Study on the synthesis new type cross-linked chitosan porous resin and the
absorption of Cd（Ⅱ）and Ni（Ⅱ）
Xu Qi* Lin KeChun Cang Hui
yancheng institute of technology
college of chemical engine- eering and biological
Yan Cheng City China
xqsteve@ycit.cn
Yao Cheng
Nanjing University of Technology
College
Nanjing China
Abstract:Chitosan is a versatile material,
its derivatives has a wide range of applications.
Chitosan resin absorption metal ions, becomes
a research hotpot in recent years. A new
chelating resin using chitosan as a base
material was synthesized. Functional moiety
of tetraethylenepentamine(TEPA) chemically
bonded to the amino group of cross-linked
chitosan (CCTS) through the arm of
chloromethyloxirane,
Ethylene
glycol
diglycidyl ether(EGDE) as the cross linker.
The risen was holed by PEG-2000 to get
porous-CCTS-TEPA.The amine resin showed
a higher affinity towards the uptake of Cd（Ⅱ）
and Ni（Ⅱ）from neutrality solution, where an
uptake value of 123.54mg/g mg/g and
262.50mg/g, porous-CCTS-TEPA uptake
value of 220.86mg/g mg/g and 315.0mg/g
respectively, which was reported at pH 7 and
room temperature.
Key Word: cross-linked chitosan
tetraethylenepentamine Cd（Ⅱ） Ni
（Ⅱ）absorption porous
carcinogen roll by International Agency for
Research on Cancer(IARC) and national
toxicology plan(NTP)[6].
Usual treatments for extraction of metal
ions from effluents consist of flotation, solvent
extraction, precipitation,ion-exchange and
electrochemical separation,these methods
sometimes suffer from problems such as
excessive time requirements, high costs and
production of highly toxic sludges[7].Chitosan
was modified by compound which have amido
and hydroxyl group to adsorb heavy metal
ions is a hotspot in recent years[8-13].
Cross-linked chitosan (CCTS) was chemically
functionalized with serine diacetic acid moiety
through
the
extension
arm
of
chloromethyloxirane, then the resin was
modified
with
Tetraethylenepentamine,
PEG-2000 as the porogen, study the absoption
Cd （ Ⅱ ） and Ni （ Ⅱ ） capacity of
etraethylenepentamine modified Cross-linked
chitosan(CCTS-TEPA).
1 Introduction
With the development of industry, the
mount of produce and use of cadimium and
nickel are continuously raise. Their
compounds are widely used in galvanization,
alloy manufacture, batteries and so on[1-2].
Heavy metal ions in natural water can bring
harmful effect to human health, as well as to
animals and plants in aquatic environment[3].
In human body, cadimium and nickel could
harm many apparatus[4-5],they was pulled into
2 experiment
2.1 Reagents and materials
Chitosan(Shang Hai Lanji corporation).
benzaldehyde(AR,Tian Jin Ke mi Ou
Chemical Corporation).EGDE(AR,Shang Hai
Ru Fa Corporation). Epichlorohydrin(AR,
Sinopharm
chemical
regent
Co.Ltd).PEG-2000(AR, Sinopharm chemical
regent
Co.Ltd).
Cadmium
standard
solution(Sinopharm
chemical
regent
Co.Ltd).Nickel standard solution(Sinopharm
chemical regent Co.Ltd). CdCl2.5H2O(AR,
Department of Education of JiangSu province industrialization item
JH09-15
Sinopharm
chemical
regent
Co.Ltd).
NiCl2.H20(AR, Sinopharm chemical regent
Co.Ltd).Tetraethylenepentamine(AR,Sinopha
rm chemical regent Co.Ltd).
2.2 Instrumentations
Nicolet-670(NEXUS
USA),
Atomic
AbsorptionSpectrometer(East
&
West
analytical,
AA-7003).SEM(KYKY-EM3900M).
2.3 Synthesis of CCTS-TEPA resin
Chitosan was reacted with benzaldehyde
(80 g) in order to protect the amino group. The
protected-chitosan was then filtered by using
filter paper, and washed with ethanol to
remove the remaining benzaldehyde, followed
by washing with water.The cross-link
structure was made by refluxing the
protectedchitosan with EGDE (30 g). The
product was then filtered and washed with
ethanol andwater, respectively. The Schiff
basewas cleaved to recover amino group by
stirring the product in 0.5M hydrochloric acid
(500 mL). The cross-linked chitosan was then
filtered and washed three times with water. In
the second step, the cross-linked chitosan was
modified by introducing serine moiety through
chloromethyloxirane extension arm. The
cross-linked chitosan (5g) was reacted with
chloromethyloxirane (10g) in order to attach
the extension arm. The product was then
filtered using filter paper, and washed each
three times with ethanol and water to remove
the remaining chloromethyloxirane[3]. The
cross-linked chitosan, which has
chloromethyloxirane as an extension arm, was
then reacted with the
Tetraethylenepentamine(TEPA). The synthesis
scheme of CCTS-TEPA is shown in Fig(1).
Put 100mLatolein,a little of span-80
and PEG-2000 into flask,stired 30mins,
put CCTS-TEPA into the flask,stired
60mins, The product was then filtered using
filter paper, and washed each three times with
ethanol and water to remove the remaining
atolein ,to get porous-CCTS-TEPA.
HOH2C
HOH2C
O
O
*
CHO
O
O *
N
n
OH
*
OH
*
EtOH 12h
NH2
n
1
2
cross-linking
O
O *
O
HCl 12h
OH
EDGE dioxane NaOH
*
rf
N
n
3
cross-linking
O
O
O *
O
Cl
*
O
O
O
OH
cross-linking
OH
water/EtOH rf 3h
n
NH2
NH
n
5
CCTS 4
Cl
OH
cross-linking
O
O
cross-linking
O
O
O *
OH O
TEPA
OH
*
water/EtOH
rf
6h
NH
n
NH
H2C
H2C
Cl
6
O
HN
OH
H2C
O
O
O
EGDE
Ethyleneglycoldiglycidylether
HO
O
n
OH
NH
CH2
CH2
3
7
NH2
OH
O
Cross-linking
Fig（1）synthesis of CCTS-TEPA
2.4 ions absorption experiment
Put 0.2g CCTS-TEPA in the solution of
2+
Cd ,stired 5h, the remaining powder was
filtered using filter paper.And then repeated
2
the experiment with the
Ni2+and porous-CCTS-TEPA.
solution of
3 result and discussion
3.1 Characteristics of CCTS-TEPA resin and
CCTS-TEPA-Cd
The IR spectrum of CCTS-TEPA resin and
CCTS-TEPA-Cd resin(which have been
absorbed Cd2+)were shown in Fig(2), depicted
several
absorption peak removed.The
overlapped absorption peak removed to low
wavenumber
from
3300cm-1.The
transmogrification absorption peak removed to
1650cm-1 from 1600 cm-1,the phenomenon
indicated the Cd-N bond was founded.The
electron doublet moved to the Cd2+.The
absorption peak was not evident changed in
1000 cm-1,it show that the absorption process
did’t breach the glucose ring. The IR spectrum
of
CCTS-TEPA-Ni
is
similar
with
CCTS-TEPA-Cd. The transmogrification
absorption peak removed to 1612cm-1 from
1600 cm-1,the phenomenon indicated the Ni-N
bond was founded.
solutions were 2,3,4,5,6,7
It is calculate that CCTS-TEPA could absorb
123.54mg/g Cd2+ at room temperature and
pH=7,while the porous-CCTS-TEPA could
absorb 220.86mg/g Cd2+ in the same
condition. Use Ni2+ repeat the experiment. It is
calculate that CCTS-TEPA could absorb
262.50mg/g Cd2+ at room temperature and
pH=7,while the porous-CCTS-TEPA could
absorb 315.00mg/g Cd2+ in the same
condition. The absorption ability of the resin
was get the maximum in pH=7.In acidity
condition, the electron doublet of N atom
could found coordinate bond with H+ rather
than metal ions.
3.2.2 time affecting the absorption prosess
Absorption rate of CCTS-TEPA was
increased In the first hour of absorption
prosess,and then the rate was decrease one
hour by another. The rate of absorption and
desorption was balanced in the firth hour,as
shown in Fig(3).The absorption is a fast
process.
80
CCTS-TEPA-Cd
ug/ml
transmittance（%）
100
60
40
CCTS-TEPA
20
0
4000
3500
3000
2500
2000
wavenumber， cm
1500
1000
500
-1
Fig(2) FT-IR spectra of CCTS-TEPA
and CCTS-TEPA-Cd
3.2factor affecting the absorption prosess
3.2.1 pH affecting the absorption prosess
The absorption ability of the resin
(CCTS-TEPA and porous-CCTS-TEPA) was
mensurated at room temperature. Put 0.2g
resin into the Cd2+ solution.The pH of the
3.8
3.6
3.4
3.2
3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
Cd
Ni
1
2
3
h
4
5
Fig(3) time affecting the absorption prosess
3.3 study of Langmuir isotherm absorption
The IR indicated that Cd(II) and Ni(II)
was coordinated with CCTS-TEPA. The
absorption motivity could influence absorption
mechanism at some extent. Different
absorption mechanism fitting absorption
isotherm could measure the extent. Yuan Yan
3
Chao[14-15] studied crosslinked chitosan resin
absorbed Cu(II),Ni(II) and Co(II).Using the
Langmuir isotherm fitting the behavior of
crosslinked chitosan resin absorbed metal ions.
The equation is:
Ce/Qe＝Ce/Qm＋1/Qmb…..(1)
Qm is the resin monolayer saturation
adsorption
quantity
.Ce
is
balance
concentration, Qe is balance adsorption
quantity. The experiment fitting the absorption
isotherm at 298K,308K,318K.
It is founded that the behavior of CCTS-TEPA
absorbed Cd(II) and Ni(II) accord with
Langmuir isotherm,as shown in Fig(4),Fig(5)
and Table(1).
308K 298K
2.2
2.0
318K
1.8
Ce/Qe
1.6
1.4
1.2
Parameters for Cd(II)and Ni(II)with
CCTS-TEPA
Temperature(K)
Fitting Equations
298 Cd(II)
Ce/Qe=0.7723Ce+0.2958
308 Cd(II)
Ce/Qe=0.7815Ce+0.2692
318 Cd(II)
Ce/Qe=0.6884Ce+0.4214
298Ni(II)
Ce/Qe=0.2202Ce+0.02061
308Ni(II)
Ce/Qe=0.2126Ce+0.03382
318 Ni(II)
Ce/Qe=0.2003Ce+0.06029
3.4 SEM analysis
Fig(6) is the SEM photo of
CCTS-TEPA.It is not found holes in despite of
high power.Fig(7) is the SEM photo of
porous-CCTS-TEPA.
The
resin
was
pore-forming by PEG-2000. Obviously,there
are many holes in the resin. It is make resin
have large specific surface area.
1.0
0.8
0.6
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
Ce （ mmol/L)
Fig（4）Langmuir line at different temperatures
of Cd(II)
308K
0.8
298K
318K
0.7
0.6
Ce/Qe
0.5
Fig（6）SEM of CCTS-TEPA
0.4
0.3
0.2
0.1
0.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Ce （ mmol/L)
Fig （ 5 ） Langmuir line at different
temperatures of Ni (II)
Table（1）Langmuir Isotherm
4
Fig（7）SEM of porous-CCTS –TEPA
4 conclusion
(1) Chitosan resin modified with
tetraethylenepentamine(CCTS-TEPA)
can
absorb Cd（Ⅱ）,Ni（Ⅱ）.The absorption ability
could get best in neutral solution. It could
absorb Cd（Ⅱ）and Ni（Ⅱ）123.54mg/g and
262.50mg/g respectively. The absorption
behavior is a fast process and
accord with
Langmuir isotherm.
(2) PEG-2000 as the Pore-forming agent, it
could get porous- CCTS-TEPA, the diameter
of the hole is 10μm. It could absorb Cd（Ⅱ）
and Ni （ Ⅱ ） 220.86mg/g 和 315.00mg/g
respectively. The
absorption ability was obvious enhanced.
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