You are on page 1of 12

Cellulose (2013) 20:849–860

DOI 10.1007/s10570-013-9875-9

ORIGINAL PAPER

Chemically modified kapok fiber for fast adsorption of Pb2+,


Cd2+, Cu2+ from aqueous solution
Chunting Duan • Ning Zhao • Xiaolan Yu •

Xiaoyan Zhang • Jian Xu

Received: 28 October 2012 / Accepted: 28 January 2013 / Published online: 9 February 2013
Ó Springer Science+Business Media Dordrecht 2013

Abstract Kapok fiber, a natural hollow fiber with large specific area derived from the hollow fiber
thin shell and large cavity, has rarely been used as structure, kapok-DTPA exhibited much better adsorp-
adsorbent for heavy metal ions. In this paper, kapok tion capacity compared with many other reported
fibers were modified with diethylenetriamine pentaa- adsorbents based on natural materials.
cetic acid (DTPA) after hydrophilicity treatment. The
adsorption behavior of the resultant kapok-DTPA Keywords Kapok fiber  Chemical modification 
influenced by pH, adsorption time and initial concen- Fast adsorption  Regeneration
tration of metal ion was investigated. The results
demonstrate that adsorption equilibrium was reached
within 2 min for Pb2? and Cd2?. Adsorption kinetics
showed that the adsorption rate was well fitted by Introduction
pseudo-second-order rate model. The adsorption iso-
therms were studied, and the best fit was obtained Heavy metal pollution in water is an important issue of
in the Langmuir model. The maximum adsorption water pollution. Heavy metal pollution not only
capacities of kapok-DTPA were 310.6 mg g-1 for influences the quality of the water body, but also
Pb2?, 163.7 mg g-1 for Cd2?, 101.0 mg g-1 for affects the production and quality of the crops and
Cu2?, respectively. After eight desorption and aquatic products, and threatens the health and life of
re-adsorption loops, the lost adsorption capacities for animals and human beings through the food chain
Pb2? and Cu2? were less than 10 %. Because of the (Cheng 2003). Due to harmful effects of heavy metal
ions pollution in water, there is a pressing need to find
efficient methods to combat this kind of pollution.
C. Duan  N. Zhao (&)  X. Yu  X. Zhang  J. Xu (&) Many approaches for the removal of heavy metal ions
Beijing National Laboratory for Molecular Sciences,
from aqueous solution have been carried out, such as
Laboratory of Polymer Physics and Chemistry,
Institute of Chemistry, Chinese Academy of Sciences, ion exchange, reverse osmosis, adsorption, complexa-
Beijing 100190, People’s Republic of China tion/sequestration and precipitation-neutralization.
e-mail: zhaoning@iccas.ac.cn Adsorption is an efficient method that was extensively
J. Xu used for the removal of heavy metal ions from
e-mail: jxu@iccas.ac.cn household and industrial waste water (Yin et al.
2008). Activated carbon (Kula et al. 2008), graphene
C. Duan
University of Chinese Academy of Sciences, (Gao et al. 2011), clay (Ozdes et al. 2011), oxides (Shi
Beijing 100049, People’s Republic of China et al. 2011) and polymeric material (Jiang et al. 2012;

123
850 Cellulose (2013) 20:849–860

Neghlani et al. 2011) have been utilized as adsorbents. in adsorbing copper ion(II) (Zhang et al. 2012).
However, most of these materials are non-renewable Composite materials based on cellulose and cellulose
or non-biodegradable and may cause secondary acetate are also found to be useful in the adsorption of
pollution. CuCl2 from ethanol (Magosso et al. 2012).
Recently, natural materials have attracted increas- In this study, we prepared adsorbents based on
ing research interest as adsorbents for heavy metals kapok fiber. Kapok fiber is a natural fiber presenting a
owing to their renewable and biodegradable proper- large hollow structure. The volume porosity is more
ties. Gil and coworkers (Gurgel et al. 2008a, b; Júnior than 90 % (Hori et al. 2000). Due to its hydrophobic-
et al. 2009; Karnitz et al. 2007) modified sugarcane oleophilic characteristic, homogeneous hollow tube
bagasse and cellulose with different chelating reagents shape and low density, kapok fiber has been widely
and obtained adsorbents with good adsorption perfor- used as fiberfill in pillows, oil sorbent (Abdullah et al.
mance. Li and coworkers (Liu et al. 2010) modified 2010; Khan et al. 2004; Lim and Huang 2007b), oil/
peanut shell with epichlorohydrin and ethylenedia- water separator (Huang and Lim 2006; Lim and Huang
mine to adsorb Hg2? and Cd2?. Starch has been 2006, 2007a), reinforcement (Mwaikambo and Ansell
modified with dialdehyde o-phenylenediamine and 2002) and buoyancy materials (Zhang et al. 2013).
dialdehyde aminothiazole to prepare different adsor- However, kapok fibers are rarely used as adsorbents
bents (Yin et al. 2008; Zhao et al. 2010). Fir sawdust for heavy metal ions. Compared with other natural
lignocellulose was functionalized by copolymeriza- fibers, the large hollow structure is desirable for the
tion with N-vinylpyrrolidone, and its adsorption application as absorbents. In this publication, kapok
capacity for tea catechins was improved (Ye et al. fibers were chemically modified with diethylenetria-
2010). Wheat straw has been treated with citric acid mine pentaacetic acid (DTPA) to remove metal ions
and the adsorption properties of copper ion and from aqueous solutions. The influences of pH, adsorp-
methylene blue were investigated (Han et al. 2010). tion time and initial concentration of metal ion in the
Groundnut shell and sawdust were assessed for heavy adsorption behavior were investigated. In control
metal ions adsorption before and after being loaded experiment, absorbent cotton was treated under sim-
with dye (Shukla and Pai 2005). Besides chemical ilar conditions. The higher adsorption quantity and
modification, some natural materials can be used as shorter equilibrium time of kapok fibers than that of
adsorbents directly without any treatment. For exam- the cotton indicate the advantage of the hollow fiber
ple, juniper bark and wood have the ability of structure as adsorbents. Regeneration tests were also
adsorbing cadmium ions due to the carboxyl groups carried out to evaluate the practical utility.
on the surface (Shin et al. 2007), and banana peel
(Castro et al. 2011) can extract lead and copper ions
from water because of its carboxylic and amine Experimental section
groups. The removal of copper and lead ions in water
by biodegradable chitosan-coated sand has been Materials
reported (Wan et al. 2010). Pine cone powder was
demonstrated for its biosorption of lead ions (Ofomaja The kapok fibers used were produced in Sichuan
and Naidoo 2010), and Babu et al. (Gupta and Babu province of China. Diethylenetriamine pentaacetic
2009) used sawdust as an adsorbent to remove Cr(VI) acid (DTPA, Aladdin-reagent) was used without
from aqueous solutions. Chitin, as the second most further purification. Absorbent cotton, acetic anhy-
abundant natural polymer, can also be used for dride, pentasodium DTPA, N,N0 -dimethyl formamide
absorption with or without modification (Bhatnagar (DMF), sodium hydroxide (NaOH), acetone, diethyl
and Sillanpaa 2009; Karthikeyan et al. 2005; Tang ether, pyridine, sodium hydrogen carbonate (NaHCO3),
et al. 2012). Zhang’s group prepared biodegradable sodium carbonate (Na2CO3), ethanol, dichlorometh-
cellulose/chitin beads, which possessed higher heavy ane, copper sulfate (CuSO4), lead nitrate (Pb(NO3)2),
metals uptake capacity than pure chitin flakes (Zhou cadmium chloride (CdCl2) and nitric acid (65–68 wt%)
et al. 2004, 2005). Reusable Fe3O4/chitosan/PAA were purchased from local chemical suppliers and used
composite particles showed high adsorption capacity without any treatment.

123
Cellulose (2013) 20:849–860 851

Synthesis of DTPA anhydride of sodium hydroxide 5 % (7.2 mL) in ethanol (50 mL)
was stirred under reflux for 2 h. Then the fibers were
DTPA anhydride was synthesized following the filtered, and washed with sodium hydroxide aqueous
method described elsewhere (Júnior et al. 2009). solution (5 %), deionized water, ethanol, acetone, and
DTPA (20 g) was suspended in anhydrous pyridine followed by drying at 80 °C for 1 h. The obtained
(40 mL), then acetic anhydride (25 mL) was added product was EH-kapok.
dropwise. With strong mechanical stirring, the mix-
ture was heated and kept at 65 °C for 24 h. The solid Adsorption and regeneration experiments
product was filtered, washed with acetic anhydride,
diethyl ether, and dried under vacuum at 60 °C for 2 h. Adsorbents were added to different metal ions solu-
tions at a dosage of 1.0 g L-1 for Cd2? and Cu2?,
Preparation of kapok-DTPA and cotton-DTPA 0.8 g L-1 for Pb2?, separately. Initial pH value of the
solution was calibrated using HNO3 and NaOH
Kapok fibers were cut to a length of 50–100 lm by a solutions. The adsorption experiments were carried
commercially available juice extractor. The resultant out at room temperature. The adsorption capacity qe
short fibers were washed thoroughly with dichloro- (mg g-1) was calculated according to the equation:
methane to remove the botanic wax. 1.5 g of the short
ðc0  ce ÞV
and clean kapok fibers was dispersed into 200 mL qe ¼ ; ð1Þ
m
NaOH aqueous solution (5 M) at room temperature
and stirred for 24 h. Then the fibers were filtered, and where c0 and ce are the initial and equilibrium metal
washed with plenty of deionized water, ethanol and ions concentration (mg L-1), respectively. V is the
acetone. After being dried at 60 °C for 3 h, mercerized volume of metal ion solution, and m is the mass of
kapok fiber (Mkapok) was obtained. Mkapok (4.6 g) adsorbent used for adsorption experiment.
and DTPA anhydride (13.2 g) were suspended in Kinetic experiments of metal ion adsorption were
DMF (100 mL), and the mixture was stirred at 75 °C performed to determine the adsorption equilibrium
for 20 h. Then the fibers were filtered, and washed time at fixed concentrations (300 mg L-1 for Pb2?;
with DMF, deionized water, saturated sodium bicar- 200 mg L-1 for Cd2?; 200 mg L-1 for Cu2?), at pH
bonate solution, deionized water, ethanol 95 %, value of 4.5. Experiments of pH study were carried out
acetone, and followed by drying at 80 °C for 1 h. to determine the effect of pH on metal ion adsorption.
The product was named as kapok-DTPA. Concentrations of metal ions were 300 mg L-1 for
Absorbent cotton fibers were also cut short by the Pb2?, 200 mg L-1 for Cd2?, 200 mg L-1 for Cu2?.
juice extractor and then treated by a similar procedure The reaction time for each ion was 10 min. For
mentioned above. Mercerized cotton was termed as adsorption isotherms, the concentrations were set from
Mcotton, and DTPA modified cotton was labeled as 50 to 650 mg L-1 for Cu2?, 50 to 750 mg L-1 for
cotton-DTPA. Cd2? and Pb2?, at pH value of 4.5. The reaction time
was 10 min.
Impregnation and ester hydrolysis experiments The adsorption experiments for cotton-DTPA are
carried out in the same way as for kapok-DTPA.
Impregnation experiment was carried out as follows: Used kapok-DTPA was dealt with 1 M HCl
1.0 g Mkapok was added into pentasodium DTPA solution for regeneration. After being washed for 3
aqueous solution (4.1 g pentasodium DTPA being times, no metal ion was detected in the filtrate,
dissolved in 100 mL water), and the mixture was indicating complete desorption. Then it was reem-
stirred at room temperature for 20 h. Then the fibers ployed in metal ion removal.
were filtered, and washed with deionized water,
ethanol 95 %, acetone, and followed by drying at Characterization
80 °C for 1 h. The product was named as impregnated
kapok. The morphology of the fibers was studied by JSM-
General procedure for ester hydrolysis of kapok- 6700F field emission scanning electron microscopy.
DTPA: a mixture of 0.3 g kapok-DTPA in the solution Specific surface area and porosity were measured by

123
852 Cellulose (2013) 20:849–860

because of the hydrophobic botanic wax on the surface


(Fig. 1a). After being washed thoroughly with dichlo-
romethane to remove the botanic wax, the fibers
became hydrophilic and can be dispersed well in water
(Fig. 1b). Treatment with NaOH solution and modi-
fication with DTPA improved the hydrophilicity of the
fibers, so both Mkapok and kapok-DTPA dispersed
even better than the washed kapok (Fig. 1c, d). The
hydrophilicity and dispersibility of Kapok-DTPA
Scheme 1 Synthesis route of kapok-DTPA
promise fully contact with heavy metal in the adsorp-
AutoPore IV 9500 mercury porosimetry. Infrared tion process.
spectra were obtained from FT-IR spectrophotometer Before the modification, most of the kapok fibers
of BRUKER TENSOR 27. Elemental content was were 50–100 lm in length, 20–30 lm in diameter
analyzed by Flash EA1112. The concentrations (Fig. 2a), and with a cylindrical microtube shape
of metal ions were measured using a Varian (Fig. 2b). After treatment with NaOH solution, kapok
710-ES inductively coupled plasma atomic emission fibers were wrinkled but the hollow structure remained
spectroscopy. (Fig. 2c). From the enlarged image we can see the
microtube shrink a little and the thickness of the wall
increases from 0.7 to 1–2 lm (Fig. 2d). In contrast,
Results and discussion cotton fibers have a similar diameter but without
hollow structure, and the ends are always solid with
Preparation of kapok-DTPA and cotton-DTPA irregular shape (Fig. 2e). The morphology of the cotton
fiber does not show obvious change before and after the
The synthesis route of kapok-DTPA is shown in treatment with NaOH, as exhibited in Fig. 2e, f.
Scheme 1. The main components of kapok are cellu- In addition, specific surface area and porosity of
lose and lignin, and a small amount of hemicelluloses Mkapok and Mcotton were measured by mercury
is also contained. Lignin was removed after treatment porosimetry. Specific surface area and porosity were
with NaOH solution, and part of hydroxyls in cellulose 3.17 m2 g-1 and 89.9 % for Mkapok, 0.96 m2 g-1
turned to hydroxyl-sodium. and 84.3 % for Mcotton, respectively. Both from the
Kapok fiber is very light and has excellent buoy- SEM and mercury porosimetry results, one can judge
ancy performance. The fibers floated on the water that the hollow structure and thin shell endow Mkapok

Fig. 1 Photographs of the original kapok (a), the washed kapok (b), Mkapok (c) in water and kapok-DTPA (d) in CuSO4 solution

123
Cellulose (2013) 20:849–860 853

Fig. 2 SEM images of


kapok fiber (a, b), Mkapok
(c, d), cotton before (e) and
after (f) modification. The
insets in e and f are
magnified images to show
the cross section of the
cotton fiber

larger specific surface area and higher porosity than for cotton-DTPA. This difference can mainly be
that of Mcotton. These differences may lead to ascribed to the different specific surface area and
different contents of DTPA introduced into kapok porosity of Mkapok and Mcotton. The hollow struc-
and cotton fibers, which will further influence the ture with open ends of kapok makes Mkapok has more
adsorption capacities. specific surface area available to be reacted with
The elemental analysis results are summarized in DTPA, compared with that of solid cotton fiber.
Table 1. Nitrogen content was used to estimate the
content of DTPA (CDTPA) in the modified fibers, FT-IR characterization of kapok-DTPA
following the equation:
103  CðNÞ As depicted in Fig. 3, the band at 1,740 cm-1
CDTPA ðmmol=gÞ ¼ ð2Þ corresponding to –C=O vibration disappears for the
3  MðNÞ
Mkapok compared with the spectrum of kapok,
The calculated content of DTPA in kapok-DTPA is suggesting that lignin in kapok has been removed
1.1 mmol g-1, which is larger than that of 0.8 mmol g-1 after treatment with NaOH. The reappearance of the

123
854 Cellulose (2013) 20:849–860

Table 1 The content of C, H, N in different materials, chemical bond. After impregnated with pentasodium
obtained from elemental analysis, and the calculated content of DTPA, impregnated kapok showed no band at
grafted DTPA
1,740 cm-1 in FT-IR spectrum (Fig. 3b). It turned
Material C (wt%) H (wt%) N (wt%) CDTPA out that no pentasodium DTPA molecular was intro-
(mmol g-1) duced to Mkapok after chemical impregnation.
Kapok 44.5 6.2 0.6 – In adsorbent material of kapok-DTPA, cellulose
Mkapok 45.4 6.4 \0.3 – was combined with DTPA by ester bond. After ester
Kapok-DTPA 41.3 5.5 4.5 1.1 hydrolysis procedure, ester bond was broken, resulting
Mcotton 42.0 5.9 \0.3 –
in no band at 1,740 cm-1 in FT-IR spectrum (Fig. 3a).
Cotton-DTPA 41.6 5.8 3.4 0.8
All the results above testified to the chemical linkage
between DTPA molecular and cellulose in kapok-
Apparatus error of elemental analysis is 0.3 % DTPA.

Adsorption of kapok-DTPA for metal ions


band at 1,740 cm-1 in the spectrum of kapok-DTPA
confirms that ester bond and carboxyl were introduced
As a chelating agent, DTPA is known to form strong
onto kapok-DTPA after modification with DTPA. The
complexes with most metal ions (Byegard et al. 1999;
broad band at 1,601 cm-1 of kapok-DTPA is attrib-
Repo et al. 2009). The amine centers and carboxylates
uted to the carboxylate asymmetric stretching, also
have high affinity for metal cations (Repo et al. 2010;
indicating that DTPA was introduced onto kapok
Sillanpaa et al. 2001; Song et al. 2012).The adsorption
surface. The unchanged characteristic absorption
study of kapok-DTPA, including kinetic study, pH
bands of cellulose at about 3,410, 2,900, 1,060 cm-1
effect, adsorption isotherms, was carried out for Pb2?,
suggest the main composition of the fibers remains
Cd2?, Cu2?. Besides, adsorption capacity of other
after chemical modification. Mkapok shows absor-
metal ions was examined. The adsorption capacity
bances at 1,659 and 897 cm-1, which are indicative of
of kapok-DTPA for various typical ions followed
hemicelluloses (Mwaikambo and Ansell 2002; Sun
the sequence of Pb2? (310.6 mg g-1) [ Cd2? (163.7
et al. 1999). The adsorption at 1,659 cm-1 is due to
mg g-1) [ Cu2? (101.0 mg g-1) [ Zn2? (64.5 mg
C=O stretch of hemicelluloses, and the band at
g-1) [ Co2? (62.8 mg g-1) [ Mn2? (50.9 mg g-1) [
897 cm-1 is characteristic of b-linked hemicelluloses.
Cr3? (33.4 mg g-1). Compared with kapok-DTPA, the
Chemical impregnation experiment and ester
quantity of metal ion adsorbed on cotton-DTPA was
hydrolysis of kapok-DTPA were carried out to confirm
only 184.8 mg g-1 for Pb2?, 88.6 mg g-1 for Cd2?,
that the interaction between DTPA and kapok was
69.2 mg g-1 for Cu2?, respectively. The difference in
adsorption capacity is mainly ascribed to the different
DTPA concentration in the two modified fibers, as is
shown in Table 1.

Adsorption kinetics

Kapok-DTPA behaves relatively fast in adsorption


process for the metal ions, compared with cotton-
DTPA. As shown in Fig. 4a, the adsorption equilib-
rium is reached within 2 min for Pb2? and Cd2?, and
5 min for Cu2?, respectively. During the first minute,
the adsorption of Pb2? and Cd2? sharply increases,
with more than 90 % of the total ions being adsorbed
by the kapok-DTPA. In contrast, it takes more time for
cotton-DTPA to reach the adsorption equilibrium.
Fig. 3 FT-IR spectra of kapok, Mkapok and kapok-DTPA, Example in Fig. 4b shows that the adsorption equi-
impregnated kapok, EH-kapok librium is reached within 45 min for the adsorption of

123
Cellulose (2013) 20:849–860 855

Fig. 5 Adsorption kinetics of kapok-DTPA

Table 2 Pseudo-second-order constants and values for the


adsorption of Pb2?, Cd2?, Cu2? by kapok-DTPA, where q is
the experimental value of adsorption capacity calculated by
taking the average of qt at equilibrium
Ions Kapok-DTPA
r2 k qe,c (mg g-1) q (mg g-1)

Pb2? 0.9999 0.02899 302.1 298.0


2?
Cd 0.9999 0.2240 153.8 153.4
Cu2? 0.9990 0.01214 95.2 91.7

Fig. 4 Influence of contact time t on the absorption amount qt


of Cu2?, Pb2?, Cd2? by kapok-DTPA (a), and the comparison of The value of qe,c and k can be calculated from the
the adsorption behavior of kapok-DTPA and cotton-DTPA for slope and the intercept of the straight line (Fig. 5), and
Pb2? (b) the data are listed in Table 2. The results show that the
calculated qe,c is similar to the experimental value of
adsorption capacity (q), demonstrating pseudo-sec-
Pb2? by cotton-DPTA. The hollow structure and the ond-order equation is a good fitting model for both
high concentration of DTPA contribute to the fast adsorbents. Therefore, the adsorption process of
adsorption and high adsorption capacity of kapok- kapok-DTPA is a chemical process. (Zhang 2011;
DTPA. Tang et al. 2012; Zhou et al. 2004, 2005).
Pseudo-second-kinetic model was used to examine
the underlying mechanism of the adsorption process. Effect of pH values
Kinetic data were calculated with the following
equation: Figure 6 shows the influence of pH values on the
t t 1 adsorption amount by kapok-DTPA. The qe increases
¼ þ 2 ; ð3Þ with the increasing of pH values until after an optimal
qt qe;c kqe;c
value the adsorption capacity declines. The reason may
where k is the rate constant of the pseudo-second- be that the protonation of carboxyl groups on kapok-
kinetic (g mg-1 min-1), qt (mg g-1) is the adsorption DTPA at low pH values limits the interaction between
amount at time t (min), qe,c (mg g-1) is the calculated metal ions and DTPA, whereas the complex between
value of the adsorption amount at the adsorption metal ions and adsorbents is unstable at high pH values.
equilibrium. The hydroxyl ions in water may participate in the

123
856 Cellulose (2013) 20:849–860

Fig. 6 Influence of initial pH on the absorption amount of


Pb2?, Cd2?, Cu2? at equilibrium by kapok-DTPA

adsorption competition, which may also lead to the


decrease of adsorption capacity at higher pH values. The
differences of influence among three metal ions should
be attributed to the different complex capacities of the
carboxyl and hydroxyl groups with the metal ions.

Adsorption isotherms

As shown in Fig. 7, the adsorption amount at equilib-


rium for each metal ion increases dramatically with
increasing initial concentration at first and then tends
to level off. Fig. 8 Linear plots of adsorption isotherms of kapok-DTPA at
room temperature fitted by Langmuir (a) and Freundlich
Adsorption isotherms are used to describe how (b) models
adsorbates interact with adsorbents, and the constants
of the isotherms models are useful to determine the
amount of adsorbent needed to adsorb a required
amount of adsorbate (Tian et al. 2011). In this study,
Langmuir and Freundlich adsorption isotherm model
equations are used (see Fig. 8). Langmuir isotherm
model is suitable for monolayer adsorption on the
adsorbent surface, which supposes that all the adsorp-
tion sites are energetically uniform and adsorption
occurs on a structurally homogenous adsorbent (Gur-
gel and Gil 2009; Li et al. 2007; Tang et al. 2011). This
model can be expressed as:
ce 1 ce
¼ þ ; ð4Þ
qe qmax b qmax
where ce (mg L-1) is the concentration at equilibrium,
qe (mg g-1) is the adsorption amount at equilibrium,
Fig. 7 Influence of initial concentrations on the absorption qmax (mg g-1) and b (L mg-1) are Langmuir constants,
amount of Pb2?, Cd2?, Cu2? by kapok-DTPA the former relates to saturated monolayer adsorption

123
Cellulose (2013) 20:849–860 857

Table 3 Langmuir and Freundlich parameters for adsorption adsorption intensity, respectively. Kf is related to
isotherms of kapok-DTPA anion binding affinity, and n can be used to judge
Langmuir parameters Freundlich whether the adsorption process is favorable. The
parameters parameters calculated from the two isotherm models
qmax b (L r2 Kf (L n r2 were summarized in Table 3. According to the
(mg g-1) mg-1) mg-1) linear correlation coefficient (r2), metal ions adsorp-
tion onto kapok-DTPA belongs to the Langmuir
Cu2? 101.0 0.1765 0.9983 53.2 9 0.6994
isotherm model.
Pb2? 310.6 0.1200 0.9985 85.4 4 0.5630
From Table 3, we can see qmax of kapok-DTPA is
Cd2? 163.7 0.1017 0.9960 62.7 6 0.6928 310.6 mg g-1 for Pb2?, 163.7 mg g-1 for Cd2? and
101.0 mg g-1 for Cu2?. For Langmuir constant b [ 0,
the values of the separation factor RL are between 0
capacity and the latter relates to adsorption energy. In
and 1, indicating the adsorption process of kapok-
Langmuir model, a dimensionless parameter called
DTPA for each ion is favorable. In relation to the
separation factor RL which can indicate whether the
majority of the adsorbents derived from natural
adsorption process is favorable, is defined as follows:
materials in the literature, kapok-DTPA shows good
1 performance (Table 4). The results demonstrate kapok
RL ¼ : ð5Þ
1 þ bc0 fiber, due to its hollow structure and thin shell, is a
According to Freundlich isotherm model which is promising candidate for the fabrication of natural
based on multilayer or heterogeneous surfaces, qe is materials based adsorbents for the removal of metal
related to the concentration of metal ion in solution at ions from wasted water.
adsorption equilibrium as the following equation:
Regeneration and re-adsorption
1
ln qe ¼ ln Kf þ ln ce ; ð6Þ
n
The regeneration of kapok-DTPA with 1 M HCl
where Kf (L mg-1) and n are Freundlich con- solution had little influence on ester bond between
stants representing the adsorption capacity and the DTPA and cellulose (see Fig. 9, the content of N

Table 4 Adsorption capacities of various adsorbents for metal ions


Adsorbent Adsorption capacity and equilibrium time (mg g-1/min) References
2? 2? 2?
Pb Cd Cu

Polymer-modified magnetic nanoparticles 166/45 29.6/45 127/45 Ge et al. (2012)


Sugar beet pulp (polysaccharide)a 73.8/60 24.4/20 21.2/30 Reddad et al. (2002)
Crosslinked chitosan with epichlorohydrina 34.1/240 – 35.5/240 Chen et al. (2008)
Poly(vinyl alcohol)/chitosan 166/504 126.1/540 238/660 Li et al. (2011)
a
Dairy manure compost 95.3/\60 – 27.2/\60 Zhang (2011)
Banana peel 21.0/20 – 41.4/20 Castro et al. (2011)
Sawdusta 21.0/60 – 6.61/60 Li et al. (2007)
Modified peanut huska 29.1/60 – 10.1/60 Li et al. (2007)
Modified wheat strawa – – 397/[100 Han et al. (2010)
Modified peanut shellsa – 14.2/120 – Liu et al. (2010)
a
EDTA modified sugarcane bagasse 333/20 149/20 92.6/20 Júnior et al. (2009)
Succinic anhydride modified cellulosea 205.9/10 86.0/10 30.4/10 Gurgel et al. (2008a, b)
DTPA modified cotton 184.8/45 – – This study
Kapok-DTPAa 310.6/2 163.7/2 101.0/5 This study
a
The Langmuir maximum capacity

123
858 Cellulose (2013) 20:849–860

References

Abdullah M, Rahmah A, Man Z (2010) Physicochemical and


sorption characteristics of Malaysian Ceiba pentandra (L.)
Gaertn. as a natural oil sorbent. J Hazard Mater 177:683–691
Bhatnagar A, Sillanpaa M (2009) Applications of chitin- and
chitosan-derivatives for the detoxification of water and
wastewater—a short review. Adv Colloid Interface Sci
152:26–38
Byegard J, Skarnemark G, Skalberg M (1999) The stability of
some metal EDTA, DTPA and DOTA complexes: appli-
cation as tracers in groundwater studies. J Radioanal Nucl
Chem 241:281–290
Castro R, Caetano L, Ferreira G, Padilha P, Saeki M, Zara L,
Martines M, Castro G (2011) Banana peel applied to the
Fig. 9 Content of N, obtained from elemental analysis (appa- solid phase extraction of copper and lead from river water:
ratus error: 0.3 %), and adsorption capacity (qe) of the preconcentration of metal ions with a fruit waste. Ind Eng
regenerated kapok-DTPA at different recycle time Chem Res 50:3446–3451
Chen A, Liu S, Chen C, Chen C (2008) Comparative adsorption
of Cu(II), Zn(II), and Pb(II) ions in aqueous solution on the
crosslinked chitosan with epichlorohydrin. J Hazard Mater
fluctuated within apparatus error range). After 8 times 154:184–191
of desorption and re-adsorption loop, slight decrease Cheng S (2003) Heavy metal pollution in China: origin, pattern
was observed in adsorption capacity for Pb2? and and control. Environ Sci Pollut R 10:192–198
Gao W, Majumder M, Alemany L, Narayanan T, Ibarra M,
Cu2?. The lost adsorption capacities for Pb2? and
Pradhan B, Ajayan P (2011) Engineered graphite oxide
Cu2? were less than 10 %. materials for application in water purification. Acs Appl
Mater Interfaces 3:1821–1826
Ge F, Li M, Ye H, Zhao B (2012) Effective removal of heavy
metal ions Cd2?, Zn2?, Pb2?, Cu2? from aqueous
Conclusion
solution by polymer-modified magnetic nanoparticles.
J Hazard Mater 211–212:366–372
Kapok fiber, a natural fiber with large hollow struc- Gupta S, Babu B (2009) Modeling, simulation, and experi-
ture, has been modified with DTPA. The resultant mental validation for continuous Cr(VI) removal from
aqueous solutions using sawdust as an adsorbent. Bioresour
kapok-DTPA shows a fast adsorption for the metal
Technol 100:5633–5640
ions with the adsorption equilibrium being reached Gurgel L, Gil L (2009) Adsorption of Cu(II), Cd(II), and Pb(II)
within 2 min for Pb2? and Cd2?, and 5 min for Cu2?. from aqueous single metal solutions by succinylated mer-
Maximum adsorption capacities of kapok-DTPA are cerized cellulose modified with triethylenetetramine. Car-
bohydr Polym 77:142–149
310.6 mg g-1 for Pb2?, 163.7 mg g-1 for Cd2?, and
Gurgel L, Freitas R, Gil L (2008a) Adsorption of Cu(II), Cd(II), and
101.0 mg g-1 for Cu2?, respectively. Because of its Pb(II) from aqueous single metal solutions by sugarcane
large specific area, the modified kapok fibers have a bagasse and mercerized sugarcane bagasse chemically mod-
larger adsorption capacity than that of many other ified with succinic anhydride. Carbohydr Polym 74:922–929
Gurgel L, Júnior O, Gil R, Gil L (2008b) Adsorption of Cu(II),
reported absorbents based on natural materials. The
Cd(II), and Pb(II) from aqueous single metal solutions by
adsorption capacity of kapok-DTPA remains higher cellulose and mercerized cellulose chemically modified
than 90 % after 8 loops of desorption and re-adsorp- with succinic anhydride. Bioresour Technol 99:3077–3083
tion. All the results promise this low-cost, widely Han R, Zhang L, Song C, Zhang M, Zhu H, Zhang L (2010)
Characterization of modified wheat straw, kinetic and
available and environmental friendly natural fiber a
equilibrium study about copper ion and methylene blue
practical application in the removal of heavy ions from adsorption in batch mode. Carbohydr Polym 79:1140–1149
polluted water. Hori K, Flavier M, Kuga S, Lam T, Iiyama K (2000) Excellent
oil absorbent kapok Ceiba pentandra (L.) Gaertn. fiber:
Acknowledgments This work was supported by National fiber structure, chemical characteristics, and application.
Natural Scientific Foundation of China (No. 51073166, J Wood Sci 46:401–404
21121001), the Open Project of State Key Laboratory Huang X, Lim T (2006) Performance and mechanism of a
Cultivation Base for Nonmetal Composites and Functional hydrophobic-oleophilic kapok filter for oil/water separa-
Materials (No. 2210zxfk22). tion. Desalination 190:295–307

123
Cellulose (2013) 20:849–860 859

Jiang N, Xu Y, Dai Y, Luo W, Dai L (2012) Polyaniline Reddad Z, Gerente C, Andres Y, Le Cloirec P (2002) Adsorption
nanofibers assembled on alginate microsphere for Cu(2?) of several metal ions onto a low-cost biosorbent: kinetic
and Pb(2?) uptake. J Hazard Mater 215–216:17–24 and equilibrium studies. Environ Sci Technol 36:2067–
Júnior O, Gurgel L, de Freitas R, Gil L (2009) Adsorption of 2073
Cu(II), Cd(II), and Pb(II) from aqueous single metal Repo E, Kurniawan T, Warchol J, Sillanpaa M (2009) Removal
solutions by mercerized cellulose and mercerized sugar- of Co(II) and Ni(II) ions from contaminated water using
cane bagasse chemically modified with EDTA dianhydride silica gel functionalized with EDTA and/or DTPA as
(EDTAD). Carbohydr Polym 77:643–650 chelating agents. J Hazard Mater 171:1071–1080
Karnitz O, Gurgel L, de Melo J, Botaro V, Melo T, de Freitas Repo E, Warchol J, Kurniawan T, Sillanpaa M (2010)
GR, Gil L (2007) Adsorption of heavy metal ion from Adsorption of Co(II) and Ni(II) by EDTA- and/or DTPA-
aqueous single metal solution by chemically modified modified chitosan: kinetic and equilibrium modeling.
sugarcane bagasse. Bioresour Technol 98:1291–1297 Chem Eng J 161:73–82
Karthikeyan G, Andal NM, Anbalagan K (2005) Adsorption Shi W, Tao S, Yu Y, Wang Y, Ma W (2011) High performance
studies of iron(III) on chitin. J Chem Sci 117:663–672 adsorbents based on hierarchically porous silica for puri-
Khan E, Virojnagud W, Ratpukdi T (2004) Use of biomass fying multicomponent wastewater. J Mater Chem 21:15567–
sorbents for oil removal from gas station runoff. Chemo- 15574
sphere 57:681–689 Shin E, Karthikeyan K, Tshabalala M (2007) Adsorption
Kula I, Ugurlu M, Karaoglu H, Celik A (2008) Adsorption of mechanism of cadmium on juniper bark and wood. Bior-
Cd(II) ions from aqueous solutions using activated carbon esour Technol 98:588–594
prepared from olive stone by ZnCl2 activation. Bioresour Shukla S, Pai R (2005) Adsorption of Cu(II), Ni(II) and Zn(II)
Technol 99:492–501 on dye loaded groundnut shells and sawdust. Sep Purif
Li Q, Zhai J, Zhang W, Wang M, Zhou J (2007) Kinetic studies Technol 43:1–8
of adsorption of Pb(II), Cr(III) and Cu(II) from aqueous Sillanpaa M, Orama M, Ramo J, Oikari A (2001) The impor-
solution by sawdust and modified peanut husk. J Hazard tance of ligand speciation in environmental research: a case
Mater 141:163–167 study. Sci Total Environ 267:23–31
Li X, Li Y, Ye Z (2011) Preparation of macroporous bead Song L, Zhao X, Fu J, Wang X, Sheng Y, Liu X (2012) DFT
adsorbents based on poly(vinyl alcohol)/chitosan and their investigation of Ni(II) adsorption onto MA-DTPA/PVDF
adsorption properties for heavy metals from aqueous chelating membrane in the presence of coexistent cations
solution. Chem Eng J 178:60–68 and organic acids. J Hazard Mater 199:433–439
Lim T, Huang X (2006) In situ oil/water separation using Sun R, Fang J, Mott L, Bolton J (1999) Fractional isolation and
hydrophobic-oleophilic fibrous wall: a lab-scale feasibility characterization of polysaccharides from oil palm trunk
stud for aroundwater cleanup. J Hazard Mater 137:820–826 and empty fruit bunch fibres. Holzforschung 53:253–260
Lim T, Huang X (2007a) Evaluation of hydrophobicity/oleo- Tang H, Chang C, Zhang L (2011) Efficient adsorption of Hg2?
philicity of kapok and its performance in oily water filtra- ions on chitin/cellulose composite membranes prepared via
tion: comparison of raw and solvent-treated fibers. Ind environmentally friendly pathway. Chem Eng J 173:689–
Crop Prod 26:125–134 697
Lim T, Huang X (2007b) Evaluation of kapok (Ceiba pentandra Tang H, Zhou W, Zhang L (2012) Adsorption isotherms and
(L.) Gaertn.) as a natural hollow hydrophobic-oleophilic kinetics studies of malachite green on chitin hydrogels.
fibrous sorbent for oil spill cleanup. Chemosphere J Hazard Mater 209:218–225
66:955–963 Tian Y, Wu M, Liu R, Wang D, Lin X, Liu W, Ma L, Li Y,
Liu Y, Sun X, Li B (2010) Adsorption of Hg2? and Cd2? by Huang Y (2011) Modified native cellulose fibers-A novel
ethylenediamine modified peanut shells. Carbohydr Polym efficient adsorbent for both fluoride and arsenic. J Hazard
81:335–339 Mater 185:93–100
Magosso H, Fattori N, Arenas L, Gushikem Y (2012) New Wan M, Kan C, Rogel B, Dalida M (2010) Adsorption of copper
promising composite materials useful in the adsorption of (II) and lead (II) ions from aqueous solution on chitosan-
Cu(II) in ethanol based on cellulose and cellulose acetate. coated sand. Carbohydr Polym 80:891–899
Cellulose 19:913–923 Ye J, Dong J, Lu J, Zheng X, Jin J, Chen H, Liang Y (2010)
Mwaikambo L, Ansell M (2002) Chemical modification of Effect of graft copolymerization of fir sawdust lignocel-
hemp, sisal, jute, and kapok fibers by alkalization. J Appl lulose with N-vinylpyrrolidone on adsorption capacity to
Polym Sci 84:2222–2234 tea catechins. Carbohydr Polym 81:441–447
Neghlani P, Rafizadeh M, Taromi F (2011) Preparation of Yin Q, Ju B, Zhang S, Wang X, Yang J (2008) Preparation and
aminated-polyacrylonitrile nanofiber membranes for the characteristics of novel dialdehyde aminothiazole starch
adsorption of metal ions: comparison with microfibers. and its adsorption properties for Cu (II) ions from aqueous
J Hazard Mater 186:182–189 solution. Carbohydr Polym 72:326–333
Ofomaja A, Naidoo E (2010) Biosorption of lead(II) onto pine Zhang M (2011) Adsorption study of Pb(II), Cu(II) and Zn(II)
cone powder: studies on biosorption performance and from simulated acid mine drainage using dairy manure
process design to minimize biosorbent mass. Carbohydr compost. Chem Eng J 172:361–368
Polym 82:1031–1042 Zhang S, Zhou Y, Nie W, Song L (2012) Preparation of Fe3O4/
Ozdes D, Duran C, Senturk H (2011) Adsorptive removal of chitosan/poly(acrylic acid) composite particles and its
Cd(II) and Pb(II) ions from aqueous solutions by using application in adsorbing copper ion (II). Cellulose
Turkish illitic clay. J Environ Manag 92:3082–3090 19:2081–2091

123
860 Cellulose (2013) 20:849–860

Zhang X, Fu W, Duan C, Xiao H, Shi M, Zhao N, Xu J (2013) Zhou D, Zhang L, Zhou J, Guo S (2004) Cellulose/chitin beads
Superhydrophobicity determines the buoyancy performance for adsorption of heavy metals in aqueous solution. Water
of kapok fiber aggregates. Appl Surf Sci 266:225–229 Res 38:2643–2650
Zhao P, Jiang J, Zhang F, Zhao W, Liu J, Li R (2010) Adsorption Zhou D, Zhang L, Guo S (2005) Mechanisms of lead biosorption
separation of Ni(II) ions by dialdehyde o-phenylenedi- on cellulose/chitin beads. Water Res 39:3755–3762
amine starch from aqueous solution. Carbohydr Polym
81:751–757

123

You might also like