Duan 2013
Duan 2013
Duan 2013
DOI 10.1007/s10570-013-9875-9
ORIGINAL PAPER
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;
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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.
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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
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852 Cellulose (2013) 20:849–860
Fig. 1 Photographs of the original kapok (a), the washed kapok (b), Mkapok (c) in water and kapok-DTPA (d) in CuSO4 solution
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Cellulose (2013) 20:849–860 853
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
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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 kinetics
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Cellulose (2013) 20:849–860 855
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856 Cellulose (2013) 20:849–860
Adsorption isotherms
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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
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858 Cellulose (2013) 20:849–860
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