The Effect of Synthesis Condition of the Ability of Swelling, Adsorption, and Desorption of Zwitterionic Sulfobetaine-Based Gel
Corresponding email: eva-oktavia@chem-eng.its.ac.id
Published at : 21 Apr 2020
Volume : IJtech
Vol 11, No 2 (2020)
DOI : https://doi.org/10.14716/ijtech.v11i2.3860
Suprapto, Gotoh, T., Humaidah, N., Febryanita, R., Firdaus, M.S., Ningrum, E.O., 2020. The Effect of Synthesis Condition of the Ability of Swelling, Adsorption, and Desorption of Zwitterionic Sulfobetaine-Based Gel. International Journal of Technology. Volume 11(2), pp. 299-309
| Suprapto | Department of Industrial Chemical Engineering, Faculty of Vocational Studies, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya, 60111, Indonesia |
| Takehiko Gotoh | Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, Kagamiyama 1-4-1, Higashi-Hiroshima, 739-8527, Japan |
| Nurlaili Humaidah | Department of Industrial Chemical Engineering, Faculty of Vocational Studies, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya, 60111, Indonesia |
| Renna Febryanita | Department of Chemical Engineering, Faculty of Industrial Technology, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya 60111, Indonesia |
| Muhammad Sa’i Firdaus | Department of Chemical Engineering, Faculty of Industrial Technology, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya 60111, Indonesia |
| Eva Oktavia Ningrum | Department of Industrial Chemical Engineering, Faculty of Vocational Studies, Institut Teknologi Sepuluh Nopember, Kampus ITS Sukolilo, Surabaya, 60111, Indonesia |
This study explored the ion adsorption of heavy metals
using a copolymer gel containing zwitterionic betaine N,N'-dimethyl(acrylamidopropyl)ammonium propane sulfonate (DMAAPS)
as the ion adsorbent agent and N-isopropylacrylamide (NIPAM) as the
thermosensitive agent. We investigated the effect of ion monomer concentration
and type and of temperature on the adsorption, desorption, and swelling properties
and their correlation. A free-radical polymerization reaction was performed to
prepare the thermosensitive NIPAM-co-DMAAPS
gel using accelerators such as N,N,N',N'-tetramethylethylenediamine,
ammonium peroxydisulfate as the initiator, and N,N'-methylenebisacrylamide at a concentration of 10 mmol/L as the
cross-linker. An analysis was then performed on the gel’s adsorption,
desorption, and reversible adsorption-desorption properties using atomic
absorption spectrophotometry. The results showed that the swelling degree and
adsorption values increased as the temperature decreased in the gel with
NIPAM:DMAAPS ratios of 9:1 and 8:2. In contrast, in a 7:3 ratio, the swelling
degree increased significantly, and the adsorption ability decreased as the temperature
increased. The higher the temperature, the smaller the quantity of Zn2+
and Pb2+ ions adsorbed and desorbed. The results indicate that in
nitrate solution, Pb2+ ions are more easily adsorbed than Zn2+
ions.
Adsorption; Desorption; Swelling; Thermosensitive
Industrial
development leads to increasing metal concentrations in the environment. This
is a serious problem, given that heavy metals are non-biodegradable and persistent.
Therefore, above certain concentrations, they harm aquatic ecosystems and human
health. Various technologies have been successfully developed to decrease the
heavy metal contents of industrial liquid waste.
One of these
technologies is a conventional method of chemical precipitation and
neutralization (El Samrani et al., 2008; Amaral Filho et al.,
2016) . Although this method is commonly used, it can produce other waste
in the form of sludge containing high heavy metal ion concentrations. Other methods are reverse osmosis (Chan and Dudeney, 2008),
Kusrini et al. (2018) applied an adsorption technique with maximum iodine
absorbance of 572.2 mg/g to remove commercial lanthanide ions from an aqueous
solution using an adsorbent in the form of activated carbon extracted from a
banana peels. Olufemi and Eniodunmo (2018) reported the adsorption of nickel (II) ions from
aqueous solutions using banana peels and coconut shells. The optimal conditions
were an adsorbent dose of 4.5 g, 120 minutes of contact time, and 25°C for the banana peels and
an adsorbent dose of 4.5 g, 30 minutes of contact time, and 25°C for the coconut shells.
The adsorption was better determined by the Langmuir isotherm, with coefficient
of correlation values of 0.9821 for the banana peels and 0.9744 for the coconut
shell.
Another
adsorption method involves the use of a thermosensitive gel in the form of
zwitterionic betaine, which can bind the anions and cations in liquid waste
simultaneously (Ningrum et al., 2015 ; Ningrum et al., 2019a; Ningrum et al., 2019b). An interaction between negative
and positive charges in the same repetition unit in zwitterionic sulfobetaine
causes ion selectivity, making this method more attractive than others (Neagu et al.,
2010). In general, zwitterionic
betaine polymers are thermosensitive in water. They do not dissolve even at
temperatures above the upper critical solution temperature (UCST). This means
that when they are below the UCST and in water, they undergo coil collapse due
to inter- and intra-chain interactions. Above the UCST, the inhibition caused
by the inter- and intra-chain interactions can be overcome by the thermal
energy produced. The increase in zwitterionic polymer concentration causes an
increase in intra- and/or inter-chain interactions in the polymer, and thus
higher thermal energy is needed to overcome the interaction, causing the
polymer’s UCST to increase (Takahashi et al., 2011). Zwitterionic betaine properties
is also affected by interactions between zwitterionic containing
charged groups and aqueous salt solutions (Kudaibergenov et al., 2006).
Poly(N-isopropylacrylamide) (poly[NIPAM]) is a polymer with
thermosensitive properties characterized by a low critical solution temperature
(LCST) of 32°C (Ningrum et al., 2017a).
NIPAM has a neutral charge and swells at low temperatures and shrinks at high
temperatures because it changes from hydrophilic to hydrophobic.
Zwitterionic
polymers have great potential in a wide range of biological and medical
applications, such as antifouling coatings (Guo et
al., 2015), blood contacting sensors (Yang et
al., 2011; Joshi et al., 2015), drug delivery in vivo (Fang
et al., 2011; Cao et al., 2012), separation
membranes (Hadidi
and Zydney, 2014; Tu et al., 2015), marine coatings
(Aldred et al., 2010; Zheng et
al., 2017), catalysts (Ajmal et
al.,
2015), and absorption dyes (Sahiner and
Demirci, 2017). Liu et al. (2005) used a hybrid zwitterionic polymer for ion exchange membranes
synthesized by sol–gel
process on N-[3-(trimethoxysilyl) propyl]
ethylene diamine, with 3-glycidoxypropyltrimethoxysilane, and by a reaction
with ?-butyrolactone.
Ningrum et al. (2017b) conducted a study on the effect of monomer concentration on the
adsorption and desorption properties of thermosensitive NIPAM and N,N'-dimethyl(acrylamidopropyl)ammonium
propane sulfonate (DMAAPS) gel, comparing NIPAM:DMAAPS monomer ratios
of 2:8, 1.5:8.5, and 1:9. The temperatures used during desorption and
adsorption were 10, 30, 50, and 70?, while the solution used was NaNO3.
The results showed that the higher the concentration and temperature of the
NaNO3 solution, the lower the NIPAM monomer concentration in the
NIPAM-co-DMAAPS gel. In another study, Ningrum
et al. (2020a) investigated the properties of an NIPAM-co-DMAAPS polymer gel, such as transition temperature, molecular
structure, viscosity in water and Zn(NO3)2 solutions, and
adsorption behavior. The poly (NIPAM-co-DMAAPS)
in both water and the Zn(NO3)2 solution demonstrated a
transition period of LCST. The higher the NIPAM monomer ratio, the lower the
polymer’s LCST. In addition, its transition temperature with a lower NIPAM
concentration was not verified either in water or in the Zn(NO3)2
solution. Moreover, the higher the NIPAM concentration used in the preparation,
the higher the polymer’s viscosity, and the higher ion adsorption onto the gel,
the higher the polymer transmittance.
Several studies have
explored the copolymerization of polymers and thermosensitive zwitterionic
sulfobetaine. The use of zwitterionic polymers can improve the selectivity of ions against
adsorption since the cations and anions in the solution bind through both
negative and positive charges (Ningrum,
2019; Ningrum et al., 2020b). These studies, however,
generally focused only on the synthesis of gel and its properties. Therefore,
this research aimed to improve the adsorption capability of gel by
employing NIPAM and DMAAPS and copolymerizing them in various molar ratios such as 9:1, 8:2, and 7:3.
DMAAPS was used as the ion adsorption agent because of its charged groups,
while NIPAM acted as the desorption agent because it can change from
hydrophilic to hydrophobic. NIPAM fills the space between DMAAPS molecules in
the copolymer and allows further distances between them. Consequently, the
interaction between charged groups of DMAAPS is weakened. The weak interaction
between the charged groups causes the ions in the solution to pair easily with
charged groups, as they are not engaged in inter- or intra-chain or intra-group
interactions. Since they can adsorb and desorb ions, the gels can be used in
reverse. In addition, at higher NIPAM concentrations, the gel is expected to be
have higher swelling ability that will maximize the desorption and adsorption
efficiency of the gel. In light of this, the effects of time, temperature, and
monomer concentrations on the swelling degree, adsorption, and desorption in
Zn(NO3)2 and Pb(NO3)2 solutions
were investigated. The
reversible adsorption-desorption of Zn2+ and Pb2+ in an
aqueous solution with an NIPAM-co-DMAAPS
gel were also examined.
The copolymer gel took more than 15 hours to reach the swelling degree
equilibrium and desorption and adsorption points. In the NIPAM:DMAAPS ratios of
9:1 and 8:2, the swelling degree increased as the temperature decreased. In
contrast, the 7:3 ratio resulted in a higher swelling degree as the temperature
increased. In the nitrate solution, the swelling degree and adsorption ability
of the 9:1 and 8:2 ratios decreased with an increase in temperature.
Conversely, in the 7:3 ratio, the swelling degree increased significantly,
while the adsorption capability decreased with a temperature increase.
Furthermore, in the 9:1 ratio and a temperature of 10°C, the gel’s adsorption
ability reached its highest values of 22.16% (Zn2+) and 26.24% (Pb2+).
It can be concluded that the higher the temperature, the lower the quantity of
Zn2+ and Pb2+ ions adsorbed and desorbed. In nitrate
solution, Pb2+ ions are more easily adsorbed than Zn2+ ions.
An ion concentration of 0.0018 mmol/g of dry gel was obtained from the
reversible adsorption-desorption test using an 8:2 NIPAM:DMAAPS ratio in the
Zn(NO3)2 solution, while the Pb(NO3)2
solution reached an ion concentration of 0.0675 mmol/g of dry gel.
This research was supported by Penelitian Dasar 2019 research grant under contract number 853/PKS/ITS/2019 from the Ministry of Research, Technology,
& Higher Education of
Indonesia for ten consecutive months.
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