
Furthermore, it is expected that the chains of polyacrylic acid can
attraction forces with the negative charged sites on the network
participate during propagation with their COOH groups to further bind
structure.
cellulose and chitosan via esterification reactions with OH groups from
Fig. 3 reveals FTIR spectra of CTS/Cell-g-PAA as well as its successor
both and via radical termination as well.
after binding to a mixture of Ca(II), Mg(II) and Na(I), (CTS/Cell)-g-
It is obvious from Fig. 1 that chitosan can be linked chemically to
PAA….M(II). Before chelation with metal ions, the graft showed a
cellulose using thiourea formaldehyde (TUF) as coupling agent and the
broad band at 3000–3852 cm−1 representing overlapped OH and NH.
formation of a new chitosan-cellulose hybrid was confirmed sufficiently
The peak at 2928 cm−1 confirms CeH stretching while the peak at
in our previous report [50]. Thereby, this successor can serve as a
1715 cm−1 is affiliated to C]O groups of polyacrylic acid chains
backbone in which the grafting copolymerization of acrylic acid can be
grafted on the backbone of the hybrid. The band positioned at 1632 is
started from after inducing free radicals formation on the surface with
also indicating OH stretching whereas the peak at 1412 cm−1 is asso-
the aid of ammonium persulfate as initiator. Methylenebisacrylamide
ciated with CeN stretching. Further, the band at 1162 cm−1 refers to
was also provided to strengthen the grafting layer and prevent possible
CeOeC stretching. A first round investigation was conducted at
dissolution of the formed macromolecular network in aqueous media.
random by leaving the graft copolymer in contact with a solution
The grafting efficiency was calculated as 86.5% while the crosslinking
comprising a mixture of Ca(II), Mg(II) and Na(I) for 2 h and FTIR
level was estimated as 2.5%. The tentative chemical structure of the
spectra was collected from the dried graft after binding to the metal ion
polymeric ligand reveals many possible chelating centers in this struc-
where it was found that the graft copolymer–metal ion chelate ex-
ture towards metal ions represented by nitrogen and oxygen sites ac-
hibited very similar spectrum. However, it can be noted that the bands
quiring different chemical environments and geometries. In addition,
related to oxygenated and nitrogenated groups exhibited either slight
eCOOK sites are available for cation exchange with monovalent ions.
perturbation to higher wavenumber or became to some extent narrower
Scanning electron microscopy (SEM) imaging is a very useful
and sharper. Based on this shift, it can be initially concluded that the
technique to study details of the surface morphology (Fig. 2). The graft
nitrogen and oxygen-containing sites are target groups to bind metal
copolymer initiated from pure chitosan appeared non-coherent, loose
ions which encouraged us to start an intensive study on this context
and brittle (Fig. 2a). However, in case of grafting on the hybrid, the
under broad conditions.
copolymer became more mechanically robust with a porous surface

Fig. 8. Potential metal ions coordinating centers present in (CTS/Cell)-g-PAA.

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Fig. 9. SEM and EDS spot on the surface of the polymeric ligand after competitive removal of 20 mg/L of each metal ion from a combined mixture.

Table 5
Efficiency of the polymeric ligand for removal of 20 mg/L of each metal ion from combined mixture using 1 gm/L of the polymeric ligand at pH 7.9 for four repetitive cycles of use after
regeneration in brine solution.

Cycle W(g/L) V(mL) Cremoved Ca(II) Q (mg/g) Cremoved Mg(II) Q (mg/g) Cremoved Na(I) Q (mg/g)

1 1.0 100 17.4 17.4 16.2 16.2 1.2 1.2


2 0.905 90.5 17.4 17.4 16.2 16.2 1.2 1.2
3 0.84 84 17.4 17.4 16.2 16.2 1.2 1.2
4 0.73 73 17.2 17.2 16.0 16.0 1.0 1.0

Table 6
Efficiency of the polymeric ligand for removal of 20 mg/L of each metal ion from combined mixture using 1 gm/L of the polymeric ligand at pH 7.9 for four repetitive cycles of use after
regeneration in 0.1 M HCl solution.

Cycle W(g/L) V(mL) Cremoved Ca(II) Q (mg/g) Cremoved Mg(II) Q (mg/g) Cremoved Na(I) Q (mg/g)

1 1.0 100 17.4 17.4 16.2 16.2 1.2 1.2


2 0.90 90 17.4 17.4 16.2 16.2 1.2 1.2
3 0.83 83 17.4 17.4 16.2 16.2 1.2 1.2
4 0.72 72 17.0 17.0 15.7 15.7 0.9 0.9

Table 7
Efficiency of the polymeric ligand for removal of 20 mg/L of each metal ion from combined mixture using 1 gm/L of the polymeric ligand at pH 7.9 for four repetitive cycles of use after
regeneration in 0.1 M HNO3 solution.

Cycle W(g/L) V(mL) Cremoved Ca(II) Q (mg/g) Cremoved Mg(II) Q (mg/g) Cremoved Na(I) Q (mg/g)

1 1.0 100 17.4 17.4 16.2 16.2 1.2 1.2


2 0.89 89 17.4 17.4 16.2 16.2 1.2 1.2
3 0.825 82.5 17.4 17.4 16.2 16.2 1.2 1.2
4 0.705 70.5 16.8 16.8 15.7 15.7 0.8 0.8

3.2. Effect of time on separate removal of metal ions using the graft metal ions: Ca(II) > Mg(II) > Na(I). The uptake efficiency can further
copolymer be enhanced with increasing the adsorbent dose to 1 g/L in case of Mg
(II). No additional increase in the removal efficiency for Ca(II) and Na
The period of contact between an adsorbent and adsorbate solution (I) could be noticed for higher dosages of the adsorbent. This was ex-
under agitation is a crucial factor from which the time required for the plained previously by Ngah et al. [54] mainly due to particulate in-
adsorption process to be equilibrated can be assigned. Fig. 4 indicates teraction and aggregation which leads to collapse of the amount of
that the adsorption was very rapid in case of the divalent ions and al- adsorption sites.
most completed within the initial 5 min. In case of Na+, the uptake was
moderately fast and reached 52% of the initial concentration in 5 min.
However, reaching the equilibrium (almost 41%) took about 10 min to 3.4. Effect of initial metal ion concentration on separate removal of metal
be attained. ions using the graft copolymer

The effect of initial metal ion concentrations was explored using


3.3. Effect of the graft copolymer dosage on separate removal of metal ions
initial metal ions concentrations covering the range 20–200 mg L−1 as
displayed in Fig. 6, which reveals that the efficiency of removal col-
The dependence on the dosage of the polymeric ligand for the re-
lapses extensively with the increase of the initial concentration of all
moval of the metal ion separately was also investigated in the range
metal ions especially in the range 20–100 mg/L. Increasing the initial
0.25–1.4 g/L while keeping all other conditions constant (Fig. 5). It can
metal ion concentration closer to the adsorption capacity of the ad-
be clearly shown that the amount removed of metal ions can increase
sorbent is expected to be associated with a drop in the removal percent
significantly with increasing the ligand dosage from 0.25 to 0.5 g/L.
until reaching a plateau at high initial concentrations [46–48].
The sequence of increase can be arranged in following order for the

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3.5. Effect of pH on separate removal of metal ions using the graft preferential adsorption of the metal ions in the order: Ca(II) > Mg
copolymer (II) > Na(I). Also, the n values confirm the favourability of adsorption
with respect to Ca(II) and Mg(II) but to a much lesser extent for Na(I).
As it is obvious from Fig. 1 that the prepared polymeric adsorbent On the other hand, the fitting of the data to Langmuir model was
(ligand) is amphoteric so it is expected that the removal efficacy of this acceptable to a reasonable extent. The qmax values also confirm the
ligand toward metal ions will show high dependence on pH. Thus, the preference of adsorption in the order Ca(II) > Mg(II) > Na(I). RL
removal of metal ions under investigation in this study was studied at values were calculated according to Eq. (2) and it acquired values
different pH values and the results are collected in Table 1. A general 0.0625, 0.026, 0.013, 0.0088, and 0.0066 for the corresponding initial
trend can be observed that the uptake efficiency toward the different concentrations 20, 50, 100, 150 and 200 mg/L, respectively. As RL
metal ions is remarkably enhanced with shifting the pH from 2 until values are in the range 0–1, this proves that the adsorption reaction for
reaching maximization around pH 8. At pH 2, the coordination sites are Ca(II) is favourable. In case of Mg(II), the RL values were 0.023, 0.0094,
masked as they exist in inactive forms to work as ligands (COOH and 0.0047, 0.0032, and 0.0024 for the corresponding initial concentrations
NH3+). Near pH 4, COOH groups start ionization and the amino groups 20, 50, 100, 150 and 200 mg/L, respectively, which shows also fa-
remain protonated, while at pH 8 both convert to the active forms and vourability for adsorption of Mg(II). The same was noticed in case of Na
become ready for coordination with metal ions (COO− and NH2). The (I), whose adsorption gave rise to RL values 0.086, 0.036, 0.0185,
enhancement was greater in case of Mg(II) (22.6%) followed by Na(I) 0.0124 and 0.0093 for the initial concentrations 20, 50, 100, 150 and
(7%) and finally Ca(II) (4.5%). This may reveal a promise of this ma- 200 mg/L, respectively.
terial to separate metal ions preferentially from their mixtures on
competitive basis. Interestingly, when the pH was originally adjusted at 3.7. Kinetic modeling
acidic values, it changed spontaneously during the course of removal in
all cases to the basic direction. The extent of change was greater when Kinetic modelling of adsorption is a very important tool to foresee
the original pH was lower (2 and 4) which indicates that the removal the conditions at which the uptake process of metal ions by the che-
process involves simultaneous exchange with the internal K+. This lating graft copolymer can be optimally taken place. Pseudo-first order
assumption was confirmed by detection of K+ levels in the medium and pseudo-second order models are applied for this purpose [54,55].
after reaching equilibrium, which was found to increase noticeably. The first order Lagregen's model postulates a removal rate of metal ions
that is proportional to the number of free active sites in a sorbent [47].
3.6. Modeling of adsorption isotherms The obtained kinetic data of the different metal ions are expressed ac-
cording to this model as a function of removal rate and capacity (Eq.
Langmuir and Freundlich adsorption isotherm models are the (4)):
usually applied models for understanding the mechanism by which the
k
metal ions are adsorbed onto an adsorbent, which helps in optimum log[qe − qt ] = log[qe] − ⎡ 1 ⎤ t
⎣ 2.303 ⎦ (4)
designation of adsorption systems [54,55]. The Langmuir model pos-
tulates formation of a saturated monolayer of adsorbate molecules on Where k1 is the rate constant of the first-order sorption (min−1), qe is
the surface [54,55] while all adsorption sites have the same sorption the amount of metal ion uptake by the chelating polymer at equilibrium
activation energy. This model is represented by Eq. (1): (meq/g) while qt is the amount adsorbed at time ‘t’. Plotting log
Ce 1 C (qe − qt) versus t gives a straight line from which k1 and qe were ob-
= + e tained from the slope and intercept, respectively. The collected data are
qe KL qmax qmax (1)
shown in Table 3. qe values were fixed experimentally as 1.93, 2.44 and
Where Ce is the equilibrium concentration of the metal ion in solution 0.906 meq/g for Ca(II), Mg(II), and Na(I), respectively. However, the
(mg/L), qe is the adsorbed amount onto the polymeric adsorbent at fitted corresponding values varied by different extents, 0.93, 2.72 and
equilibrium (mg/g) while KL (L/mg) and qmax (mg/g) are Langmuir 0.93 meq/g. The difference may be accounted for by the estimation of
constants related to energy of adsorption and maximum uptake per unit qe from the intercept at t = 0. This is thought to be influenced by the
mass of adsorbent, respectively. The efficiency of adsorption according fast initial uptake of the metal ions, which is usually lower than the
to this model can be estimated by a dimensionless equilibrium para- uptake at equilibrium. The correlation coefficient (R2) was thus speci-
meter, RL, which can be calculated according to Eq. (2). fied to be less than 0.99 for the different metal ions (Table 3).
1 From another side, the pseudo-second order model postulates pro-
RL = portionality between the rate of removal and square of unoccupied sites
1 + KL Co (2)
number [47]. The pseudo-second-order model can be expressed by Eq.
Where ‘KL’ is the Langmuir constant and C0 is the initial concentration (5):
of metal ion (mg/L). When RL = 0, the sorption is considered irrever-
t 1 t
sible whereas favourable when 0 < RL < 1 and unfavourable when = +
qt k2 qe2 qe (5)
RL > 1.
Likewise, Freundlich isotherm model assumes a multilayer adsorp- Where k2 is the reaction rate constant. In case of Ca(II), a plot of t/qt
tion onto a heterogeneous surface [54,55]. The Freundlich relation is versus t gave rise to a linear relation from which k2 could be fixed from
described by Eq. (3): the intercept (1.48) while qe was obtained from the slope (2.0 meq/g).
The determined qe is in conformity with the experimental value
qe = Kf Ce1/ n (3)
(1.93 meq/g) which was also the case for the other metal ions under
Kf is the Freundlich constant corresponding to adsorption capacity investigation. This implies a practical applicability of the pseudo-
((mg/g)·(mg/L) n), n is a dimensionless heterogeneity factor for the second order model and ensures a chemisorption process to the removal
adsorption sites. When n value lies in a range 1–10, the adsorption process in particular that the correlation coefficient was close to unity
process is regarded favourable. in all cases (Table 3).
The adsorption data were fitted according to the equations de-
scribing the different isotherm models as shown in Fig. 7 and the de- 3.8. Effect of time on competitive removal of the metal ions using the graft
rived isotherm parameters for both models are collected in Table 2. The copolymer
correlation coefficients (R2) indicate that the adsorption data are better
fitted by the Freundlich model for all metal ions. Kf values signify the The contact time between the polymeric ligand and a mixture

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combining 20 mg/L of each metal ion was studied at pH 7.9 in order to data to isotherm models using MATLAB.
investigate whether it is possible to preferentially separate the metal
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