International Journal of Engineering Research And Management (IJERM)

ISSN: 2349- 2058, Volume-05, Issue-07, July 2018

Novel Low Cost Adsorbent for the Removal of Rhodamine

B Dye from Wastewater
Shweta Mitra, Tirthankar Mukherjee

 photo-degradation, chemical oxidation, membrane filtration

Abstract— This study deals with the preparation of methods, ozonation, and biosorption [3]. Although the
Activated Carbon (AC) from spent tea leaves collected aforementioned process may be suitable in many cases but for
from local shops and stalls. 5% NaOH solution was used dye removal either the methods are inefficient or have
to chemically activate the tea leaves in a ratio of 1.5:1 abnormally high costs which prevent their acceptance on a
(NaOH: Carbonized tea). The activated tea leaves were larger scale. Adsorption provides an alternative to these
further subjected to carbonization at 350°C for 2hrs. The methods and is found suitable for the purpose of dye removal
prepared AC was impregnated with iron nano-particles from wastewater. The suitability of activated carbon for these
(TAC/Fe). This TAC/Fe was used to adsorb Rhodamine B processes remains unchallenged due to added advantages of
dye aqueous solution. The effect of different parameters operation over high temperature, a wide range of pH, easy
such as pH, adsorbent dosage (g/l), the initial separation and an enormous porosity which helps it in
concentration of dye (ppm) and temperature (°C) were adsorbing large amounts of impurities [4]. One of the most
studied. The removal % decreases as the initial dye popular methods of modifying activated carbons is to make a
concentration increases and with increase in pH it also metal oxide-activated carbon composite which provides
decreases as obtained from the effects of the individual added enhanced desirable characteristic of porosity having
parameters. The removal of RB dye increases with the the advantage of greater control in terms of pore structure and
increase in adsorbent dosage. From the thermodynamic surface functional groups thus altering its adsorption
study it has been observed that at a low temperature of properties. Extensive reports of literature can be noted where
30°C the molecular motion was very low and the removal metal oxides such as aluminum oxide, iron oxide, zinc oxide,
efficiency was 85.25 % but at higher temperatures manganese oxide, copper oxide and vanadium oxide have
around 80-100°C, the removal efficiency increased to been used to modify the properties of activated carbons [5-6].
90.2%. These metal oxides are impregnated in the activated carbon
matrix to enhance its adsorption capacity or to make a
Index Terms— Spent tea leaves; Chemical Activation; noticeable improvement in its ability in bringing about
Activated Carbon; temperature
catalytic oxidation for dye wastewater.
The precursor for the production of activated carbon plays a
I. INTRODUCTION
huge role in its quality as an adsorbent. Many agro-related
The environment has sustained negative impacts since the wastes have been in use as a precursor for the production of
advent of industrialization. Application of dyes on major note activated carbon like agricultural waste, wood, leaves,
can be seen in industries like leather, food, textile, and paper. baggase, various seeds etc [7]. One of most low-cost beverage
An estimate of 700000 tons of dyes is produced each year out tea is perhaps the oldest and most widely consumed beverage
of which around 2 % is reported to make it to the environment in the world after water. With more than 2000 various variants
and hamper the balance of the ecosystem [1]. These effluents of tea available for consumption in the global market, it is
that are carrying contaminants in the form of dyes must be regarded as one of the major contributors to the world
treated to accepted standards from the different industries beverage market. India known traditionally for its different
before their release into the ecosystem. Rhodamine B (RB) is authentic varieties of tea is also one of the leading producers
a dye encountered very frequently in the textile industry for and consumers of tea in the global market [7]. Spent tea leaves
the purpose of dyeing wool, silk, and cotton. RB upon contact which are a waste product of industrial and domestic
with eyes causes a highly irritable sensation and a feeling importance can serve as a source of activated carbon as the
resembling burning may be felt as well which may lead to carbon content of 30% can be noted in spent tea leaves [8].
severe damage to the eyes of both animals and humans With proper physical and chemical activation, this potential
leading to permanent damage [2]. could be tapped into and design of low-cost adsorbent could
Methods of treating wastewater have been an ongoing happen that would have the ability to remove various dyes
research and many methods have been tried for the successful from their aqueous solution.
removal of impurities present in wastewater. Some methods In this study activated carbon was prepared from spent tea
to have been applied include coagulation, reverse osmosis, leaves collected collected from local shops and stalls. 5%
NaOH solution was used to chemically activate the tea leaves
Manuscript received July 22, 2018 in a ratio of 1.5:1 (NaOH: Carbonized tea). The activated tea
Shweta Mitra, Department of Chemical Engineering, Jadavpur leaves were further subjected to carbonization at 350°C for
University, Kolkata, India 2hrs. The prepared AC was impregnated with iron
Tirthankar Mukherjee, Department of Chemical Engineering, nano-particles (TAC/Fe). This TAC/Fe was used to adsorb
Jadavpur University, Kolkata, India
Rhodamine B dye aqueous solution. The effect of different

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 Novel Low Cost Adsorbent for the Removal of Rhodamine B Dye from Wastewater

parameters such as pH, adsorbent dosage (g/l), the initial of the solution was maintained by adding 0.1M HCl and 0.1M
concentration of dye (ppm) and temperature (°C) were NaOH solution before adding the activated carbon. After a
studied. certain fixed time of adsorption, the solution was filtered. The
final RB solution concentration was measured using
II. MATERIALS AND METHODS UV-Visible Spectrophotometer (Perkin Elmer UV/VIS
A. Chemicals Lambda 365) at a wavelength of 554nm. The percentage
All chemical reagents were of analytical grade and were used removal of dye was calculated using the following equation:
without further purification. Spent tea leaves were collected
from the local market and were washed thoroughly before use.
Iron Sulphate Heptahydrate (Fe2SO4, 7H2O) used for iron
impregnation was purchased from Merck, India. Rhodamine
B was obtained from SRL Chemicals. Hydrochloric acid Where Ci and Cf are the initial and final concentrations of RB
(HCl), 37%, and sodium hydroxide (NaOH) required for solution, respectively
monitoring the pH was also purchased from Merck.
III. RESULT AND DISCUSSION
B. Preparation Activated Carbon from spent tea leaves (TAC) A. Characterization
Spent tea leaves were collected from the local shops and
stalls. Then it was repeatedly washed to remove dirt and loose
soil particles. Afterward, it was dried for 48 hours at 80°C in a
hot air oven (Make: Spac n Services). The dried mass was
carbonized at 450°C for 2 hours in a muffle furnace (Make:
Spac n Services). The carbonized tea was sieved with a
250µm mesh and fine particles were obtained which was
subjected to chemical treatment with 5% NaOH. The NaOH
solution was added to the carbonized tea leaves in a ratio of
1.5:1. The mixture was kept for 12 hours for the activation.
After the process was complete the mixture was washed
repeatedly until it became neutral. The partially activated
carbon was then dried in a hot air oven for 24 hours. The dried Figure 1: SEM images of (A) Activated Carbon (B) TAC/Fe
material was put into the muffle furnace for further
carbonization at 800°C for 2 hours.
Fig. 1 depicts the morphological characteristics of TAC/Fe
material obtained from SEM images. Fig. 1A and Fig. 1B
C. Preparation of iron impregnation in TAC (TAC/Fe)
A weighed amount of the prepared AC was blended with iron depicts the structure at 10µm magnification. It can be seen
salt (Fe2SO4, 7H2O) in a solution of 1:5 (w/w) ratio. The with distinct clarity that the surface morphology of the
formed mixture was stirred in a magnetic stirrer (Make: Remi) activated carbon has been modified by a deposition of iron
and heated to 100°C for 2 hours while 10% NaOH solution particles. Visibility of pores can be deemed distinct encircling
was added dropwise for 5 min to precipitate the hydrated iron which the iron at different states of oxidation can be seen to be
oxides. The final product (TAC/Fe) was repeatedly washed present. It can also be concluded that the pores obtained are
with water until its pH became neutral. The final product was micropores.
dried and kept for further use.

D. Characterizations
To find the surface topographical characterization of the
prepared activated carbon Scanning Electron Microscope
(FEI INSPECT F50 FESEM) consisting of Tungsten filament
was employed for the surface characterization. The scan
settings were set at an accelerator voltage of 10 kV and an
emission current of 100mA˚. Furthermore, the
physicochemical characterization was obtained via XRD
spectroscopy (Rigaku Ultima III). The copper filament was Figure 2: XRD image of (A) Activated Carbon (B) TAC/Fe
used with 40kV and 30mA.
showing the peaks of Fe
E. Experimental procedure
Fig. 2A shows the XRD profile of the neat AC produced from
All the adsorption experiments were carried out in batch
spent tea leaves. The prepared activated carbon exhibits a
mode. 200 ml of aqueous solution of RB dye was taken in a
very broad band of diffraction peaks along with the absence of
flask for each of the experiments. The flask was placed on a
sharp peaks which indicated that it is predominantly an
temperature controlled magnetic stirrer. A known amount of
amorphous structure. There are two broad diffraction peaks
activated carbon was added and the stirrer was started
around 2θ = 24.6° and 43.1° in the spectrum, corresponding to
immediately. Same stirring speed (300 rpm) was maintained
the diffraction of (0 0 2) and (1 0 0), respectively.
for all the experiments. The experiments were conducted with
Fig. 2B shows the XRD patterns as obtained for TAC/Fe.
different initial concentrations of the dye solution. Initial pH

29 www.ijerm.com
 International Journal of Engineering Research And Management (IJERM)
ISSN: 2349- 2058, Volume-05, Issue-07, July 2018

Two crystalline phases can be distinctly determined from the attained a maximum at a pH of 2 in the current study. Similar
XRD pattern. The two characteristic crystalline phases are of trends have been noted in other studies of RB removal where
magnetite and hematite. Magnetite is an oxidized crystal form a lower pH has been preferred for the adsorption study. RB
of iron with an inverse spinel type cubic structure having two removal using pine needles being one such example. RB at pH
active sites that are not equivalent in symmetry. The two lower than 4 tends to exist as a cationic monomer while at
nonequivalent structures being tetrahedral and octahedral greater pH RB tends to exist in zwitterion form. The
while hematite being a crystalline solid of the hexagonal zwitterions have a dimeric nature thus being a lot greater in
compact structure. 29.8, 35.5, 43.4, 57.1 and 62.9 are the size are not easily absorbed into the porous structure of the
intensities obtained at 2θ values. Furthermore, a higher degree activated carbon while at the same time the much smaller
cationic monomer has an easy access to the active sites of the
of crystallinity is observed at the magnetite portion of the
activated carbon [9]. Thus all the experiments for RB removal
material. It may be worth mentioning here about another
in the current study were conducted at pH 2
member of the iron oxide family namely maghemite,
comprising of cubic structure of inverse spinel type having a
B.2. Effect of Adsorbent Dosage on the removal efficiency
similar structure to that of magnetite only differing in the fact of Rhodamine B
that exclusively contains Fe(III) oxide. Similarly in the
structure of maghemite and magnetite makes it very difficult
for the distinct identification of one from the other using XRD
alone as a characterization method.

B. Effect of Different Parameters on the removal efficiency of

Rhodamine B using TAC/Fe
B.1. Effect of pH on the removal efficiency of Rhodamine
B

Figure 4: Removal Efficiency of Rhodamine B at different

Adsorbent Dosage (g/l). Initial Dye Concentration: 10ppm,
Temperature: 30°C, Time: 40 mins., pH: 2

The adsorbent dosage varied from 0.1 – 0.5 g/L. From Figure
4. it is evident that there was a steady increase in the removal
of RB as the amount of adsorbent dosage increased. This is
due to the fact that with the increase in dosage the number of
Figure 3: Removal Efficiency of Rhodamine B at different pH free pores and surface area increased greatly and thus
values. Initial Dye Concentration: 10ppm, Adsorbent Dosage: adsorption increased resulting in higher removal efficiency.
0.5g/l, Temperature: 30°C, Time: 16 hours This is probably due to the conglomeration of

The pH of wastewater solution is considered by far on the adsorbent particles which results in no further increase in
greatest factors that have an extremely significant effect on surface area of the AC [10]. Thus the removal efficiency
the process of adsorption during impurity removal and has becomes almost constant. Highest removal efficiency of
been considered perhaps the most important parameter in 85.25 % was observed at 0.5g/L and the least of 58.9 % was
determining optimum conditions for the removal of dyes from found at 0.1g/L.
water solutions. pH plays such a huge role in the adsorption
process majorly because of its contribution towards
B.3. Effect of Initial Dye Concentration on the removal
controlling the surface charge of the adsorbent. This basically
efficiency of Rhodamine B
has a pronounced effect on the electrostatic interaction
between adsorbent and adsorbate which plays a role in the
dissociation and association of the adsorbate molecules on the
active sites. Figure 3 depicts the effect of pH on the removal
efficiency of the prepared adsorbent with respect to RB
removal. As the figure depicts pH had a pronounced effect on
the removal of the dye from the aqueous solution. The
removal efficiency was seen to be slightly increased in the
range of 1-3 pH. Removal percentage was seen to attain a
highest of 85.25% at 2 pH while a contrasting removal
percentage of only 48.7% was noted at 12 pH. Removal
percentage was seen to be progressively decreased as the pH
increased towards a more basic zone. Removal efficiency

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 Novel Low Cost Adsorbent for the Removal of Rhodamine B Dye from Wastewater

parameters that are evaluated are the changes in standard

enthalpy (ΔH°), standard entropy (ΔS°) and standard free
energy (ΔG°). The ΔH° and ΔS° are determined from Van’t
Hoff equation:

Whereas ΔG° is confirmed using the following equation:

Where R is the universal gas constant (8.314 J/mol K), T is

the absolute temperature and K is the equilibrium constant.
The slope and encounter of the plot of ln K vs 1/T resulted
within the values of ΔH° and ΔS°, respectively. The
calculated values of ΔH°, ΔS°, and ΔG° are given in Table 2.
Figure 5: Removal Efficiency of Rhodamine B at different A negative worth of ΔG° suggests the viability and
Initial Dye Concentration (ppm). Adsorbent Dosage: 0.5g/l, spontaneous nature of the surface assimilation method with a
Temperature: 30°C, Time: 40 mins., pH: 2 high preference of RB onto the TAC/Fe. A positive worth of
An initial concentration range of 2ppm – 10ppm was taken ΔH° indicates the energy-absorbing nature of the surface
where absorption onto TAC/Fe was carried out. From Fig. 5 assimilation method. The low values of each ΔG° (20 to 0
we can see that the removal efficiency has a steady decrease kJ/mol) and ΔH° correspond to physical surface assimilation.
trend as the concentration of the dye increases. At low A positive worth of ΔS° reflects the inflated randomness at the
concentrations, there will be unoccupied active sites on the solid-aqueous interface with some structural changes in
adsorbent surface. Initially, the removal percentage was adsorbate and adsorbent.
96.3% due to the presence of abundant free pores but as the Temp.
concentration increased the pores become blocked and the (K)
removal efficiency decreased. The highest removal efficiency 303 -10.5755 0.004988 0.034919
was 96.3% at 2ppm and least was 85.25% at a 10ppm 313 -10.9247
concentration of RB solution. 323 -11.2738
333 -11.623
B.4. Effect of Temperature on the removal efficiency of 343 -11.9722
Rhodamine B Table 1: Thermodynamic parameters for adsorption of RB
onto TAC/Fe Initial Dye Concentration: 10ppm, Adsorbent
Dosage: 0.5g/l, Time: 40 mins. , pH: 2

B.5. Effect of Time on the removal efficiency of

Rhodamine B

Figure 6: Removal Efficiency of Rhodamine B at different

Temperatures (°C). Initial Dye Concentration: 10ppm,
Adsorbent Dosage: 0.5g/l, Time: 40 mins., pH: 2

From Fig. 6 it is evident that with the rise in temperature there Figure 7: Removal Efficiency of Rhodamine B at different
has been a continuous increase in the removal efficiency of Time (min.). Initial Dye Concentration: 10ppm, Adsorbent
the dye. Increase in temperature results in random motion of Dosage: 0.5g/l, Temperature: 30°C., pH: 2
fluid particles. The intermolecular distance increases and
there is a constant rapid motion of the molecules. Due to this, A 50-minute time range was taken where the removal % of
as the temperature rises the RB molecules start to vibrate RB solution onto TAC/Fe was studied. From the figure 7. it is
rapidly and their probability of getting absorbed into the evident that there is a continuous increase in the removal
TAC/Fe pore increases [11]. At a low temperature of 30°C the efficiency with time. The change in the rate of adsorption
molecular motion was very low and the removal efficiency might be due to the fact that initially all the adsorbent sites are
was 85.25 % but at higher temperatures around 80-100°C, the vacant and a solute concentration gradient is very high. Later,
removal efficiency increased to 90.2%. The thermodynamic the lower adsorption rate is due to a decrease in a number of

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 International Journal of Engineering Research And Management (IJERM)
ISSN: 2349- 2058, Volume-05, Issue-07, July 2018

vacant sites of adsorbent and dye concentrations. The

decreased adsorption rate, particularly, toward the end of
experiments, indicates the possible monolayer formation of
RB on the adsorbent surface. This may be attributed to the
lack of available active sites required for further uptake after
attaining the equilibrium.

CONCLUSION
From the above study we can conclude that pH, Initial Dye
Concentration (ppm), Dosage (g/L) and Temperature (°C)
play a significant role in adsorption of RB using TAC/Fe. The
removal % decreases as the initial dye concentration increases
and with increase in pH it also decreases as obtained from the
effects of the individual parameters. The removal of RB dye
increases with the increase in adsorbent dosage. From the
thermodynamic study it has been observed that at a low
temperature of 30°C the molecular motion was very low and
the removal efficiency was 85.25 % but at higher
temperatures around 80-100°C, the removal efficiency
increased to 90.2%.
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