International Journal of Biological Macromolecules 123 (2019) 70–80

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Crown ether modification of starch for adsorption of heavy metals from

synthetic wastewater
B.M. Ibrahim a,⁎, N.A. Fakhre b
a
Department of Chemistry, College of Science, University of Raparin, Iraq
b
Department of Chemistry, College of Education, Salahaddin University-Erbil, Iraq

a r t i c l e i n f o a b s t r a c t

Article history: The adsorbent resin was prepared by grafting copolymerization of dibenzo 18 crown 6 onto corn starch
Received 4 August 2018 under microwave irradiation and was used to adsorb Cd2+, Zn2+, Ni2+ and Cu2+ from aqueous solution.
Received in revised form 23 September 2018 Microwave assisted synthesis method, which uses only microwave radiation to generate free radical in
Accepted 11 November 2018
the polymer backbone, is fast, and reliable. It can produce high-quality product as compared to the conventional
Available online 12 November 2018
method. The resultant microwave produced modified starch was characterized by FTIR, UV–Vis, XRD and
Keywords:
SEM devices. Adsorption of heavy metal ions on adsorbent could be well fitted by the pseudo-second-order
Microwave irradiation and Freundlich equations. The influences of pH, contact time, adsorbent dose, temperature and metal ion
Corn starch concentration were studied in batch method experiments. Grafted corn starch could be reused by HNO3 as
Dibenzo 18 crown 6 eluting agent. All the results show that St:DB18C6 is a good adsorbent for the removal of heavy metal ions
Metal ions from wastewater.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction biosorbents have been used as adsorbent to purify aqueous solutions

from metal ions. Immobilized functional groups play an important
In recent years, water pollution has become the main concern of role in enhancing the efficiency of adsorbents [9]. High affinity of
environmental scientist. Among the pollutants, heavy metal ions have chelating agents such as crown ethers towards metal ions is well
been the main focus. Both natural sources and anthropogenic activities recognized. They have been widely used in selective transport and
have their role in contaminating water with heavy metals [1]. High selective extraction of metal ions because of their good complex
toxicity and non-biodegradability are characteristics of heavy metals selectivity for various metal ions [10,11]. The applications of crown
in water that makes them highly hazardous [2,3]. ethers in industrial processes are limited by their high cost, and
While certain quantities of heavy metals are essential for living difficulty of recovering them. However, these limitations could be
organisms, higher concentrations would make them toxic. Various reduced by chemically reacting or cross-linking CRs onto synthetic
diseases such as cancer, developmental retardation, kidney damage, polymers. Stronger complex with higher metal ion selectivity has
autoimmunity, and even death in severe cases are associated with been expected from crown ether modified polymers that could
exposure to heavy metals. Thus, it is of prime importance to remove surpass corresponding crown ethers and polymers alone, the driving
them from water and waste water [4]. force for the crown ether affinity refers to the presence of the oxygen
The reduction of heavy metals from waste water is performed by atoms of the cyclic species as the driving force towards starch
several methods such as ion exchange, precipitations, membrane [12–15].
filtration, electrolytic method and adsorption. Nevertheless, high Methods of graft copolymerization on natural polysaccharides have
cost and low adsorption capacity of heavy metals in these conven- been developed to synthesize advanced materials which have enhanced
tional methods have restricted their use [5–7]. Adsorption methods functional properties. The most important methods are the use of redox
are considered the most effective because of their removal efficiency grafting, microwave irradiation, γ-ray irradiation or by utilizing electron
and recyclability [8]. The most important component of the adsorp- beams [16].
tions process is the adsorbents. Charcoal, clays, oxide minerals and In conventional grafting methods, free radical locations were pro-
duced on the polymer backbone using chemical free radical initiators,
where the graft chain is produced from mixed up monomers of the
⁎ Corresponding author. graft. This technique of synthesis has low reproducibility and it is costly
E-mail address: [email protected] (B.M. Ibrahim). for commercial-scale synthesis. The use of gamma rays or electron beam

https://doi.org/10.1016/j.ijbiomac.2018.11.058
0141-8130/© 2018 Elsevier B.V. All rights reserved.
 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80 71

Dibenzo-18-crown-6 Starch

Scheme 1. Compounds used in this study.

as free radical initiators might be a better way for graft copolymer Kraft GmbH, Duisburg, Germany). Dibenzo 18 crown 6 (Scheme 1),
synthesis [17]. However, radiolysis can occur from the high energy (Solarbio), was employed as received. All other chemicals utilized in
radiation that would damage the polysaccharide backbone [18]. In the this work were of analytical grade and supplied by Scharlau. Arrange-
presence of a suitable photosensitizer, UV rays can also be applied. But ment of pH was performed using 0.1 M HNO3 or 0.1 M NaOH.
it is only suitable for surface grafting as it cannot penetrate deep into
the material. 2.2. Characterization
The use of microwave radiation in graft copolymer synthesis is the
best technique to produce free radical sites on the back-bone polymers. 6705 UV/vis spectrometer was used for UV–vis spectra measure-
There are two types of microwave-based methods of grafting. ments. FTIR spectrometer was employed to analyze the surface groups
of the modified starch before and after metal ion adsorption. It was
1. Microwave initiated synthesis methods which produce free radical
achieved using Shimadzu Spectrophotometer with KBr pellets.
sites on the polysaccharide backbone using microwave radiation
The heavy metal ion concentration of the solutions before and after
alone.
adsorption was determined by Inductively Coupled Plasma optical
2. Microwave assisted synthesis methods generate free radial sites on
emission Spectrophotometer (Spectro arcos Germany). Hanna pH
the polysaccharide backbone using chemical free radical initiator
meter was used for measuring pH of the solution. X-ray diffraction
and microwave radiation [19,20].
(XRD) analysis of the raw and chemically modified starch was taken
In the study, DB18C6 modified chelating fiber based on starch was on a Rigaku MiniFlex II diffractometer utilizing the Nifiltered CuK radia-
synthesized through microwave irradiation. The reaction conditions tion (1.54059 Å). The samples were scanned within the two angles
such as temperature, time and monomer concentration were optimized range from 2.0 to 60.0° with a scan rate of 5 min−1.
completely. The influence of various parameters including contact time, Morphology images of surface and cross-section of the raw starch
pH, initial concentration and temperature on the adsorption process and grafted starch were taken under vacuum with an accelerated
was intensely studied. voltage of 3 kV using Hitachi S-4100 scanning electron microscope
(SEM).
2. Materials and methods
2.3. Preparation of chemically modified starch
2.1. Materials
As shown in Scheme 2, maize starch (1.0 g) in 10 mL distilled
Starch (Scheme 1) was purchased from local market and used as re- water was heated at 85 °C for 30 min in a 100 mL conical flask in a
ceived. Multi-element stock solutions containing 1000 mg/L of nickel, thermostatic water bath to be gelatinized. The produced gelatin
zinc, cadmium and copper were obtained from Bernd Kraft (Bernd was then cooled.

1.0 gram of starch paste

at 85 oC for 30 min Mixture washed with
chloroform then filtered Drying

Microwave irradiaon at
600 was for 6 min

DB-18-crown-6

Scheme 2. Procedure used to prepare the [St + DB18C6] composites.

72 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80

A known amount of dibenzo 18 crown 6 and water were added to percentage of metal ions removed of modified starch was calculated ac-
the reaction mixture with continuous shaking of the reaction solution. cording to [21]
The reaction vessel was then placed in the microwave oven at 600 W
for 6 min in order to perform grafting reactions. As the reaction mixture ðRÞ% ¼ ððCo −Ce Þ∕Co Þ  100
started to boil, the microwave irradiation was periodically paused and
cooled and then started again to keep homopolymer formation to the
lowest and prevent vapor formation. where C0 and Ce (mg/L) are initial and final equilibrium concentra-
This process was repeated until a gel like mass was left at the bottom tions of metal ions in the solutions respectively.
of the conical flask. When this happened, the reaction vessel and its con-
tents were cooled and left for 24 h for the grafting reaction to be com- 2.5. Regeneration study
pleted. To remove unreacted reagents, the grafted product was
washed with chloroform. The resulting graft copolymer was then Regeneration experiments were carried out in 250 mL of 0.1 M HNO3
dried at 40 °C and grinded to get a fine product. solution. To maximize the desorption percentage of metal ions on the
modified starch, the solution was left on water bath shaker for 24 h at
room temperature. It was then centrifuged to separate the St:DB18C6
2.4. Adsorption studies from the aqueous solution. Later, the St:DB18C6 was filtered and dried
to be reused again.
Batch adsorption experiments were achieved by mixing 0.1 g of The filtrate was examined using ICP-OES to determine the concen-
grafted starch for 60 min in 10 mL solution containing 2.0 mg/L of Cd2 tration of metal ions. The desorption percentage (%) was calculated as
+
, Zn2+, Ni2+ and Cu2+ ions using water bath shaker (MODEL YCW- follows [22]:
012S, GEMMYCO) at 230 rpm. After filtration, the remaining metal
ions in the filtrate were determined using Inductively Coupled Plasma
optical emission Spectrophotometer (Spectro arcos Germany). The D% ¼ ðAmount of desorbed metal ion∕Amount of adsorbed metal ionÞ  100

Fig. 1. FTIR spectrum of St (a) and modified starch (b), and St:DB18C6 with Cu (c).
 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80 73

3. Results and discussion of the starch and Cu2+ ions. Furthermore, the stretching vibration of
\\O decreased from 1132 cm−1 to 1124 cm−1 after metal adsorption.
3.1. Characterization of St:DB18C6 The metal ion chemically interacts with both the oxygen atoms of
DB18C6 and the oxygen of hydroxyl group of the starch to form a
Incorporation of crown ether into the polysaccharide matric was more stable complex [23].
spectroscopically confirmed by FTIR results. Fig. 1 displays the FTIR Fig. 2 shows UV–vis spectra of 100% St, St:DB18C6 and DB18C6. A
spectra of pure cornstarch (a) and modified starch (b). In spectrum distinct absorption band (Fig. 2a) at 278 nm is observed in DB18C6
a, it is being noticed that a broad band at 3493.09 cm −1 is due to due its benzene rings. In contrast, 100% St doesn't show any absorption
the stretching vibrations of O\\H, a smaller peak at 2931.80 cm−1 peaks (Fig. 2c) because it lacks UV–vis chromophore.
is due to the C\\H stretching vibrations. The peaks at 1157.29 cm−1 Analogous to DB18C6, spectra of [St + DB18C6] composite also
and 1080.14 cm−1 are assigned to C\\O\\C stretching vibrations shows absorption peak at 278 nm (Fig. 2b) which indicates the success-
[19]. ful cross link of DB18C6 into corn starch matric.
In case of St-g-DB18C6 (Fig. 1(b)), the O\\H stretching Fig. 3 shows XRD spectra for DB18C6 powder, 100% St and [St +
band intensity of hydroxyl group of starch was decreased and DB18C6] composites.
lead to a peak at 3394.72 cm −1 . A small peak at 3064.89 cm−1 is As demonstrated in the figure, the spectrum of 100% St can be
attributed to the C\\H stretching vibration of crown ether. The divided into four bands, a major band at 150° and double bands at
band at 1080.14 cm−1 is refers to C\\O\\C stretching vibrations of 17.19°, 17.950° also another band at 22.90°. Encapsulating DB18C6
starch. into St leads to change in XRD spectrum of the composite. The
The appearance of a sharp peak at 1597.06 cm−1 indicated the obtained results show that DB18C6 has several sharp peaks and
presence of a benzene ring in modified starch. In addition, another the structure of St:DB18C6 is different from 100% pure starch. This
peak at 1132.21 cm−1 exists which is refers to stretching vibrations may have caused by DB18C6 fitting well into St:DB18C6. The structure
of \\O\\ of crown ether. The appearance of aforementioned peaks of [St + DB18C6] is more similar that of the 100% St than of DB18C6
from the grafted starch proves that crown ether chains were success- powder.
fully crosslinked on to starch's backbone. Crown ether was bonded to The morphological characteristic of the corn starch and grafted
the starch by hydrogen bonding between OH groups of the polymer starch was examined with SEM. A typical surface morphology
and the oxygen atoms of crown ether. for both grafted and ungrafted starch is shown in Fig. 4. Grafted
The FTIR spectra of the sorption of Cu2+ on modified starch are also starch surface is rough, more irregular and has open holes in
examined by FTIR and the spectrum is shown in Fig. 1. A shift in \\OH the composition. The probability of metal ion adsorption may
stretching vibration from 3394 cm to 3421 cm−1 has occurred which have increased by the existence of the pores in the grafted starch
suggests the formation of a coordination bond between the OH group [24].

Fig. 2. UV–vis absorption spectra of DB18C6 (a), St:DB18C6 (b) and 100% St (c).
74 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80
Intensity

2 Theta (Degree)
Fig. 3. Shows XRD spectra for DB18C6 powder (red line), 100% St (blue line) and St + DB18C6 (green line).

The SEM images St:DB18C6 (Fig. 4b) illustrate that modification of 3.2. Adsorption studies
starch leads to increased surface roughness. They also indicate that
DB18C6 layers have coated the surface of the starch. This demonstrates 3.2.1. Effect of adsorption medium temperature
that the treatment by BD18C6 was successful and the surface area of the The temperature is an important parameter to consider as the de-
product has increased. gree of adsorption relies on the temperature of its components.

a- St

b- St:DB18C6

Fig. 4. SEM images of St (a), St:DB18C6 (b).

 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80 75

90
80
70

Removal%
60
50 Zn
40 Ni
30
Cu
20
10 Cd
0
25 35 40 45 55

Temperature C0

Fig. 5. Effect of temperature on Cd2+, Zn2+, Ni2+ and Cu2+ ion removal onto modified starch surfaces, (metal ion concentration = 2 mg/L, pH = 4.5).

Adsorption measurements were carried out from 25 to 55 °C. Fig. 5 saturated and occupied by the metal ions. Thus, this period was used
shows that the removal percentage of metal ions increased with in- as the optimum contact time for all further experiments.
creasing temperature from 25 to 40 °C, However, when the temperature
further increased, the adsorption extent decreased accordingly. This can 3.2.3. Effect of adsorbent dose
be explained on the basis that the adsorption is endothermic process The adsorbent dosage affects the availability of active site for metal
and there is an abundant active adsorbent site at moderate temperature. ions. Fig. 7 shows the effect of adsorbent quantity on the removal of
Hence, 35 °C was chosen as the optimum adsorption temperature. Cd2+, Zn2+, Ni2+ and Cu2+ ions with changing adsorbent amount
Heat of adsorption is the basis for any changes of adsorption capacity form 0.05 g to 0.4 g in 10 mL metal ion solution. The percentage removal
with temperature. If the adsorption decreases with increase the temper- rises as the quantity of adsorbent rises until 0.2 g and further rising of
ature the adsorption reaction is exothermic, weak bond is formed be- adsorbent dose; the removal percentage remains constant. This con-
tween adsorbent surface and metal ions which suggests physisorption firms that more active sites were available up to 0.2 g of adsorbent
[25,26]. However, if the adsorption capacity increased with increasing which lead to easier contact between the metal ions and the removal
temperature the process will be endothermic and chemisorption occurs site. However, it seems that accumulation occurs when the amount of
[27]. adsorbent was further increased. This will stabilize the number of va-
cant sites [28]. Thus, the amount of 0.2 g adsorbent was selected for fur-
3.2.2. Effect of time on adsorption ther removal experiments.
Another significant parameter in adsorption process is the contact
time as it provides the idea of equilibrium time for the adsorption 3.2.4. Effect of pH
process. The influence of pH on metal ion removal from aqueous solution was
The contact time was studied for different duration ranging from studied. Since, H+ ion concentration increases with higher acidity of the
30 to 240 min to investigate the effect of time on removal of metal solution, the removal of metal ions relies on the available oxygen atoms of
ions by modified starch. The removal percentage of metal ions (Cd2+, crown ethers and hydroxyl groups of the Starch which have affinity for
Zn2+, Ni2+ and Cu2+) as a function of time is illustrated in Fig. 6. the positive metal ions. The more H+ ions present would compete with
Also, with rising adsorption time to 120 min, the removal percentage the metal ions and lower the adsorption rate of the metal ions. Hence, de-
was raised. This is due to a large number of vacant sites that is present termining the optimal pH of the solution is of a great importance.
on the surface for adsorption during the initial stage, after 120 min, no To investigate the effect of H+ concentration on metal removal, the
important variation on the adsorption percentage was observed, indi- solution pH was changed ranging from 3 to 7. The influence of pH on the
cating that the equilibrium was achieved and more molecules built up removal of Cd2+, Zn2+, Ni2+ and Cu2+ ions by the grafted starch is
on the adsorbent surface and the surface adsorption sites become shown in Fig. 8.

90
80
70
60
50 zn
40 Ni
30
20 Cu
10 Cd
0
30 60 120 180 240

Time (min)

Fig. 6. Influence of contact time on the removal of Cd2+, Zn2+, Ni2+ and Cu2+ ions on to modified starch surfaces, (metal ions concentration = 2 mg/L, pH = 4.5, T = 35 °C).
76 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80

100
90
80
70

Removal %
60
zn
50
Ni
40
30 Cu

20 Cd
10
0
0.05 0.1 0.2 0.3 0.4

Adsorbent dose (g)

Fig. 7. Effect of adsorbent quantity on the removal of Cd2+, Zn2+, Ni2+ and Cu2+ ions (metal ion concentration = 2 mg/L, pH = 4.5, T = 35 °C).

102

92
Removal %Ax

82

72
zn
62 Ni
Cu
52
Cd
42

32
3 4 5 5.5 6 6.5 7

pH

Fig. 8. Effect of pH solution on Cd2+, Zn2+, Ni2+ and Cu2+ ion removal onto modified starch, (metal ion concentration = 2 mg/L, T = 35 °C).

98
96
94
Removal %

92
90 Ni
88 Cu
86 Cd
84 zn
82
80
0.05 0.5 1 1.5 3 4 6 8

Concentraon (mg/L)

Fig. 9. Effect of metal concentrations on the removal of Cd2+, Zn2+, Ni2+ and Cu2+ onto modified starch surface, (pH = 6.5; T = 35 °C).
 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80 77

1.6
(a )
1.4
Zn Ni Cu Cd
1.2

log (qe-qt)
1
0.8
0.6
0.4
0.2
0
30 60 180 240

7 (b)
6
Zn Ni Cu Cd
5
4
t/qt

3
2
1
0
60 120 180 240

Fig. 10. Pseudo-first order kinetic (a) and Pseudo-second order kinetic (b) for Cd2+, Zn2+, Cu2+ and Ni2+ ions adsorption on St:DB18C6.

As it can be seen from Fig. 8, at lower values of pH (pH b 4), the ad- concentrations in the range of 0.05–8.0 mg/L at pH 6.5, at 35 °C with
sorption of metal ions is low because of higher proton concentration of 120 min of contact time.
the acid which reduce the metal ion adsorption. Since, the adsorbent As can be seen from Fig. 9, the initial metal ion concentrations of
surface was surrounded by positive charge protons and metal ions are Cd2+, Zn2+ and Cu2+ were increased from 0.05 to 8.0 mg/L except,
positively charged, electrostatic repulsion occurs and metal ions can't Ni2+ concentration increased from 0.05 to 4.0.
approach the functional groups [4]. It is found that at lower metal ion concentration, more than enough
The removal percentage of metal ions increases with increasing pH of adsorption active sites are available. As the concentration of metal
due to the fact that the number of protons decreases and the surface ions rises, the adsorption percentage also rises until all the active sites
of adsorbent will be negatively charged thus the metal ions will be are used [29]. Then the removal percentage drops down gradually be-
strongly attracted by the adsorbent. The highest adsorption of metals cause all the active sites from modified starch are saturated with
observed at pH range from 4 to 6.5. Thus, pH 6.5 was chosen as optimal metal ions.
pH for the other measurements.
3.3. Adsorption kinetics and isothermal studies
3.2.5. Effect of concentration on the removal
The effect of Cd2+, Zn2+, Ni2+ and Cu2+ metal ion concentration on The prediction rate of metal ions by modified starch is greatly depen-
the adsorption process was examined by changing the initial metal ion dent on knowing the adsorption kinetics.

Table 1
Pseudo first-order and pseudo second-order kinetic models for the adsorption of Cd2+, Zn2+, Ni2+ and Cu2+ on modified starch.

Metal ions Pseudo first order Pseudo second order

qe cal qe exp k1 R2 qe cal qe exp k2 R2

(mg/g) (mg/g) (min−1) (mg/g) (mg/g) (g/mg·min)

Cd2+ 24.43 45 0.0135 0.9959 44.84 45 0.0018 0.9992

Cu2+ 17.87 84 0.0135 0.8094 84.74 84 0.0038 0.9997
Zn2+ 28.11 42 0.0142 0.9873 43.85 42 0.001 0.9996
Ni2+ 30.83 50 0.0147 0.9617 56.81 50 0.00058 0.9991
78 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80

Table 2 Table 3
The Langmuir and Freundlich parameters for Cd2+, Zn2+, Ni2+ and Cu2+ ions adsorption. Comparison of our result with other adsorbents.

Metal ions Langmuir Freundlich Grafted Grafting agent (chelating group) Adsorption Reference
adsorbent capacity (mg/g)
qm (mg/g) KL R2 n Kf R2
Porous cellulose 1. Glycidyl methacrylate Cu2+ 60.0 [34]
Cd2+ −172.41 −2.23 0.9030 0.87 741.3 0.9992
2. Polyethyleneimine Zn2+ 27.0
Cu2+ −117.64 −3.86 0.9248 0.84 1174.8 0.9992
Cellulosic okra Acrylonitrile/methacrylic acid Cu2+ 76.82 [35]
Zn2+ −188.67 −2.3 0.9124 0.83 954.9 0.9993
fibres Zn2+ 62.89
Ni2+ −158.73 −1.8 0.9351 0.86 588.8 0.9996
Cd2+ 141.73
Cellulose Glycidyl methacrylate Cu2+ 68.5 [36–38]
(Imidazole) Ni2+ 48.5
Starch Cyclodextrin Cu2+ 135 [39]
The pseudo first order (Eq. (1)) and pseudo second order (Eq. (2)) Banana stalk Acrylonitrile Cd2+ 90.1 [40]
(Fe2+–H2O2)
models were used to study the sorption rate of metal ions by the grafted
Mercerized Triethylenetetramine Cu2+ 56.8 [41]
starch [30]. cellulose Cd2+ 68.0
Corn starch Dibenzo 18 crown 6 Cd2+ 368.5 Present
log ðqe −qt Þ ¼ log qe –K∕2:303t ð1Þ Ni2+ 182.5 study
Zn2+ 377.5


Cu2+ 385
t=qt ¼ 1∕ K2  qe 2 þ ðt∕qe Þ ð2Þ

where qt and qe (mg/g) are the amounts of metal ions adsorbed onto the
modified starch at different time durations and at equilibrium, respec- The experimental correlation coefficients obtained are better consistent
tively. k1 (L/min) and k2 (g/mg·min) are the corresponding adsorption with Freundlich isotherm model than Langmuir isotherm model as
rate constants. The values acquired from pseudo first order and pseudo shown in Table 2. This concludes that the adsorbent surface is heteroge-
second order models are shown in Fig. 10 and collected in Table 1. It can neously covered by metal ions. Furthermore, information such as suit-
be observed that the sorption kinetics of metal ions clearly follows ability of adsorbate/adsorbent system and adsorption system can be
pseudo second order model as the experimental data of the correlation obtained from Freundlich isotherm constants such as Kf and n values
coefficients (R2) for metal ions are larger for pseudo second order [32]. The adsorption capacity is high when Kf value is high. The relation
models than for those of the pseudo first order and the values calculated between concentration and adsorption capacity of a system can be de-
from the pseudo second order model were closer to the values obtained termined by n value. When n N 1 the system is more efficient at low con-
from experimental Qe. centration. However, at n b 1, higher concentration is more favored and
The adsorption data were applied to both the Freundlich and Lang- the adsorption system is more heterogeneous [33].
muir equations (Eqs. (3) and (4)) [22,31], respectively.
3.4. Regeneration study
Ce =Q e ¼ ðCe ∕Q max Þ þ ð1∕KL Q max Þ ð3Þ
Other important features of any adsorbent are its regeneration and
lnQ e ¼ lnK F þ 1=n lnCe ð4Þ reusability from both environmental and economical perspective. Four
adsorption/desorption studies were performed for metal ions on the
where Qmax (mg/g) is the maximum amount of adsorption correspond- St:DB18C6 using 0.1 M HNO3 solution eluting agents (Fig. 11). The re-
ing to complete monolayer coverage, KL (L/mg) is the Langmuir con- moval efficiencies of Cu, Zn, Cd and Ni are 96.2%, 94.3%, 92 and 91.2% re-
stant associated with the sorption energy, KF is the Freundlich spectively in the first cycle. As the process was repeated a slight
constant associated with the capacity of sorption, and n is a constant re- decrease in the removal efficiency were observed in each process
lated to sorption intensity. The relative parameters obtained from the reaching 92%, 90%, 95% and 88% respectively in the fourth cycle. Incom-
Langmuir and Freundlich isotherm models are recorded in Table 2. plete desorption of metal ions which lead to decrease in number of

120
Adsorpon Desorpon

100 Cu Zn Cd Ni Cu Zn Cd Ni
Sorption and Desorption %

80

60

40

20

0
1 2 3 4
Number of cycles

Fig. 11. Recycling of the St:DB18C6 in removal of Cd2+, Zn2+, Ni2+ and Cu2+.
 B.M. Ibrahim, N.A. Fakhre / International Journal of Biological Macromolecules 123 (2019) 70–80 79

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