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CELLULOSE CHEMISTRY AND TECHNOLOGY

MODIFIED HYDROXYETHYLCELLULOSE: A REGENERABLE SUPER-


SORBENT FOR Cd2+ UPTAKE FROM SPIKED HIGH-HARDNESS
GROUNDWATER

AZHAR ABBAS, MUHAMMAD AJAZ HUSSAIN, MUHAMMAD SHER,


NAZIA SHAHANA ABBAS and MUHAMMAD ALI

Department of Chemistry, University of Sargodha, Sargodha 40100, Pakistan



Corresponding author: M. Ajaz Hussain, majaz172@yahoo.com

Received October 11, 2015

A benign super-sorbent, i.e., the sodic form of succinylated hydroxyethylcellulose (HEC-Suc-Na), was investigated for
the sorption efficiency to remove cadmium (Cd) from spiked high-hardness groundwater (HGW).
Hydroxyethylcellulose succinate (HEC-Suc) was synthesized and converted into its sodic form by treating with
saturated NaHCO3 solution. Batch-wise methodologies were used to sorb Cd2+ from HGW solution by HEC-Suc-Na.
The results show that more than 90% Cd2+ removal was achieved within the first 30 min at pH 6 from HGW at 298 K.
The Langmuir isotherm model and the pseudo-second order kinetic model provided the best fit for the sorption data of
Cd2+ uptake. The estimation of the thermodynamics parameter indicated the spontaneous and exothermic nature of the
sorption. As compared with other polysaccharidal sorbents, HEC-Suc-Na suggested its highest efficiency for Cd2+
uptake from HGW (666.66 mg g-1). The sorbent showed high selectivity for Cd removal over background ion naturally
present in HGW. The sorbent was easily regenerated using mild conditions and used for Cd2+ uptake over three cycles
with no significant decrease in its sorption capacity. It suggests the possibility for manifold use of the sorbent before it
needs to be replaced.

Keywords: adsorption, cadmium uptake, groundwater, hydroxyethylcellulose, regenerability, succinylation

INTRODUCTION
Heavy metals cause environmental stands on top among these methods due to its
contamination, which affects human health selectivity, efficiency and regenerability.6
badly.1 Cd is one of the most hazardous metals Recently, cellulose-bearing materials, such as
among the highly toxic heavy metal.2 According saw dust,7 plant barks, fruit peels,8 agricultural
to WHO, the permissible limit of cadmium in waste,9 etc., have been investigated for the
drinking water is 0.003 mg L-1. Any concentration removal of heavy metal ions. The advantages of
of Cd greater than this affects human health. these sorbents include their low cost, renewable
Owing to its non-biodegradable nature, it nature and abundance. However, these low-cost
accumulates in human vital organs and poses sorbents contain functional groups of several
serious health hazards, including cancer, mental types and it is difficult to decide that which
disorder, renal, lung and liver dysfunction.3 functional group is responsible for the removal of
Industries that discharge Cd into water streams metal ions from aqueous solutions. Another
include Ni-Cd batteries, mining, smelting, disadvantage associated with the use of low-cost
electroplating and metallurgy.4 sorbents, such as agricultural waste material, is
Precipitation, adsorption, ion exchange, their low sorption capacity. Therefore, it is
filtration, electrochemistry, chelation and reverse currently very important to use sorbents
osmosis are some methods for the elimination of containing a single type of functionalities, so that
Cd from an aqueous environment. Chemical it can be established which functionalities are
methods used for the removal of heavy metals are responsible for metal uptake. Moreover, new
more expensive and less efficient.5 Ion exchange sorbents to be introduced must be more selective
and efficient with higher sorption capacity.

Cellulose Chem. Technol., 51 (1-2), 167-174(2017)


AZHAR ABBAS et al.

Cellulose, a naturally occurring biopolymer, Synthesis of HEC-Suc conjugate and HEC-Suc-Na


which is renewable, biocompatible and nontoxic, HEC-Suc was synthesized by esterification of HEC
has ample hydroxyl (OH) groups that have with succinic anhydride using dimethylaminopyridine
affinities for heavy metal ions.10,11 Chemically by a reported method.22 HEC-Suc showed a fairly high
degree of substitution (DS 2.84) as calculated by acid-
modified cellulose has excellent heavy metal
base titration after saponification by a method adopted
removal capacity due to incorporation of new elsewhere.23 The HEC-Suc was converted into its sodic
functional groups with better ion exchange form (HEC-Suc-Na) by treating it with saturated
properties.12,13 However, intermolecular hydrogen NaHCO3 solution.24 The HEC-Suc-Na was used for the
bonds among hydroxyl groups of unmodified removal of Cd2+ from HGW. In the FTIR spectrum of
cellulose decrease its sorption capacity.14 HEC-Suc, the appearance of distinct ester carbonyl
Chemical modification of cellulose includes direct signals at 1728 cm-1 is the indication of successful
conversion of the hydroxyl groups of cellulose succinylation of HEC. Moreover, the appearance of the
into some useful functional groups with more characteristic carboxylate anion peak at 1587 cm-1 in
binding sites.15,16 Many researchers have used the spectrum of HEC-Suc-Na is a direct indication of
sodium salt formation. The surface charge of HEC-
succinylated cellulose as a sorbent for the removal
Suc-Na was monitored by calculating the pHZPC (pH
of heavy metal ions from aqueous solution and corresponding to the point of zero charge), which was
acquired useful results.17-21 found to be 4.2. Above this pH, the surface of the
So far, cellulose ether derivatives have not sorbent has negative charge, which favors metal
been exploited for heavy metal uptake. Keeping uptake.
in mind the presence of free hydroxyls outside of
the main cellulose chains, hydroxylethylcellulose Sorption experiments
(HEC) is reported for metal uptake after The stock solution of Cd2+ (1000 mg L-1) was
modification. Therefore, HEC-succinate (HEC- prepared in HGW and diluted to required
Suc) was synthesized, followed by its conversion concentrations. The pH of the solutions was adjusted
using HCl (0.1M) and NaOH (0.05M) solutions. The
to the sodic form (HEC-Suc-Na) by treatment
concentration of Cd2+ was recorded by using an atomic
with NaHCO3. Then, HEC-Suc-Na was used for absorption spectrophotometer (AAS) AA 6300
the removal of Cd2+ from HGW solution. The (Shimadzu, Japan) at 228.8 nm wavelength using
effects of contact time, pH, initial concentration flame (air-acetylene). In order to optimize sorbent
and temperature on the sorption capacity have dosage, 10, 20, 40, 60, 80 and 100 mg of the sorbent
been investigated. To assess the feasibility of were added to Cd+2 (100 mg/L) solutions and stirred at
sorption, thermodynamic parameters, such as, 298 K for 30 min at a speed of 130 rpm in HGW. It
∆G°, ∆H° and ∆S°, were estimated. Kinetic was found that the sorption capacity was maximum for
studies were carried out to establish the 20 mg sorbent dose. So, this optimized amount of
mechanism of Cd2+ removal from HGW. sorbent was chosen for further studies. To optimize the
pH for Cd2+ uptake, the optimized amount of the
Furthermore, the reproducibility of the novel
sorbent (20 mg) was stirred over a range of 5-120 min
super-sorbent HEC-Suc-Na was also investigated. in HGW (100 mL) containing Cd2+ (140 mg L-1) at a
speed of 130 rpm at 298 K over a pH range of 2-8.
EXPERIMENTAL FAAS was used to determine the Cd2+ from the
Materials supernatant.
Natrosol hydroxyethylcellulose (HE10K, The effects of contact time and temperature on
Belgium) was purchased from a local market. HEC Cd2+ adsorption from HGW were investigated using a
was dried at 110 °C for 2 h before use. Cadmium fixed amount of HEC-Suc-Na (20 mg). The mixture
nitrate, NaOH, HCl, NaHCO3 and diethylether was stirred over a time range of 5-150 min and
provided by Fluka were of analytical grade. The temperature range of 298-343 K in HGW (100 mL)
chemical characteristics of the HGW, collected from containing Cd2+ (140 mg L-1) at a speed of 130 rpm.
Sargodha city suburbs (pH 7.3, Total Hardness = 1425 The percentage metal ions uptake was assessed by
mg L-1 (as CaCO3), Magnesium Hardness = 926.5 mg using AAS. The effect of initial concentration on
L-1, Calcium Hardness = 498.5 mg L-1, Total Alkalinity sorption was evaluated by stirring sorbent (20 mg) in
= 563.2 mg L-1, P-Alkalinity (CO3-2) = 0 mg L-1, M- HGW (100 mL) containing Cd2+ (140, 170, 200, 230
Alkalinity (HCO3-1) = 563.2 mg L-1, Chlorides = 1435 and 260 mg L-1) for 30 min at 130 rpm. The
mg L-1, Sulphates = 197.2 mg L-1, Nitrates = 28 mg L- equilibrium concentrations of metal ion were analyzed
1
, Phosphates = 20.3 mg L-1, Bicarbonates = 699 mg L- by AAS. The adsorption capacity and % Cd2+ uptake
1
, Carbonates = 0 mg L-1, Iron = 0.134 mg L-1) were was determined utilizing the following relations:
determined using different analytical techniques that Ci − C f
are widely used for routine water analysis. qe = ×V (1)
m

168
Hydroxyethylcellulose

Ci − Ce models. It is well established that the sorption


Percentageuptake = ×100 (2)
Ci mechanism depends on the physical and chemical
where Ce and Ci are the equilibrium and initial characteristics of the sorbent and also on the mass
concentrations of Cd2+ in mg L-1, respectively, qe is the transfer process. The pseudo-first, pseudo-second
equilibrium adsorption capacity in mg g-1, V is the order and the Weber-Morris intraparticle diffusion
volume of the solution in L and m is the mass of models were applied to the data obtained from the
sorbent in grams. contact time experiments in order to establish the
kinetics of sorption. The linear form of the
Statistical analysis pseudo-first order model is described by the
The isotherm data were fitted to various models by following relation:
non-linear regression analysis using the STATISTICA k
software package (release 6) for Windows. The log ( qe − qt ) = logqe − 1 t (6)
significance of the data fit by various models was 2.303
evaluated by the t-test. It has been found that the pseudo-first order
equation is applicable to a limited range of
Regeneration of sorbent sorption processes only. So, the experimental data
The sorbent HEC-Suc-Na was easily regenerated obtained from the initial rapid phase of sorption
using saturated aqueous NaCl solution. The was chosen to fit the pseudo-first order kinetic
regenerated sorbent was thoroughly washed with equation. The time range for the initial rapid
deionized water, then air-dried. The absence of the
phase was 5-60 min, so this time range was
NaCl in the sorbent was verified by the negative
AgNO3 test. The regenerated sorbent was reused over
chosen for Cd uptake from HGW solution to fit
three cycles for Cd2+ uptake. the pseudo-first order kinetic equation. Figure 2
shows the plots of log(qe - qt ) against t for Cd
Thermodynamics determination uptake from HGW solutions. The values of k1 and
The effect of temperature on Cd2+ uptake was used qe are obtained from the slope and intercept of the
to estimate different thermodynamic parameters such
straight line, respectively. The values of k1, qe and
as change in free energy (∆G°), enthalpy (∆H°) and
entropy (∆S°) by using the following relations: R2 are listed in Table 1. The low value of the
correlation coefficients, around 0.86, and the
∆ G ° = − R T ln K c (3) deviation of calculated qe value from the
∆ S ° ∆H ° (4) experimental value suggest the inadequacy of the
lnK c = −
R RT pseudo-first order model to fit the experimental
∆S ° ∆H ° (5) data, even for the initial phase of the sorption
lnK c = −
R RT process. The intraparticle diffusion equation is
where Ce is the equilibrium Cd concentration and Cads described as:
is the amount of Cd2+ adsorbed. A plot of lnK against qt = k2t 1/2 + kd (7)
1/T (K-1) gives ∆S° as slope and ∆H° as intercept.
This equation may be applied to determine the
RESULTS AND DISCUSSION intraparticle diffusion rate constant, k2, and the
Kinetic study of Cd2+ removal by HEC-Suc-Na boundary resistance, kd. The plots of qt versus t1/2
Effect of contact time for the Weber-Morris intraparticle diffusion
The effect of contact time showed that more model are shown in Figure 3. From the figure, it
than 90% Cd was removed within the first 30 min is noted that the sorption kinetic data does not fit
from the HGW solution by HEC-Suc-Na (Fig. 1). well to this kinetic model. The pseudo-second
The presence of several sodic-succinate order model provided the best fit to the Cd uptake
functionalities was the main reason for this initial data obtained from the contact time
prompt phase. When adsorption equilibrium time experiments.25 The linear form of the pseudo-
was reached, almost all vacant sites were engaged second order model is described by the following
by Cd2+, which caused a decrease in the rate of relation:
adsorption after 30 min. t 1 t
= + (8)
qt k3 qe 2 qe
Kinetic modeling where qt and qe are the amounts of Cd sorbed at
In order to evaluate the mechanism that time t and equilibrium, respectively, k3 is the
controls the sorption phenomenon, sorption pseudo-second-order rate constant (g mg-1 min-1).
experimental data were fit to various kinetic Plotting t/qt versus t gives the best fit pseudo-

169
AZHAR ABBAS et al.

second order kinetic model as evident from the The effect of pH on the removal of Cd2+ from
high correlation coefficients (Fig. 4). The qe value HGW solution by HEC-Suc-Na was investigated
calculated from the plot agrees well with the to identify the pH at which maximum adsorption
experimental values (Table 1). Thus, it can be takes place. It was evident from the plot (Fig. 5)
confirmed that the adsorption of Cd on HEC-Suc- that there was a low uptake of Cd2+ at lower pH,
Na followed the pseudo-second-order kinetic which can be attributed due to protonation of
model. Moreover, it can be concluded that the HEC-Suc-Na to form carboxylic acid and the
rate-limiting step is chemisorption, which unavailability of Na functionalities to exchange
involves the exchange of electrons between Cd with Cd2+. Cd uptake increased abruptly as the pH
and the adsorbent HEC-Suc-Na. was increased from 4 onward. The maximum
removal was witnessed at pH 6 from HGW
Effect of pH on Cd uptake solution, which favored an enhanced ion
exchange mechanism at higher pH values.

6
600
5
500
4
400

log (qe-qt)
qt

3
300
2
200

100 1

0 0
0 25 50 75 100 125 0 20 40 60
t, min t, min
Figure 1: Plot of Cd uptake from HGW on HEC- Figure 2: Fitting of pseudo-first order model for
Suc-Na as a function of contact time Cd uptake from HGW on HEC-Suc-Na

12 0.2

10 0.16
t/qt, min/mg g-1

8
0.12
6
0.08 y = 0.0015x + 0.0053
qt

4 R² = 0.9977
2 0.04

0 0
500 550 600 650 0 25 50 75 100 125
t1/2 t, min

Figure 3: Fitting of intra-particle diffusion model Figure 4: Fitting of pseudo-second order model
for Cd uptake from HGW on HEC-Suc-Na for Cd uptake from HGW on HEC-Suc-Na

Table 1
Values of qe, k, k1 and R2 calculated from pseudo-first and pseudo-second order kinetic models
for Cd2+ removal from HGW using HEC-Suc-Na

Experimental Pseudo-second order Pseudo-first order


Solution
qe(mg g-1) qe(mg g-1) k1 R2 qe(mg g-1) k3 R2
HGW 630.0 666.66 0.00080 0.9997 8.993 0.025 0.9175

170
Hydroxyethylcellulose

700 650

600
600
500
550

Qmax
400
qe

300 500
200
450
100
400
0
295 305 315 325 335 345
1 2 3 4 5 6 7
pH T, K
Figure 5: Effect of pH on Cd uptake from HGW by Figure 6: Effect of temperature on % Cd uptake from
HEC-Suc-Na HGW by HEC-Suc-Na

Effect of temperature Ce C 1
The sorption of Cd decreased by 9% as the = e + (10)
qe Qmax Qmax × b
temperature increased from 298 to 338 K (Fig. 6).
where qe (mg g-1) is the amount of a metal
This was due to the fact that at lower
adsorbed, Ce (mg L-1) is the equilibrium Cd
temperatures, the Cd ions present in the solution
concentration, Qmax (mg g-1) is the maximum
were less mobile and could interact more with the
sorption capacity when a complete monolayer is
exchange sites. Thus, there was an augmented ion
formed on the adsorbent surface and b is the
exchange at lower temperature. As the
Langmuir constant. The values of Ce/qe were
temperature was increased, the ions became
plotted against Ce. A straight line with high
highly mobile and there was less attraction
correlation coefficients was obtained, which
between the adsorbent and the adsorbate, resulting
shows that the sorption data best fitted to the
in diminished ion exchange.
Langmuir model (Fig. 8). The slope and intercept
of the straight line give the values of Qmax and b.
Sorption isotherm
The maximum adsorption capacity of Cd2+ from
The equilibrium sorption isotherm describes
HGW solution was found to be 666.66 mg g-1.
the interactive behavior between the sorbate and
The high value of Qmax is due to the larger
the sorbent. The main parameter to design a
concentration of succinate moieties on the sorbent
sorption system is the sorption capacity of a
HEC-Suc-Na (Table 2). A literature review
sorbent. Sorption isotherms also predict the value
reflected that HEC-Suc-Na appeared as
of sorption capacity. The experimental data
reasonably superior to other reported
obtained for the sorption of Cd2+ ions from HGW
polysaccharide sorbents (Table 3).
by the sorbent HEC-Suc-Na was subjected to the
The t-test results showed that the Langmuir
Freundlich and Langmuir isotherms. The linear
model described the isotherm data at 95%
form of the Freundlich isotherm is described as:
confidence level.
1
logqe = logkF + logCe (9)
n Ion exchange mechanism
A straight line with a low correlation The involvement of the ion exchange
coefficient was obtained by plotting values of mechanism was evidenced from the fact that
logqe against logCe (Fig. 7). The values of kF and HEC-Suc showed a low Cd uptake (11.2%), while
n are obtained by the slope and intercept of the HEC-Suc-Na showed a reasonably high Cd
straight line. The values of R2, kF and n obtained uptake (90.02%) from HGW due to the exchange
from the plot are presented in Table 2. The of Cd2+ with Na ions present in the sodic form of
adsorption isotherm data were best fitted to the the sorbent (Fig. 9). It is also worth mentioning
Langmuir model. It assumes that the adsorbed that such a high Cd uptake was due to the high
ions form a monolayer on the adsorbent surface, degree of substitution (2.84) of succinate groups
as all adsorbent sites are energetically identical onto HEC that resulted in the high concentration
and there is no attraction between the adsorbed of Na ions, which, in turn, augmented the ion
ions. The linearized form of the Langmuir model exchange phenomenon during the rapid initial
is represented as: phase of adsorption.

171
AZHAR ABBAS et al.

Table 2
Frendlich and Langmuir parameters for Cd2+ removal from HGW sorption using HEC-Suc-Na

Parameters HGW
Experimental
qe(mg g-1) 630
Qmax(mg g-1) 666.66
Qmax(mmol g-1) 5.9444
Langmuir
b (mg L-1) 0.1095
parameters
b (mmol L-1) 12.279
R2 0.9995
RL 0.0612
n 158.73
Freundlich
kF 640.212
parameters
R2 0.0055

Table 3
Comparison of HEC-Suc-Na with other reported polysaccharide sorbents for Cd2+ removal

Sorbent (treatment) Sorption capacity (mg g-1)


Bagasse pith (SO2 and H2S, heat)26 149.9
Sugarcane bagasse (1,3-diisopropilcarbodiimide, 313
triethylenetetramine)27
Polymer-modified magnetic nanoparticles28 29.6
Filter aid cellulose (succinic anhydride, sodic)24 185.6
Mercerized cellulose29 87
Poly(vinyl alcohol)/chitosan30 126.6
Mercerized cellulose (succinic anhydride)31 256.4
Kapok (DTPA)32 163.7
Carboxylated cellulose nanocrystals18 344.8
Hydroxyethylcellulose (succinic anhydride, sodic) 666.6 from HGW Present work (highest)

6.48 0.45
Ce/qe, mg L-1/mg g-1

0.4

6.44 0.35
log qe

0.3

6.4 0.25
y = 0.0016x + 0.0086
0.2 R² = 0.9857

6.36 0.15
4.8 5 5.2 5.4 5.6 5.8 110 140 170 200 230 260
log Ce Ce, mg L-1

Figure 7: Freundlich sorption isotherm for Cd uptake Figure 8: Langmuir sorption isotherm for Cd uptake
from HGW by HEC-Suc-Na sorbent from HGW by HEC-Suc-Na sorbent

172
Hydroxyethylcellulose

100 2.4

80
2.2
Cd-uptake, %
2
60

LnKc
1.8 y = 1413.5x - 2.4986
40
R² = 0.9568
1.6
20
1.4
0
HEC-Suc HEC-Suc-Na Regenerated Regenerated Regenerated 1.2
HEC-Suc-Na HEC-Suc-Na HEC-Suc-Na 0.00293 0.00302 0.00311 0.0032 0.00329 0.00338
(1st cycle) (2nd cycle) (3rd cycle)
1/T, K-1
Figure 9: Percentage Cd uptake by acidic (HEC-Suc), Figure 10: Effect of temperature on equilibrium
sodic (HEC-Suc-Na) and regenerated sodic forms constant for Cd uptake from HGW by HEC-Suc-Na
(three cycles) from HGW by sorbent HEC-Suc-Na

Table 4
Thermodynamics parameters for Cd2+ sorption using HEC-Suc-Na

∆S° ∆H° R2 ∆G°


Solution
(J/mol/K) (kJ/mol) (kJ/mol)
HGW -20.77 -11.75 0.9568 -5.44

Regeneration studies capacity for Cd uptake (666.66 mg g-1) from


The sorbent was regenerated using green HGW. More than 90% Cd removal achieved
conditions, i.e., by treating the sorbent with brine. within 30 min indicated an augmented ion
This resulted in desorption of the sorbed Cd ions. exchange mechanism. The estimation of the
This regenerated HEC-Suc-Na was again used for thermodynamics parameter showed that Cd
Cd uptake from HGW solution. There was a adsorption is spontaneous and exothermic. The
negligible decrease in the adsorption capacity of sorbent showed high selectivity for Cd removal
Cd2+ from the HGW solution after regeneration. over background ions naturally present in HGW
This process was repeated over three cycles and (Ca2+ and Mg2+). The sorbent was efficiently
the total decrease in the adsorption capacity after regenerated by using brine and was reused with
three cycles was found to be of 1.22%. This result no significant decrease in the sorption capacity
has suggested the potential for manifold use of the after three cycles. Therefore, it can be established
sorbent before it needs to be replaced (see Fig. 9). that HEC-Suc-Na is a highly efficient,
regenerable and reusable sorbent for Cd uptake
Thermodynamics determination from HGW.
The effect of temperature on the adsorption of
Cd2+ from the HGW solution was used to estimate ACKNOWLEDGEMENTS: A. Abbas
the values of ∆G°, ∆S° and ∆H°. A plot of lnK acknowledges the financial support of the Higher
against 1/T (K-1) gives ∆S° as slope and ∆H° as Education Commission of Pakistan (HEC) under
intercept (Fig. 10). The negative values of ∆G° the “HEC Indigenous 5000 PhD fellowships
and ∆H° were indicative of spontaneous and program”. Authors are grateful to Mr.
exothermic nature of sorption. The negative value Muhammad Sarfraz, Research Officer, PCRWR
of ∆S° revealed a decrease in randomness at the (Pakistan Council of Research in Water
adsorbent-adsorbate interface during the sorption Resources) Laboratories, Sargodha, Pakistan, for
(Table 4). valuable discussion.

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