Synthesis of Porogen adsorbent Pectin

Carboxymethy Chitosan Modified with

BADGE NaCl and its application
as removal of Pb(II)

Budi Hastuti1),2), Mudasir, Dwi Siswanta, Triyono

1) Chemistry Department, Universitas Gadjah Mada , Yogyakarta, Indonesia
2) Chemistry education, Universitas Sebelas Maret, Surakarta, Indonesia

The 2nd International Conference on Separation Technology

Johor Bahru, Malaysia, 15-16 April 2017
Background
Industrial growth
in developing countries

Heavy metal pollution Effect on ecosystem

(Pb) Effect on biota
Effect on human

Treatment for heavy Filtration

metal pollution Precipitation
Electrodeposition
Solvent extraction
Membrane
Adsorption
Background (cont.)
Adsorption Interaction between
metal and functional
Method groups of adsorbent

Pectin Chitosan
BADGE
(-OH, -COOH) (-OH, -NH3)

Pec-CMC- Na Pec-CMC-
BADGE BADGE-Na

Adsorben Pectin-CMC Synthesis

BADGE-Na Characterization
as a novel heavy metal Adsorption test
adsorbent
Pectin
HOOC H3COOC
Polimer of complex
O
O O
O
O
heterosaccharide
HO OH HO OH
Several active groups:
n hydroxyl, carboxyl,
and methoxyl.
Source of biosorbent
Bind heavy metals,
especially hydroxyl
groups.
Chitosan

Polymer of glucosamine and N-acetylglucosamine,

deacetilated derivative of polysaccharide
Amine and hydroxyl groups
Cationic copolimer, chelating agent for heavy
metal by complex formation
Carboxymethyl Chitosan (CMC)
OCH2COOH One of the modified
chitosan
O Made through
O O esterification process
HO NH2 Water-soluble, forming
semi permeable
n membranes and films
Widely used in the
pharmaceutical and
cosmetic industry
BADGE (Bis phenol A Diglicidyl Ether)

BADGE have a cyclic ester on both of ends so it can

be used to bind the-OH group chitosan and pectin
through a cross-link mechanism
BADGE is rigid (stiff) so it is expected to result in a
stable crosslinked product.
Materials and Method
Pectin Chitosan

CMC

BADGE

Pectin-CMC-BADGE- Characterization
Na (IR spectra, sem]

Adsorption test Effect of pH

on Pb (II) Effect of contact time
Effect of adsorbent dosage
 Materials and Method
Synthesis of CMC-Pectin-BADGE
Pectin

Dissolving (acetic acid, 5%)

BADGE CMC-Pec-BADGE
CMC
+
NaCl

Dissolving (acetic acid, 5%)

CMC-Pec-BADGE-Na
Result and Discussion
IR spectra of CMC-Pectin-BADGE
Wave number
Interpretation
(cm-1)
3464 OH
1635 COOH
1740 stretching C=O
2877 Stretching CH

a. Pektin-CMC-BADGE, b. Pektin-
CMC-BADGE-Na:1:1, c. Pektin-
CMC-BADGE-Na:3:1
 The Charaterization of SEM

a b

c d
SEM image of a. Chitosan, b. Pectin,
c. Pec-CMC-BADGE-Na 1/1, d. Pec-CMC-BADGE-Na 1/3
The Charaterization of SEM

the surface of the chitosan and CMC shows

smooth, fibrous, and non porous appearance
The porogen adsorbent of Pec-BADGE-CMC-
Na has a surface is more porous than the
chitosan or Pectin adsorbent
the porous adsorbent of Pec-BADGE-CMC-Na
will be easier binding Pb (II) metal ions than
chitosan and pectin without modification
 Parameters of Langmuir and Freundlich isotherm
adsorption of Pb(II)

Parameter
Langmuir Freundlich
Adsorben
b K G Kf
n
(mol/g) (L/mmol) (kJ/mol) R2 (mg/g) R2

Chitosan 1.9210-3 2.53 19.54 0.616 3.38 0.691 0.976

Pectin 4.1210-3 0.19 16.60 0.150 1.04 0.936 0.866

CPB-Na 1/1 1.4510-3 14.13 23.83 0.976 5.35 1.229 0.365

CPB-Na 1/3 1.6110-3 6.99 22.08 0.944 3.15 1.246 0.427
Result and Discussion

Effect of pH on Pb (II) ion adsorption

60
Adsorption capacity (mg/g)

50

pectin
40

30 chitosan

20 BADGE : Na = 1:1

10
BADGE Na = 1:3

0
0 1 2 3 4 5 6 7
pH

Optimum pH was 5, where the adsorption capacity was

45,03 mg/g and 98% of Pb (II) ion was adsorbed.
Result and Discussion

Effect of Contact Time Pb (II) ion adsorption

Adsorption capacity (mg/g)

50

Pectin
40

Chtosan
30
CMC

20 CPB-Na 1/1

CPB-Na 1/3
10

0
0 120 240 360 480 600 720

Contact time (min)

Optimum contact time was 60 min, where the adsorption

capacity was 44,33 mg/g and 99% of Pb (II) ion was adsorbed.
Table 2. The Kinetic Parameters of adsorption of Pb(II)
by the adsorbents
Parameter
Pseudo orde -1 Pseudo orde 2
Adsorbent qe110-6 K1(x10-4) qe2 K2
(mol/g-1) (1/min) R2 mol/g-1) (g/mmol min) R2

Pectin 79.7 15 0.676 10.4 4.48 0,896

Chitosan 6.39 34 0.729 1.20 0.60 1

CMC 59.8 55 0.995 1.20 1.11 1

CPB-Na 1/1 10.3 145 0.982 2.24 12.3 1
CPB-Na 1/3 2.76 56 0.898 2.24 15.1 1
 The results of the evaluation of kinetic constants of the
adsorption are presented in Table 2. All of the
adsorbent, Pectin, chitosan, CMC, CPB-Na 1/1 and
CPB-Na 1/1 were well-suited with a pseudo-second-
order kinetic model

Therefore, the adsorption mechanism of Pb(II) ion by

all of the adsorbent, pectin, chitosan,CMC, CPB-Na
1/1 and CPB-Na 1/3. The reaction mecanism of CPB-
Na toward Pb(II) would fit with the combination of
chemisorption and physisorption, e.g. chelation and
electrostatic adsorption.
PectinCMCBADGE has potential to be applied as an
adsorbent primarily due to the presence of the active group
-OH and COOH
Structure of PectinCMCBADGE bind Pb(II)
metal ions
Adsorption of the
adsorbent to Pb (II)
metal ion occurs by
interaction between the
COOH groups of
pectin-OH and COOH
Adsorption of the
adsorbent to Pb (II)
metal ion occurs by
interaction CMC with Pb
(II) metal ions by
chelating agent reaction
Summary
The Carboxymethyl Chitosan-Pectin crosslinked BADGE
(CC-Pec-BADGE) membranes prepared by using NaCl
particles as porogen exhibited excellent sorption capacity
The porogen adsorbent of Pec-BADGE-CMC-Na in
absorption of Pb (II) metal ions follows the Langmuir
isotherm models. It occurs chemically through covalently
and ionic bonded mechanism.
The adsorption process could be best described by
pseudo-second order kinetic model show that The CC-
Pec-BADGE-CMC-Na membrane adsorbent was a good
adsorbent of Pb(II) ion, which potentially provides a new
way for removal of heavy metal ions for the treatment of
industrial waste water.
ACKNOWLEDGMENT

The authors would like to thank to Directorate

General of Higher Education (DGHE), Department of
National Education Republic of Indonesia for the
financial support.
Thank you for your attention