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BAYERO JOURNAL OF ENGINEERING AND TECHNOLOGY (BJET) VOL.15 NO.1, JANUARY, 2020 pp7-14

ASSESSMENT OF CADMIUM ADSORPTION FROM WASTEWATER ONTO SUGARCANE BAGASSE

ACTIVATED CARBON

Adamu, Aliyu Dandajeh*1 and Adie, Donatus Begianpuye2

1, 2
Department of Water Resources and Environmental Engineering, Ahmadu Bello University Zaria-Nigeria

*Corresponding author’s address: adamualiyu@abu.edu.ng

ABSTRACT

The presence of abundant agricultural wastes in our environment coupled with the attendant pollution they generate call for
concern and as such their applications for removal of heavy metals from wastewater is very significant. Sugarcane bagasse
was converted to activated carbon using both thermal and chemical methods. The sugarcane bagasse was carbonized at the
temperature of 350oC and heating rate of 10oC/min for the residence time of 1hour. It was then mixed with (1M) H 3PO4 acid
at the ratio of 2:1 stirring continuously for the period of 3hours after which it was filtered and dried in the electrical oven.
The batch adsorption experiment was conducted under the initial cadmium concentration of 5-25 mg/l, adsorbent mass of
0.2-1.0 g, agitation time of 10-120 mins, pH of 2-10 and operating temperature of 30-50oC. The batch adsorption experiment
revealed the optimum initial cadmium concentration of 25 mg/l, adsorbent mass of 1.0 g, agitation time of 10 mins, pH of 4
and operating temperature of 30oC. In addition, the adsorption data fitted well to the Freundlich, Temkin and D-R model
with Freundlich and D-R models having maximum adsorption capacities of 2.0137 and 2.0140 mg/g, respectively. Similarly,
the mean free energy of 1.1307 kJ/mol obtained suggests that the adsorption process was physical. However, the adsorption
kinetic data fitted well to pseudo-second order; while the adsorption thermodynamic data revealed that the adsorption
process was exothermic with corresponding △H value of -5.080kJ/mol. It was concluded that the sugarcane bagasse activated
carbon was good for effective removal of cadmium from wastewater.
Keywords: activated carbon; cadmium; adsorption; sugarcane bagasse and wastewater

I. NTRODUCTION

Sugarcane (Saccharum officinarum) is a global agricultural
product because it plays significant role as food in many
countries including Nigeria (Girei and Giroh, 2012). As a
result, the production of high quantities of sugarcane is
accompanied by the generation of significant amounts of
sugarcane bagasse which pollute the environment. Sugarcane
bagasse is the residue left behind after the extraction of sugar
from the sugarcane (Adamu and Ahmadu, 2015). The
presence of agricultural wastes in our environment coupled
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with the attendant pollution they generate calls for concern
and as such their subjection into useful areas is very
significant. On the other hand, the increase in the population
growth coupled with the attendant industrial development,
lead to the release of many heavy metals into the
environment which are toxic to human beings and wild life.
They build up in the human body due to prolong exposure
and cannot be metabolized by our bodies; hence their
removal is crucial. However, amongst the heavy metals that
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BAYERO JOURNAL OF ENGINEERING AND TECHNOLOGY (BJET) VOL.15 NO.1, JANUARY, 2020 pp7-14
are found in the environment, lead, cadmium and mercury
are the most toxic (Giwa et al., 2013). In addition, sources of
cadmium include: rechargeable batteries, paints, metals
smelting, mining and electroplating (El Said et al., 2015; Niu
et al., 2014). Additionally, heavy metals can lead to several
health challenges which include: hypertension, kidney
disease, lung failure and cancer (Niu et al., 2014).
Moreover, the production of activated carbon from
agricultural waste is receiving great attention owing to the
fact that the commercial activated carbons are costly.
However, the aim of the research was to produce activated
carbon from sugarcane bagasse and use it for the removal of
cadmium from wastewater, which in turn played role in
reducing the quantities of sugarcane bagasse in the
environment thereby reducing the solid disposal challenges,
hence reduction in environmental pollution.
2. MATERIALS AND METHOD
2.1 Materials
Measuring cylinders (50, 100 and 1000 ml) and 250 ml flask,
distilled water, de-ionized water, 0.1M sodium hydroxide
(NaOH), 0.1M hydrochloric acid (HCl), 1M
tetraoxophosphate (V) acid (H3PO4) all of analytical grade,
electrical weighing balance (Mettler P160N), electric furnace
o
(Nabertherm, 30-3000 C), centrifugation machine
(Gallenramp Junoir), magnetic stirrer (79-1 stirrer), scan
electron microscope (Phenom ProX), fourier transform
infrared spectroscopy (FTIR-8400S, Shimadzu), pH meter
(Pocket size, Hanna), gas sorption analyzer (NOVA 4200e
Quantachrome), atomic absorption spectroscopy (AA6800
Shimadzu), membrane micro filter (0.45µm), filter paper, 30
mesh sieve (0.60mm).
2.2 Methods
2.2.1 Production of sugarcane bagasse activated carbon: The
sugarcane bagasse was washed thoroughly with tap water,
followed by distilled water to remove impurities and then
placed into electrical oven where it was oven dried overnight
at 100oC as reported by (Gaikwad and Mane, 2013; Mohd
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Adib et al., 2014; Pareira et al., 2010). It was grinded using
electrical blender and then sieved using standard sieve test
(30mesh sieve). The prepared sugarcane bagasse was then
placed into an electrical furnace and carbonized at the
temperature of 350oC and heating rate of 10oC/min for
residence time of 1 hour. It was placed into Desiccator and
allowed to cool. It was then impregnated with H3PO4 (1M) at
ratio of 2:1 and stirred continuously for 3hours in accordance
with Mohammad (2015) and Pradhan (2011). It was then
filtered with filter paper and washed thoroughly with distilled
to remove excess acid until the pH was 7 and dried at 100oC
for the period of 4 hours.
2.2.2 Preparation of stock solution of cadmium (100mg/l):
100 mg/l cadmium (Cd) solution was prepared by dissolving
0.2774 g of Cd(NO3)2.4H2O in 10 ml of 0.1M HNO3 in the
1000 ml volumetric flask. The de-ionized water was added to
make it 1000 ml. From this, desired solutions of 5, 10, 15, 20
and 25 mg/l of Cd were prepared by diluting 95, 90, 85, 80
and 70 ml of de-ionized water in 5, 10, 15, 20 and 25 ml of
100 mg/l Cd solution.
2.2.3 Batch adsorption of Cd onto sugarcane bagasse
activated carbon: 1.0 g of sugarcane bagasse activated carbon
was placed into 250 ml flask containing 100 ml of 25 mg/l of
Cd solution and agitated continuously in the magnetic stirrer
at the speed of 150 rpm during which samples were
withdrawn at 10, 30, 60, 90 and 120 mins agitation times,
respectively and centrifuged at 2000 rpm for 20 minutes. In
a similar vein, 0.2, 0.6, and 1.0 g were placed into the flask
containing 25 mg/l of Cd and agitated at 30 mins. Similarly,
1.0 g was placed into the flasks containing 5, 10, 15, 20 and
25 mg/l and agitated at 30 mins. The residual Cd
concentrations were analyzed using atomic absorption
spectrophotometer (AA 6800). The experiment was also
carried out at pH values of 2, 4, 6, 8 and 10 and operating
temperatures of 30, 40 and 50oC.
The Langmuir, Freundlich, Temkin and Dubinin-
Radushkevich (D.R) adsorption isotherm parameters were
obtained using equations (1), (2), (3) and (4), respectively:
𝐶𝑒 1 𝐶𝑒
= + … (1)
𝑞𝑒 𝑏𝑞𝑚 𝑞𝑚
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1 𝑞𝑒
log qe = log k f + log 𝑐𝑒 … (2) 𝑘𝑜 = … (9)
𝑛 𝐶𝑒

𝑞𝑒 = 𝐵𝑡 ln 𝐴𝑡 + 𝐵𝑡 ln 𝐶𝑒 … (3) ∆𝐺 𝑜 = ∆𝐻𝑜 − 𝑇∆𝑆 𝑜 … (10)

2
ln 𝑞𝑒 = ln 𝑞𝑚 − BD 𝜇 (4) Where △ 𝑆 is the entropy change (kJ/mol), △ 𝐻 is the
enthalpy change (kJ/mol) and ∆𝐺 is the free energy change
Where 𝐵𝑡 , 𝜇 and 𝐸 were obtained using equation (5), (6)
(kJ/mol).
and (7), respectively;
3. RESULTS AND DISCUSSION
𝑅𝑇
𝐵𝑡 = … (5)
𝑏
Table 2 shows the characteristics of the sugarcane bagasse
1
𝜇 = RTln(1 + ) … (6) activated carbon produced. The Table indicated that the
Ceq
sugarcane bagasse carbon possessed average pore diameter,
1
𝐸= … (7) micro pore volume, surface area and pH of: 5.272 nm,
√(−2BD)
0.647cm3/g, 1470.44 m2/g and 7.2, respectively. The

Where 𝐶𝑒 is the effluent concentration at equilibrium (mg/l), possession of average pore diameter of 5.272 nm implied that

𝑞𝑒 is the adsorption capacity at equilibrium (mg/g), 𝑏 is it possessed mesoporous structure, owing to the fact that an

Langmuir constant, 𝑞𝑚 is the maximum monolayer average pore diameter of 5-50 nm possessed by activated

adsorption capacity (mg/g), k f is the maximum multilayer carbon, suggests the presence of mesopores. In addition,

adsorption capacity (mg/g), n is the adsorption intensity, 𝐵𝑡 surface area of the sugarcane bagasse carbon was very high,

is related to the heat of adsorption (J/mol), 𝐴𝑡 is the temkin which suggested that it can be used to adsorbed solute from

adsorption intensity (l/mg), 𝑏 is the energy constant of the wastewater.

model, 𝑅 is the molar gas constant (8.314 J/k/mol); 𝑇 is the Table 2: Characteristics of the SBAC
Characteristics Results
absolute temperature (k), BD is the D-R isotherm constant
Surface area (m2/g) single 1142.00
(𝑚𝑜𝑙 2 /𝑘𝐽−2 ), 𝑞𝑚 is the maximum adsorption capacity point
(mg/g) and 𝐸 is the mean free energy. Surface area (m2/g) multi 1470.44
point
The adsorption kinetic models used are depicted in Table 1
Micro pore volume (cm3/g) 0.647
Average pore diameter 5.272
Table 1: Adsorption kinetics (nm)
pH 7.2
Adsorption Equation Parameters
Moisture content (%) 3.21
kinetics
Ash content (%) 3.78
Pseudo- first log (𝑞𝑒 − 𝑞𝑡 ) 𝑞𝑒 and 𝑘1
order 𝑘1 𝑡
= log 𝑞𝑡 −
2.303 Figure 1 and 2 depicted the effects of initial cadmium
Pseudo- second 𝑡 𝑡 1 𝑞𝑒 and 𝑘2
= + concentration on the adsorption capacity and removal
order 𝑞𝑡 𝑞𝑒 𝑘2 𝑞𝑒2
efficiency, respectively. From Figure 1, the adsorption
Where t is the time (min), 𝑞𝑡 is the adsorption capacity at
capacity increased from 0.4999 to 2.4998 mg/g when the
time t (mg/g), 𝑘1 (𝑚𝑖𝑛 −1 ) and 𝑘2 (g/mg/min) are the pseudo-
initial cadmium concentration increased from 5 to 25 mg/l,
first order and second order rate constant.
respectively. The result revealed that, increased in the initial
The adsorption thermodynamic data were obtained using
cadmium concentration was accompanied with increased in
equations (8), (9) and (10)
the adsorption capacity. This could be attributed to the fact
△𝑆 0 △𝐻 0
ln 𝑘𝑜 = − … (8) that, increase in the initial cadmium concentration resulted to
𝑅 𝑅𝑇
upward in driving force that checked the resistance of
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adsorbate transport from the aqueous solution to the
adsorbent surface, hence the increase in the adsorption of
cadmium. This result agreed with the findings of Mohammad
(2015); Mopoung (2015) and Chi (2013).
3 20
qe (mg/g)
2
1 0
0 w (g)
0 10 20 30
Co (mg/l)
Figure 1: Effects of initial concentration of cadmium on
adsorption capacity
In Figure 2, when the initial cadmium concentrations rose
from 5 to 25 mg/l, the removal efficiency also improved from
99.982 to 99.992%, respectively. The increased in the
removal efficiency as the initial cadmium concentrations
increased suggest the presence of multilayer surface
adsorption in which the solute could be adsorbed on the layer
that was preoccupied by solute. This result agreed with
Mohammad (2015).
99.995
R.E. (%)
99.99
99.985
99.98
0 10 20 30
Co (mg/l)
Figure 2: Effects of initial concentration of cadmium on
removal efficiency
Figures 3 and 4 depict the effect adsorbent mass on
adsorption capacity and removal efficiency, respectively. In
Figure 3, when the adsorbent mass increased from 0.2 to 1.0
g, the adsorption capacity declined from 12.4882 to 2.4998
mg/g, respectively. The decreased in the adsorption capacity
as the adsorbent mass inclined could be due to the fact that at
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constant initial cadmium concentration, the rise in the
adsorbent mass translated into decreased in the ratio of
amount of cadmium removed in relation to unit mass of
adsorbent.
qe (mg/g)
10
0
0.5 1 1.5
Figure 3: Effects of adsorbent mass on adsorption capacity
In Figure 4, when the adsorbent mass rose from 0.2 to 1.0 g,
the removal efficiency also rose from 99.905 to 99.992%,
respectively. The increased in the removal efficiency as the
adsorbent mass increased could be attributed to the increased
in the sorption sites, making more cadmium to be removed
from the aqueous solution onto the adsorbent. This
observation is in agreement with Dargo (2014) and
Mohammad (2015).
100.1
R.E. (%)
100
99.9
0 0.5 1 1.5
w (g)
Figure 4: Effects of adsorbent mass on removal
efficiency
Figures 5 and 6 contain the effect of agitation time on the
adsorption capacity and removal efficiency, respectively.
From the Figures, the adsorption capacity and removal
efficiency attained maximum values of 2.4648 mg/g and
98.592%, respectively at 30 mins. In addition, the cadmium
adsorption was rapid initially because there were many
vacant sites for cadmium adsorption, which thereafter
become limited as the agitation time increased due to
occupation of the sorption sites. This result agreed with Giwa
et al. (2013) and Mohammad (2015).
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3 12.498
qt (mg/g)

2
12.497

qe (mg/g)
1
12.496
0
0 50 100 150 12.495
t (mins) 12.494
0 5 10 15
Figure 5: Effects of agitation time on adsorption capacity pH

Figure 7: Effect of pH on adsorption capacity

150
R.E. (%)

100 99.985
50 99.98
99.975

R.E. (%)
0
0 50 100 150 99.97
99.965
t (mins) 99.96
99.955
Figure 6: Effects of agitation time on removal efficiency 0 5 10 15
Figure 7 and 8 show the effect of solution pH on the pH
adsorption capacity and removal efficiency of cadmium onto
sugarcane bagasse activated carbon. From the Figures, the Figure 8: Effect of pH on removal efficiency
adsorption capacity and removal efficiency recorded lowest Figures 9 and 10 depict the effect of operating temperature
values of: 12.4950 mg/g and 99.960%, respectively at pH of from 30 to 50oC on the adsorption capacity and removal
2. However, the highest adsorption capacity and removal efficiency of cadmium onto sugarcane bagasse activated
efficiency of 12.4976 mg/g and 99.980%, respectively were carbon. From the Figures, adsorption capacity and removal
recorded at pH of 4. This indicated that the optimum solution efficiency of 12.4946 mg/g and 99.957%, respectively were
pH for adsorption and removal of cadmium onto sugarcane obtained at the operating temperature of 30oC; while the least
bagasse activated carbon was 4. It is important to note that, adsorption capacity and removal efficiency of: 12.4939 mg/g
at lower pH value, the hydrogen ions compete with the and 99.951% were recorded at 50oC. This signified that the
cadmium ion at the sorption site which resulted to low adsorption process of cadmium onto sugarcane bagasse
adsorption of cadmium ion. However, at higher pH, there activated carbon was exothermic because it decreased with
were more negative ions that neutralized the hydrogen ions, increased in the operating temperature.
which in turn enhanced the adsorption of cadmium ion. This
12.4948
result agreed with Saritha et al. (2011) and Niu et al. (2014).
12.4946
qe (mg/g)

12.4944
12.4942
12.494
12.4938
0 20 40 60
T (oC)

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Figure 9: Effect of operating temperature on adsorption Table 3: Adsorption isotherm data

capacity Adsorption Parameters Values
isotherm
Langmuir -b (l/mg) 0.6667
isotherm
qm (mg/g) 5000
99.958 R2 0.2809
99.956 Freundlich 1/n 0.1698
isotherm
R.E (%)

99.954 kf (mg/g) 2.0137

99.952 R2 0.9471
Temkin isotherm At (l/mg) 1.0013
99.95 Bt (J/mol) 2.4976
0 20 40 60 b 992
T (oC) R2 1.0000
D-R isotherm BD (mol2/kJ2) 0.3911
qm (mg/g) 2.0140
Figure 10: Effect of operating temperature on removal E (kJ/mol) 1.1307
R2 0.9472
efficiency
Table 4 shows the adsorption kinetic data. From the Table,
the pseudo-first order and pseudo-second order kinetics
Table 3 shows the adsorption isotherms data for the batch
possessed R2 values of: 0.5873 and 0.9995, respectively
adsorption process of cadmium onto sugarcane bagasse
which indicated that the adsorption kinetic data fitted well to
activated carbon. The Table indicated that the adsorption data
pseudo-second order than the pseudo-first order. In addition,
fitted well to Freundlich, Temkin and D-R models than the
the pseudo-second order recorded rate constant (K2) value of:
Langmiur model owing to the fact they have higher R2
0.0612 mg/g/min with the corresponding experimental
values. The R2 values of Freundlich, Temkin and D-R models
adsorption capacity value of 10.070 mg/g.
were: 0.9471, 1.0000 and 0.9472, respectively. In addition,
the Freundlich isotherm recorded maximum adsorption
Table 4: Adsorption kinetic data
capacity (kf) of: 2.0137 mg/g with the corresponding 1/n
Kinetic model Parameters Values
value of: 0.1698, which suggested that the adsorption process Pseudo-first order K1 (min-1) 0.0099
was favourable. Moreover, the D-R model recorded qe (mg/g) 0.8748
R2 0.5873
maximum adsorption capacity (qm) of 2.0140 mg/g, with the
Pseudo-second order K2 (mg/g/min) 0.0612
corresponding mean free energy of 1.1307 kJ/mol which qe (mg/g) 10.070
suggested that the adsorption process was physical. On the R2 0.9995
other hand, the Temkin isotherm recorded adsorption Table 5 depicts the adsorption thermodynamic data. From the
intensity value of 1.0013 l/mg with the corresponding heat Table, enthalpy change (△H) recorded value of -5.080
adsorption value of 2.4976 J/mol. kJ/mol, which signified that the adsorption process was
exothermic. In addition, the △H value obtained also
suggested that the adsorption process was physical reported
by Rahman and Sathasivam (2015). However, the change in
entropy (△S) also recorded positive value of 0.0149 kJ/mol,
which suggested that there were increased in affinity at
solute-adsorbent interface as reported by Chowdhury et al.
(2015) and Zhang et al. (2017). Similarly, the Gibbs free

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BAYERO JOURNAL OF ENGINEERING AND TECHNOLOGY (BJET) VOL.15 NO.1, JANUARY, 2020 pp7-14
energy (△G) also recorded negative values of - 17.776 to -
18.604 kJ/mol. The negative value of △G implied that the
adsorption process was spontaneous and feasible (Purkait et
al. 2007).
Table 5: Adsorption thermodynamic data
T 1/T (K-1) ln k -△G △S △H
(K) (g/l) (kJ/mo (kJ/mol) (kJ/mol)
l)
303 0.00330 2.871 17.776 0.0149 -5.080
313 0.00319 2.292 18.185 0.0149 -5.080
323 0.00310 1.749 18.604 0.0149 -5.080
CONCLUSION
Based on the laboratory work carried out on the production
of activated carbon from sugarcane bagasse and its
application for cadmium adsorption from wastewater, the
sugarcane bagasse had been converted to low cost adsorbent
which was effectively used to adsorbed cadmium from
wastewater. Similarly, the research identified the optimum
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