Accepted Manuscript

Title: Removal of Mn(II) from water using chemically

modified banana peels as efficient adsorbent

Author: Ashraf Ali

PII: S2215-1532(16)30087-3
DOI: http://dx.doi.org/doi:10.1016/j.enmm.2016.12.004
Reference: ENMM 76

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Received date: 25-11-2016

Revised date: 21-12-2016
Accepted date: 23-12-2016

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1

Removal of Mn(II) from water using chemically modified banana peels as efficient
adsorbent

Ashraf Ali

Department of Chemistry & Chemical Engineering, Inha University, Incheon 402-751, South

Korea

*Corresponding Author

ashrafaliswati@gmail.com or ashrafchemist12@gmail.com or ashraf@inha.edu

Graphical abstract

A C E

B D F
2

Highlights

 The grafting co-polymerization of acrylonitrile onto the bleached pulp was carried out
using Fenton’s reagent (Fe+/H2O2) as initiator.
 Acrylonotrile grafted banana peels are used as adsorbent for the removal of Mn(II) ion
from aqueous solution.
 The effect of pH, adsorbent dose, concentration and contact time were studied on
adsorption of Mn(II) onto grafted banana peels.
 The adsorption of Mn(II) onto grafted banana peels (GBPs) was recorded to be 94% at
optimized conditions.
3

ABSTRACT
In this study a novel acrylonitrile grafted cellulosic adsorbent is prepared from bleached banana
pulp. Banana peels were hydrolyzed with alkali followed by bleaching with sodium chlorate
(NaClO3). The grafting co-polymerization of acrylonitrile onto the bleached pulp was carried out
using Fenton’s reagent (Fe+/H2O2) as initiator. The acrylonitrile grafted cellulosic adsorbent was
used for Mn(II) removal from aqueous solution. The adsorption of Mn(II) onto grafted banana
peels was recorded to be 94 %. The adsorption equilibrium is fitted well by Langmuir isotherm
model. Owing to high efficiency and low cost, grafted banana peels (GBPs) can be used as
effective adsorbent for Mn(II) removal from aqueous solution and industrial waste water.
Key words: Banana peel, Adsorbent, Acrylonitrile, Grafting co-polymerization.
Introduction
Heavy metals are introduced into the environment through natural phenomena and human
activities, resulting in the contamination of environment. The discharge of industrial effluents
into water bodies is a major environmental problem worldwide, because it contains toxic heavy
metals and other organic and inorganic pollutants. Industrial wastewater often contains heavy
metal ions which are non-biodegradable and many of them are soluble in aqueous media and
easily available to living organisms. Heavy metals removal from aqueous media is an important
and challenging task (Jiwan and Kalamdhad 2011; Barkat 2011). Manganese exists in water as a
Mn2+ (divalent ion) and due to its organoleptic properties it is considered a pollutant. Manganese
contamination affect the appearance, color, taste and odor of water. The recommended limit of
manganese in drinking water is 0.05 mg/L. It causes neurological disorder when inhaled at a rate
of about 10 mgday-1 (Adeogun et al. 2011). The chronic exposure to manganese produces
lethargy, tremors, psychological disturbances and respiratory infections (Abdeen et al. 2015).
The removal of Mn(II) from water is still a serious problem in various countries and it is a
challenging task. Numerous methods and techniques have been utilized for the removal of heavy
metals from solution such as chemical precipitation, ion exchange, phytoextraction, ultra-
filtration, reverse osmosis, and adsorption (Bailey et al. 1999; Sud et al. 2008; Demirbas 2008;
Chiban et al. 2012; Choi et al. 2007; Badmus et al. 2007). However, most of these methods have
some limitations, such as high operational cost, complicated design, ineffective at low metal
4

concentrations, production of secondary wastes, slug formation and inapplicable to a wide range
of pollutants (Fenglian & Qi 2011; Zhang 2009; Yasmin & Zeki 2007). In contrast, adsorption
has been found to be one of the most effective method for the removal of metal ions from
solution due to its simple operation design with sludge free environment and low cost
(Lakherwal 2014; Adelaja et al. 2014). In past, researchers have used activated carbon as
adsorbent for the removal of heavy metals from aqueous media and industrial wastewater. The
high cost of activated carbon and other conventional adsorbents stimulate the researchers to use
agricultural products and by-products as low-cost adsorbents. Agricultural products and by-
products have been used as adsorbents for the removal of heavy metals from aqueous media by
many researchers (Bhatnagar et al. 2015; Liu et al. 2012). For the past few decades, researchers
have used the agricultural wastes such as, rice husk, baggas, sugar beet pulp, soya bean hulls,
clay, tea waste, natural zeolite, wheat bran, sawdust, peanut shells, and fruits peels as adsorbents
for heavy metals removal from aqueous solution (Lata & Samadder 2014; Ibrahim et al. 2006;
Mata et al. 2009; Sheng-quan et al. 2012; Anirudhan et al. 2012; Mohammed 2012; Shaheen et al.
2012; Barati et al. 2014; Krowiak 2013; Salam et al. 2011; Mallampati et al. 2015; Kamel et al.
2012; Hossain et al. 2012). These adsorbents have great affinity for heavy metal ions due to the
presence of several potential groups such as alkoxy, hydroxyl, carbonyl and amino groups (Nagh
&Hanafiah 2008; Abdel-Halim & Al-Deyab 2012; Werkneh et al. 2014). Chemically treated
agricultural adsorbents are mostly used for the removal of heavy metals, dyes and other organics
and it has been noted that their adsorption capacity is much better than untreated adsorbents. In
untreated agricultural adsorbents the pores and gapes between cellulose fibers are covered by
viscous compounds such as lignin and pectin (Nemr 2009; Yang et al. 2009; Gupta & Rastogi
2009) which have surrounds the available active functional groups and it can’t interact well with
the adsorbates. The adsorption capacity of such adsorbents can be enhanced by chemical
treatment, such as hydrolysis with dilute acides, alkalies or bleaching with various bleaching
agents. In our previous work a comparative study on the removal of Cr(VI) and Mn(II) by four
adsorbents, untreated banana peels (UTBP), acid hydrolyzed banana peels (AcBP), bleached
banana peels (BBP) and alkali hydrolyzed banana peels (AlBP) have been carried out (Ali &
Saeed 2015). The results showed that UTBP has the minimum adsorption capacity while that of
AlBP has maximum adsorption capacity for Mn(II). The surface of cellulose can be modified by
grafting copolymerization with various monomers to change the physical or chemical properties
5

of cellulose. The insertion of a side chain into cellulose backbone occurs during grafting
copolymerization and the monomer covalently bound to cellulose backbone to form a branched
copolymer. The adsorption capacity of chemically modified cellulose pulp is found to be more
than raw agricultural adsorbents, the pulp contains 99% cellulose which can be easily modified
with a ligand/monomer such as vinyl monomers, ethyl methacrylate AN/methyl methacrylate
mixture, amino, methyl acrylate, ethyl acrylate and acrylamide or any other monomer.
Incorporation of side chains into cellulose skeleton enhance various properties such as water
absorption, ion-exchange, metal adsorption capability, thermosensitivity and elasticity. Banana
peels biomass containing various chemical groups such as carboxylic acid, phosphate, and
hydroxyl groups which act as active centers for the adsorption of metal ions from aqueous media
and industrial wastewater. Several research groups have used raw and chemically treated banana
peels and banana stalks for the removal of toxic heavy metal ions from aqueous solutions and
industrial wastewater (Hameed et al. 2008; Memon et al. 2008; Achak et al. 2009; Liu et al.
2014; Ali & Saeed 2016).
In another study, we have used five adsorbents (UTBPs, AcBPs, BBPs, AlBPs and GBPs) for
phenol removal from aqueous media, among these adsorbents GBPs have shown maximum
adsorption capacity at optimum conditions (Ali & Saeed 2016). In our previous study,
acrylonitrile grafted banana peels have been used for the removal of Cr(VI) from aqueous
medium and 96 % metal ions have been removed at optimized conditions (Ali et al, 2016).
In the present work, banana peels are treated with bleaching agents (NaClO3, H2O2) and then the
bleached pulp is functionalized with acrylonitrile (CH2=CH-C≡N) monomer. The grafted banana
peels (GBPs) are used as adsorbent for the removal of Mn(II) from aqueous solution. The
adsorption capacity of GBPs for Mn(II) is found to be 94% at optimized conditions, which is
much higher than those of other four adsorbents (UTBP, AcBP, BBP, AlBP) used in our
previous work. The enhancement in adsorption capacity of banana peels after chemical treatment
may be due to the removal of viscous compounds like lignin and pectin and the exposure of
active functional groups of cellulosic skeleton such as hydroxyl, carbonyl, epoxy, carboxylic, etc
which are responsible for the binding of positively charged divalent Mn(II) ions. The
incorporation of acrylonitrile (-CH2=CH-C≡N) monomer to cellulosic skeleton also enhanced its
interaction with Mn(II) ions due to the interaction between lone pair of electrons on nitrogen
atom in (-CH2=CH-C≡N) group and positively charged Mn(II) ions.
6

1. Materials and methods

1.1 Adsorbent preparation
Dried banana peels (500g) were boiled in (10% V/V) NaOH(aq) at 100˚C for 3 h and washed
thoroughly with deionized water. The pulp was dried in oven at 70˚C for 24 h. The dried pulp
(100g) were treated with 10 g sodium chlorate, 5 mL glacial acetic acid and 0.5 mL H2O2 in 1L
flask and heated in a water bath for 5 h followed by washing with deionized water.
1.2. Grafting of acrylonitrile monomers onto banana’s cellulose pulp

The grafting of acrylonitrile monomer onto cellulose pulp from banana peels was carried out by
treating the bleached banana pulp with acrylonitrile (CH2=CH-C≡N) using Fenton’s reagent
(Fe+2/H2O2) as initiator. The bleached banana peels (100g) were mixed with 3mL hydrogen
peroxide, 10 g ferric sulfate and 1mL glacial acetic acid in 1500mL distilled water and heated at
40˚C for 5 h. The product was filtered and washed thoroughly with deionized water and dried at
100˚C for 12 h. Acrylonitrile grafted banana peels were put in small cotton bags and extracted
with toluene at 110˚C for 12 h in soxhlet device, washed with deionized water and dried in an
oven at 70˚C for overnight.
1.3. Adsorption of Mn(II) on modified banana peel
The adsorption of Mn(II) were carried out by shaking 100 mg/L test solution of KMnO4 at pH
8.0, with 4 g adsorbent (GBP) in 250mL flask at 30˚C. The Mn(II) ions concentration was
determined by using Nicolet evolution 300 UV-visible spectrophotometer by the standard
persulfate method (Marczeko & Balcerzak 2000). The amount of Mn(II) adsorb per gram of
adsorbent was calculated by the following equation.

(6)

Where “qe” is the amount of metal ions, “V” is the solution volume (L), “W” is the adsorbent
dose (g), and “Co” and “Ce” are the initial and equilibrium metal ions concentration in solution
respectively. The percent metal removal was calculated using the following equation.

(7)

1.4. Scanning electron microscopy (SEM)

Scanning electron microscopy (SEM) was carried out to observe the changes in the morphology
of adsorbents after adsorption. The SEM images of banana peel were taken by HITACHI (Tokyo
Japan) S-4200 field emission scanning electron microscopy (FE-SEM).
7

1.5. Adsorption isotherm

The adsorption equilibrium data of Mn(II) on GBPs was computed by Langmuir and Freundlich
isotherm models. The Freundlich isotherm model explains the interaction between adsorbate
molecules and adsorbents with multilayer adsorption on heterogeneous surfaces (Freundlich
1906). It shows that if the concentration of adsorbate increases, its accumulation on adsorbent
surface will also increases. The Langmuir model suggests the monolayer adsorption on a
homogenous surface, equivalent sorption energies and no interaction between adsorbed species
(Langmuir1918). The regression coefficient values were judged to find the applicability of these
models to the adsorption data.
2. Results and discussion
2.1 Effect of metal ion (Fe+2) concentration on grafting co-polymerization
Free radicals are produced from (Fe+2/H2O2) through redox reaction, these free radicles produce
more reactive cites on the cellulose backbone and also activate the monomers by producing free
radicals from monomers units which react with cellulose to form the graft co-polymers. The
production of free radicals by an indirect method can be represented as,

Fe+2 + H2O2 Fe+3 + OH- + .OH

- - -2 -.
Fe+2 + O3SOOSO3 Fe+3 + SO4 + SO4

SO4-2 + H2O HSO4- + OH-

The grafting copolymerization reaction of acrylonitrile with banana cellulose is shown in scheme
1.

Increasing the amount of (FeSO4) increases the rate of grafting reaction as shown in (Table 1).
The increase in reaction yield with increasing (FeSO4) may be due the production of more
reactive sites on cellulosic chain and the monomer units can easily react with it to form grafted
copolymer as shown in Scheme 1. The grafting yield increases with increasing (FeSO4)
concentration up to certain level (3.5 g/10g pulp), further increase in the amount of (FeSO4) in
reaction mixture don’t bring a notable increase in grafting reaction as the equilibrium achieved
8

already and the active sites on cellulose surface have already been occupied by monomer units as
shown in scheme 1. (Bhatt et al. 2011; Hajeeth et al. 2013)

Table 1. Effect of initiator (FeSO4) concentration on grafting co-polymerization

2.2 Effect of Temperature on grafting co-polymerization
The effect of temperature on grafting co-polymerization is shown in Table 2, it is clear that
increasing the temperature up to 90˚C increases the diffusion of monomers through cellulose
chains, swelling of cellulose, as well as the rate of initiation and propagation of the grafting.
Increasing the temperature beyond 90˚C, decreases the grafting copolymerization, it may be due
to the oxidation of free radicals, and mutual termination of growing macro radicals favors more
homo polymer formation (Ibrahim et al. 2002; Routray & Tosh 2012)
Table.2. Effect of temperature on grafting co-polymerization

2.3. Effect of acrylonitrile concentration on grafting co-polymerization

The change in grafting yield with monomer concentration is shown in the Table 3. The results
showed that increasing the acrylonitrile concentration up to 3g increase the grafting yield. The
increase in grafting yield with increasing acrylonitrile concentration may due to the increase in
the number of monomer molecules for grafting co-polymerization. Further increasing monomer
concentration above 4mL, decreases the grafting yield. The decrease in grafting yield at higher
acrylonitrile concentration may be due to the viscosity of reaction mixture which retard the
penetration of monomer to the active sites of cellulosic backbone (Batacharia & Misra 2004;
Zhang & Chen 2002)
Table.3. Effect of acrylonitrile concentration on grafting co-polymerization
2.4. Effect of time on grafting co-polymerization
The graft yield increases with increasing reaction time up to 4h and the equilibrium establish in 3
h as shown in in Table 4. During grafting reaction, the monomers interact with the active site of
cellulosic skeleton to form graft co-polymers as the available functional groups on cellulosic
skeleton fully saturate in 3h, then there is no further increase in graft yield. The reaction time
was further increased to 4 h but there was no considerable increase in the grafting yield (Giri et
al. 2014; Elkholy et al. 2012)
Table.4. Effect of time on grafting co-polymerization
9

2.5. Scanning electron microscopic (SEM) studies

The scanning electron micrographs of raw, bleached and grafted banana peels are shown in the
Fig.1. The SEM micrographs of raw banana peels (Fig.1A), showed that the fibers are stick
together due to the presence of lignin, pectin and other viscous compounds. The bleached banana
peels (Fig.1B), shows that the viscous compounds are removed during chemical treatment. The
morphology of grafted banana peels (Fig.1C) looks different from raw and bleached. The close
view of GBPs before adsorption is shown in (Fig.1D), which show some open pores and fibers
and the surface is not too much smooth. The surface morphology of adsorbent became much
smother after the adsorption of Mn(II) (Fig.1E and F), and the pores and caves are filled by metal
ions (Pathak et al. 2016; Massocatto et al. 2013; Gupta & Gupta 2016).
Fig.1.
2.6. Effect of Mn(II) concentration on adsorption
The Mn(II) solutions of different concentration (100, 200, 300, 400 and 600mg/L) were taken at
constant temperature 25˚C, pH 8, agitation speed 300 rpm, contact time 2h, and 4g adsorbent
dose. The adsorption of Mn(II) increases initially by increasing Mn(II) concentration, and reach
to maximum at 400mg/L (Fig2). The equilibrium was established at 400mg/L, and there was no
further increase in the adsorption of Mn(II) by further increasing metal ions concentration up to
600mg/L. The ratio of number of moles of metal ions to the surface area of adsorbent is large at
optimum concentration (400mg/L), so adsorption takes place without any interruption. The
adsorbent surface area saturates at higher concentration and the ions diffusion from the solution
bulk to the adsorbent surface decreases (Piispanen & Sallanko 2010).
Fig.2
2.7. Effect of adsorbent dose on Mn(II) removal
The fixed quantity of adsorbent is very important for the removal of particular concentration of
metal ion from solution and it determined the capacity of adsorbent for the given concentration
of adsorbate. The increase in the adsorption of metal ions depends upon the number of available
sites on adsorbent. The effect of adsorbent dose on Mn(II) removal is shown in Fig 3. The results
showed that the percentage of adsorption of Mn(II) initially increases with the increasing the
GBPs amount up to 4g/L. The increase in Mn(II) adsorption with increasing GBPs amount may
be due to the availability of more active sites for the uptake of metal ions at higher adsorbent
10

dose (Sharma et al. 2007). The adsorptions of Mn(II) was not affected by further increasing
adsorbent amount because the available metal ions are already adsorbed by the adsorbent.
Fig.3
2.8. Effect of contact time on Mn(II) removal

The effect of contact time on Mn(II) removal by grafted banana peel (GBPs) is presented in Fig
4. The adsorption was carried out for several time intervals by taking 400mg/L Mn(II) solution at
optimum pH 8, adsorbent dose 4g and agitated at 300 rpm at 25oC. The Mn(II) removal initially
increased up to 60min. The increase in Mn(II) ions removal with increase in adsorption time may
be due to the higher interaction between the adsorbent surface and metal ions. The increase in
adsorption rate is due to the availability of large number of active sites on the surface of GBPs
and the metal ions rapidly diffuses from the bulk of the solution to the adsorbent surface (Phatai
et al. 2010). However further increase in contact time (up to 120min) brings no significant
change in Mn(II) removal. Hence 60min was chosen as optimum time for the removal of metal
ions.
Fig.4
2.9. Effect of pH on Mn(II) removal
The pH of solution is important variable for the adsorption of metal ions because it affects the
protonation/deprotonation of the functional groups of the adsorbent. The effect of pH on Mn(II)
removal by (GBPs) was investigated and the results are presented in Fig. 5. Mn(II) exist in
aqueous solution as Mn+2(H2O)6 ion which interact with negatively charged adsorbent. The
adsorption of Mn(II) at lower pH was low due to the development of positive charge on the
active sites of adsorbent. At low pH the H+ ions concentration is high so there is competition
between H+ ions and Mn2+ (H2O)6 ions in the bulk of solution to bind with the with negatively
charged surface of adsorbent (GBPs) (Phatai et al. 2014; Taffarel et al. 2010). The adsorption of
Mn(II) increased with increasing the solution pH up to 8. The adsorption of Mn(II) decreases at
pH >8, due to hydroxide ions Mn(II) precipitated and forming manganese hydroxide precipitate.
Fig.5
2.10. Adsorption isotherm study
Adsorption isotherm shows the amount of adsorbate adsorbed by unit mass of adsorbent from the
liquid phase at a constant temperature. For the optimization of the design of an adsorption system
the analysis of adsorption equilibrium data is very important. Adsorption isotherm represent the
11

relationship between metal ions adsorbed onto the adsorbents and its concentration in the
solution. Various isotherm models have been widely used to analyze the adsorption data. In this
studyFreundlich and Langmuir adsorption models were used to study the interaction of Mn(II)
ions with adsorbent (GBPs).
2.11. Freundlich adsorption isotherm
Freundlich isotherm presumes that the adsorption of metal ions takes place on heterogeneous
surface with multilayer adsorption and the adsorption increases with increase in concentration.
The linear form of Freundlich adsorption isotherm is given as (Freundlich 1906),

(8)

Where “Kf” and “n” are Freundlich constants, 1/n and Kf indicate the adsorption intensity and ad
sorption capacity respectively. The affinity between adsorbate and adsorbent will be greater if 1/
n is higher and the surface will be more heterogeneous. The value of 1/n represent the relative d
istribution of energy sites and it depend on the nature of adsorption process. Linear plots were ob
tained by plotting lnq vs lnCe with slope 1/n (Fig 6) at different Mn(II) ions concentrations. The
n and K (L mg-1) (adsorption capacity) were calculated from (Fig 6). The value of “n” indicate th
e adsorption is favorable over entire concentration range. The “n” values show that the adsorbent
is effective; surface is heterogeneous and possesses great affinity for metal ions (Abideen et al. 2
013; Katsoyiannis & Zouboulis 2004). The values of Kf, n and R2 are presented in Table 5. The s
aturation of GBPs surface by Mn(II) ions was not observed, so it indicates multilayer adsorption
on heterogeneous surfaces.
Fig.6.
2.12. Langmuir adsorption isotherm
The Langmuir isotherm model is based on the monolayer adsorption of Mn(II) ions onto GBPs
surface. The linear form of Langmuir adsorption isotherm is given as (Langmuir1918),

(9)

Where Ce (mg L-1), is the equilibrium concentration of adsorbate, qe (mgg-1) is the amount of
adsorbate per unit mass of adsorbent, qmax (mgg-1) is the maximum adsorption capacity, and
????(L mg−1) is Langmuir constant related to energy of adsorption.
The plot of Ce/q against Ce gives straight lines with intercept 1/qmaxk and slope 1/qmax, binding
energy constant. The isotherm constants were calculated from the linear regression of the
12

experimental data. The characteristics of the Langmuir isotherm can be represented in terms of a
dimensionless equilibrium parameter (????) which is given as
(10)

The isotherm constants and regression values (Table 5) show that the adsorption data is in close
agreement with Langmuir isotherm model. As the value of RL decreases, the affinity of adsorbate
towards the adsorbent surface increases. The RL values are less than one which shows that the
adsorption data is fully fitted with Langmuir isotherm model and the adsorption of Mn(II) onto
GBPs is favorable.

Fig.7.
Table 5 Freundlich and Langmuir isotherms parameters for Mn(II) adsorption onto GBPs

3. Conclusions
Banana peels biomass containing various chemical groups such as carboxylic acid, phosphate,
and hydroxyl groups which act as active centers for the adsorption of metal ions from aqueous
media and industrial wastewater. Chemical treatment of banana peels with acids, alkali or
bleaching agents such as hydrogen peroxide increase its adsorption capacity. During chemical
treatment the peptic and viscous compounds removes from the cellulosic skeleton and expose the
functional groups for the binding of metal ions. The incorporation of additional monomer chain
(-CH2=CH-C≡N) during grafting copolymerization to cellulosic skeleton can further increase its
interaction with metal ions. The efficiency grafting copolymerization depends upon monomer
concentration, temperature, initiator (Fe+2) concentration and time. The adsorption data is fully
fitted with Langmuir isotherm’s model and follow pseudo-second order kinetic model. The
adsorption capacity of grafted banana peels is much better than other agricultural adsorbents. The
low-cost GBPs can be used as an alternative to expansive activated carbon. Chemically treated
banana peels can be used as efficient adsorbent for Mn(II) ions removal from aqueous media.
Chemically modified banana peels can be used as a cheap alternative to activated carbon and
other expansive adsorbents for the removal of toxic heavy metals and organic pollutants from
aqueous media and industrial wastewater.

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Figure Legends
Fig.1. (A) SEM image of raw banana peel (B) Bleached banana peel (C) Acrylonitrile grafted
banana peel (D) GBPs before adsorption (close view) (E) GBPs after Mn(II) adsorption (close
view)
Fig.2 Effect of concentration on the removal of Mn(II) from aqueous solution by GBPs
Fig.3 Effect of adsorbent dose on the removal of Mn(II) from aqueous solution by GBPs
Fig.4 Effect of contact time on Mn(II) removal of from aqueous solution by GBPs
Fig.5 Effect of pH on the removal of Mn(II) from aqueous solution by GBPs
Fig.6. Freundlich adsorption Isotherm of Mn(II) onto GBPs
Fig.7. Langmuir adsorption Isotherm model for Mn(II) onto GBPs
20

A C E

B D F

Fig.1.
21

Fig. 2

Fig. 3
22

Fig. 4
23

Fig. 5

Fig.6.
24

Fig.7 .
25

.
Ban O + nCH2 CH Ban O (CH2 CH)n
CN CN (A)
Acrylonitrile Acrylonitrile grafted banana peels
.OH
+ nCH2 CH (CH2 CH)n
CN CN
Homopolymer (Polyacrylonitrile)

Main reaction
OH-
Ban-OH + CH2 CH-CN Ban-O-CH2-CH2 CN
Side reaction
(B)
OH-
Ban-O-CH2-CH2 CN Ban-O-CH2-CH2-CO-NH2

OH-
Ban-O-CH2-CH2-CO-NH2 Ban-O-CH2-CH2-COO-

Scheme 1. The grafting reaction of acrylonitrile with banana cellulose, (A) Radical initiated
grafting reaction. (B) Base catalyzed reactions of acrylonitrile with banana peels cellulose
26

Table 1 Effect of initiator (Fe+2) concentration on grafting co-polymerization

Amount of Graft yield Graft Total Homopolymer Grafting

initiator (Fe+2) conversion conversion formation efficiency
(%)
(g )/2g pulp
(%) (%) (%) (%)

0.3 40 13.33 16.32 5.78 49

0.6 80 26.66 38.25 11.35 69.5

0.9 135 45 45.81 25 78.33

1.2 170 56 81.20 38 85.44

1.5 150 46.66 75.16 32 77.21

Table 2 Effect of temperature on grafting co-polymerization

 27

Table 3 Effect of acrylonitrile concentration on grafting co-polymerization

Grafting temp (˚C) Graft yield Graft Total Homo Grafting

conversion conversion polymer efficiency
(%)
formation
(%) (%) (%)
(%)

30 10 15 05 15 40

40 60 23 33.33 23 55.23

50 70 31 45.32 32 66.31

60 125 45 90 45 74.23

70 120 43 85 38 68
28

Table 4 Effect of time on grafting co-polymerization

Acrylonitrile Graft yield Graft Total Homo polymer Grafting

(mL) conversion conversion formation efficiency
(%)
(%) (%) (%) (%)

1 05 10 30 20 33.33

2 25 25 35 22 71.42

3 40 26.66 37 25 80

4 75 37.5 55 30 86

5 60 32 50 28 70

Time (h) Grafting yield Grafting Total Homo polymer Grafting

conversion (%) conversion formation (%) efficiency (%)
(%)
(%)

0.5 45 15 35 18 42.85

1 70 26.66 45 20 54.48

2 85 35.23 51.66 28 58.33

3 140 46.66 80 37 65.78

4 132 42 74 33 60

Table 5 Freundlich and Langmuir isotherms constants for Mn(II) adsorption onto GBPs
29

Isotherm Parameters Mn (II)

Freundlich 1/n 0.9741

KF (mg/g) 2.9861

R2 0.982

Langmuir qmax (mg/g) 5.7306

K (L/mg) 0.99995

K (L/mg) 0.999