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European Journal of Applied Sciences – Vol. 10, No. 4
Publication Date: August 25, 2022
DOI:10.14738/aivp.104.12764. Ochiagha, K. E., Eboagu, N. C., Eze, U. G., Odidika, C. C., & Aralu, C. C. (2022). Comparative Study of the Adsorption Effects of
Activated Carbons from Coconut Shell and Groundnut Shell as Absorbents for Metal Ions. European Journal of Applied Sciences,
10(4). 492-507.
Services for Science and Education – United Kingdom
Comparative Study of the Adsorption Effects of Activated Carbons
from Coconut Shell and Groundnut Shell as Absorbents for Metal
Ions
Ochiagha, K. E.
Department of Pure and Industrial Chemistry
Nnamdi Azikiwe University, Awka
Eboagu N. C.
Department of Pure and Industrial Chemistry
Nnamdi Azikiwe University, Awka
Eze, U. G.
Department of Pure and Industrial Chemistry
Nnamdi Azikiwe University, Awka
Odidika, C. C.
Department of Pure and Industrial Chemistry
Nnamdi Azikiwe University, Awka
Aralu, C. C.
Department of Pure and Industrial Chemistry
Nnamdi Azikiwe University, Awka
ABSTRACT
The main objective of this research was to compare the effect of contact time,
concentration, and temperature in preparing activated carbon from coconut shells
and groundnut shells. The research was carried out at a temperature range of 35°C-
65 °C and the maximum adsorption capacities for Pb(II) and Cd(II) ions were
respectively 3.61 and 3.34 mg/g for coconut shell, 3.21 and 3.13 mg/g for groundnut
shell at the optimum temperature of 35°C. Thus the maximum ion adsorption
capacities followed the trend: coconut shell>groundnut shell. These results were
obtained using the following optimum conditions: initial metal ions concentration
of 100 mg/dm3, adsorbents weight of 0.5g, time of 30 min, and pH of 6. The
adsorption of the metal ions by the adsorbents was found to decrease with an
increase in the initial concentration of the metal ions in an aqueous solution. Also,
the adsorption rate increased with temperature. The result of the work revealed
that activated carbons derived from coconut shells and groundnut shells can be
used as a low-cost alternative to commercial adsorbents in the removal of Pb(II)
and Cd(II) ions from water and wastewater.
Keywords: Adsorption, temperature, concentration, coconut shell, and groundnut shell.
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Ochiagha, K. E., Eboagu, N. C., Eze, U. G., Odidika, C. C., & Aralu, C. C. (2022). Comparative Study of the Adsorption Effects of Activated Carbons
from Coconut Shell and Groundnut Shell as Absorbents for Metal Ions. European Journal of Applied Sciences, 10(4). 492-507.
URL: http://dx.doi.org/10.14738/aivp.104.12764
INTRODUCTION
Environmental pollution of the ecosystem has been on the rise for the past decades due to
industrialization [1]. Pollution of the environment especially water has been attributed to poor
waste management practices [2]. Heavy metals are one of the pollutants of interest to the
research community that has been extensively researched in recent years [3,4]. Rapid
industrial, urbanization and economic growth have contributed to the increase in heavy metals
in the environment [5]. The accumulation of these heavy metals in the environment can pose a
negative effect on the populace which can result in human health risks [6,7]. Different
conventional techniques have been utilized in the removal of these heavy metals from the
environment, and adsorption has proved to be more successful than the others [8,9].
Adsorption of these heavy metals on conventional absorbents such as activated carbon has
frequently been employed, but just like the other conventional absorbents, the methods are
often expensive and difficult to maintain [10,11]. This is a result of the high capital and
operational costs, as well as the extra cost of treating the resultant sludge generated before
disposal [12,13]. A good absorbent can be considered low cost or cheap if it is abundant in
nature, requires little processing, has high regeneration capacity and is a by-product or waste
material from the industry [14, 15].
The recent search for low-cost and easily available materials with high absorptive capacities
has led to the investigation of materials of agricultural origin as potential metal absorbents [16-
18]. The use of agricultural materials such as agricultural waste or by-products as absorbents
for the treatment of wastewater as a potential alternative to the conventional treatment
method has been reported in the literature [19-23].
The adsorption of heavy metals using agricultural wastes might be attributed to their proteins,
carbohydrates, and phenolic compounds which have carboxyl, hydroxyl, sulphate, phosphate,
and amino groups that can bind metal ions [19]. Research has shown that modifications of these
agricultural wastes through chemical and physical methods such as carbonization can also
increase their functional groups which will strengthen their adsorption potentials [15, 24].
The agricultural wastes of interest in this work are groundnut shells and coconut shells. These
materials are renewable/biodegradable agricultural wastes available abundantly in large
quantities at little or no cost. The paper seeks to compare the adsorption effects of using
coconut shells and groundnut shells as absorbents for the adsorption of lead and cadmium ions.
The influence of adsorption parameters such as pH, absorbent mass, contact time, initial
concentration of metal ions, and temperature were evaluated.
MATERIALS AND METHODS
Materials
Analytical grade reagents were used for the study and were purchased from Sigma- Aldrich,
USA. The equipment used for this study was a muffle furnace (S30 2AU), pH metre (Labtech
Photic 20), centrifuge (CF-30), weighing balance (Mettler Toledo Ag 204), Thermostatic water
bath (HH-2) and Atomic Absorption Spectrophotometer (AAS) (FS-244AA). The experiments
were done using standard methods [25].
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Collection and preparation of the adsorbents
The adsorbents were collected at a market in Enugu, Nigeria. The coconut shell was soaked for
about two hours in distilled water, well-scrubbed using a sponge and distilled water, and then
air dried for twenty-four hours. The dried shell was then placed on a clean hard surface and
broken into smaller pieces with the use of a hammer and then preserved in a clean polythene
bag pending carbonization. The groundnut shell was soaked for about two hours in the water,
well cleaned with the aid of the hand and distilled water, and then air dried for twenty-four
hours and later stored in a polythene bag.
Carbonization of the adsorbents
The shell was burnt in a muffle furnace at a temperature of 550 °C for 1 hour. The carbon was
then left to cool for 24 hours. The material was then ground with the aid of a mortar and pestle
and sieved using a sieve of 7.1 mm. A similar experimental procedure was adopted for the
preparation of groundnut shells.
Activation of the adsorbents
About 600 g of each adsorbent carbon was mixed with 0.6 dm3 of HCl solution (72% acid). Each
of the carbonized adsorbents was washed with distilled water until the washing was free of
acid, and then the pH of the washed adsorbents was close to neutral. The washed adsorbents
were air-dried for 24hrs. It was sieved using a 7.1 mm sieve and then stored in air-tight
containers for use.
Ash content determination
The crucibles to be used were thoroughly washed, oven-dried, and then left to cool. The weight
of each crucible was recorded as W1. Then 2g of each sample was placed in a pre-weighed
crucible and the weight of both the sample and crucible was recorded as W2. The sample was
ignited at 550°C in the muffle furnace for an hour and the weight of the sample and crucible
after charring was recorded as W3. The ash content for each sample was calculated according
to the following formula:
Ash content = "
!!"!#
!!"!$
# × 100 (1)
Moisture content determination
The determination of the ash content was employed for moisture content determination (Eq.
2), except that the drying of the sample was carried out at 105°C using an electric oven.
Moisture content = "
!!"!#
!!"!$
# × 100 (2)
Where: �"= weight of empty crucible, �#= weight of crucible + sample before drying, �$=
weight of crucible + sample after drying.
pH determination
10 g of each adsorbent was dissolved in 0.09 dm3 of distilled water. The solution was thoroughly
agitated and then filtered. The pH of the filtrate was then measured. Freshly prepared buffer 7
solutions were used to calibrate the pH meter before the measurement.
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Ochiagha, K. E., Eboagu, N. C., Eze, U. G., Odidika, C. C., & Aralu, C. C. (2022). Comparative Study of the Adsorption Effects of Activated Carbons
from Coconut Shell and Groundnut Shell as Absorbents for Metal Ions. European Journal of Applied Sciences, 10(4). 492-507.
URL: http://dx.doi.org/10.14738/aivp.104.12764
Preparation of the metal solutions (adsorbate)
All reagents used for this study were analytical reagent grade. The stock solution of lead and
cadmium ions was prepared by mixing 1000 mg of the lead nitrate and cadmium chloride each
in a small amount of distilled water in a 1L volumetric flask and made up to the mark with
distilled water. From the stocks, working solutions of various concentrations (100, 120, 140,
and 160 mg/dm3) of each ion were prepared by serial dilution. The total concentration of each
metal ion in the aqueous solution was confirmed by analysis using AAS.
Experimental procedure
Batch adsorption experiments were carried out to obtain equilibrium data because of their
simplicity. Batch adsorption was performed to study the effect of adsorbent mass, contact time,
pH, initial metals ion concentration, and temperature on the adsorption of Pb(II) and Cd(II) ions
on coconut shells and groundnut shells.
Variation of adsorbent mass, contact time and adsorbate pH
Adsorbent mass, pH, and contact time are among the important parameters in the adsorption
process that determine the capacity of the adsorption under a given set of conditions. The
adsorptions of the metal (lead and cadmium) ions on each adsorbent were studied by varying
the mass of the adsorbent (0.2g, 0.5g, and 1.0g). The adsorption studies were carried out using
0.02 dm3 of each metal ion solution and were measured into three labelled beakers, with each
containing 0.2g, 0.5g, and 1.0g of the adsorbent respectively. The mixtures were uniformly
stirred at 35°C for 10 min. The experimental setup was thereafter repeated various times; 20
min, 30 min, and 40 min. after the predetermined time interval; the content of each tube was
centrifuged and filtered through Whatman filter paper (No 4). The concentration of metal ions
in the filtrates was determined using AAS and the number of metal ions adsorbed was
calculated.
The whole experimental set up repeated at varying pH (2, 4, 6, and 8), and the desired pH of the
metal ions solutions was obtained by adding HCl or NaOH as the case may be. At the end of each
pH analysis, the content of each tube was centrifuged and filtered through Whatman filter paper
(No. 40). The concentrations of the metal ion of the filtrates, Ce, were determined using AAS
and the number of metal ions absorbed was calculated.
Variation of initial metal ion concentration
Adsorption studies were carried out by varying the initial metal ions concentrations of lead
solution from 100 to 160 mg/dm3 at intervals of 20 mg/ dm3, at a pH of 6, the adsorbent mass
of 0.5g, and maintaining a temperature of 35°C. 0.5g adsorbent (coconut shell) was weighed
into each of the four (0.1 dm3) beakers and 0.02 dm3 of each of the various concentrations of
the metal ion (Pb) were measured in the beakers. The adsorption mixtures were uniformly and
continuously stirred at a fixed temperature of 35°C for 30 minutes after which the content of
each beaker was filtered into clean sample bottles. The content of each tube was centrifuged
and filtered. The concentrations of metal ions in the filtrates, Ce, were determined using an AAS.
The number of metal ions adsorbed from the solution was then determined using equation 4.
The experimental setup was repeated using the same adsorbent (coconut shell) and cadmium
ion. Similar experiments were carried out using activated carbons of groundnut shells.
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Variation of temperature
The adsorption of the metal ions on the adsorbents was studied at various temperatures (35-
65°C) with the aid of a thermostatic water bath and using adsorbents mass of 0.5g, pH of 6,
contact time of 30 min, and 0.02 dm3 of each metals ion solutions of initial concentration of 100
mg/dm3. The metal ion (lead or cadmium) solution was measured into two labelled beakers
each containing 0.5g of coconut shell and groundnut shell respectively. The mixtures were
uniformly stirred at 35°C for 30min. At the end of each temperature analysis, the content of
each tube was centrifuged and filtered through Whatman filter paper (No 4). The concentration
of metal ions in the filtrates was determined using AAS and the number of metal ions adsorbed
was calculated. The procedure was repeated at 45°C, 55°C, and 65°C to study the effect of
temperature on the process.
Data evaluation
The removal efficiency (% of adsorption or rate of adsorption) of the metal ions, Pb and Cd,
were calculated using equation 3.
Removal efficiency = "
��"��
��
# × 100 (3)
The amount of the metal ion adsorbed was obtained from the differences between the metal
quantity adsorbed by the adsorbent and the metal ion content of the synthetic wastewater by
using the following equation [26].
�& = "
��"��
� # × � (4)
Where, qe (mg/g) is the amount adsorbed; also known as the equilibrium adsorption capacity,
Co and Ce are the initial and equilibrium concentrations of metal ion (mg/dm3), V is the volume
(dm3) of the metal ion solution used and M is the weight (g) of the adsorbent.
RESULTS AND DISCUSSION
Physico-chemical properties
The physic-chemical parameters of the adsorbents determined are the pH, moisture, and ash
contents. The values obtained are represented in Table 1.
Table 1: Physico-chemical properties of activated carbons from coconut shell and groundnut
shell
Parameters Coconut shell Groundnut shell
Moisture content (%) 10 10
Total Ash (%) 5 15
pH 7.2 6.8
Table 1 shows the percentage compositions of the moisture, total ash and pH of the adsorbents.
It can be seen that the pH of the adsorbent is generally close to neutral pH.
Effect of pH
The effect of adsorbent pH on the adsorption rate of lead and cadmium can be seen as presented
in Fig. 1 and Fig. 2 respectively under the following conditions, the concentration of Pb(II):
100mg/dm3, time: 30min, temp: 35°C, the weight of each adsorbent: 0.5g, particle size: 1.10mm.
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Ochiagha, K. E., Eboagu, N. C., Eze, U. G., Odidika, C. C., & Aralu, C. C. (2022). Comparative Study of the Adsorption Effects of Activated Carbons
from Coconut Shell and Groundnut Shell as Absorbents for Metal Ions. European Journal of Applied Sciences, 10(4). 492-507.
URL: http://dx.doi.org/10.14738/aivp.104.12764
100 –
95 – Coconut shell
90 – Groundnut shell
85 –
80 –
75 –
70 –
65 –
60 –
55 –
50 –
0 2 4 6 8 10
pH
Fig. 1: Effect of pH on Pb(II) ion adsorption
Fig. 1 shows the effect of pH on the adsorption of Pb(II) ions onto the adsorbents. The pH of the
hydrogen ion concentration was examined over the pH range of 2 to 8. It was observed that
with the increase in the pH of the Pb(II) ion solution, the rate of adsorption increased from pH
of 2 to 6 attaining maximum values of 90.2% and 80.33% respectively for coconut shell and
ground nut shell around pH of 6. The peak percentage adsorption of lead was attained around
a pH of 6. But after pH 6, there was a decrease in the adsorption rate.
100 –
95 – Coconut shell
90 – Groundnut shell
85 –
80 –
75 –
70 –
65 –
60 –
55 –
50 –
0 5 10
pH
Fig. 2: Effect of pH on Cd(II) ion adsorption.
In Fig 2, it could be observed that the % of Cd(II) ion adsorbed increased between pH 2 to 6 and
attained a maximum value of 83.5% and 78.2% respectively for coconut shell and ground
nutshell at pH of 6. But after a pH of 6, there was a decrease in the adsorption. Among the
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reasons for the decrease in the rate of adsorption as pH increased beyond neutral, may be due
to the weakening of electrostatic force of attraction between the oppositely charged adsorbate
and adsorbent ultimately leading to a reduction in adsorption capacity [27,28]. Therefore pH
of 6 was used in all subsequent experiments.
Generally, for both Pb and Cd ions adsorbed, as shown in Figures 1 and 2, the trend for the
adsorption rate is coconut shell > groundnut shell. Again, it could be observed that the
percentage of lead ion adsorbed is greater than the cadmium ion.
Effect of adsorbent weight
The effect of the adsorbent on lead and cadmium adsorption rate is presented in Figures 3 and
4 respectively. Adsorbent weight is one of the important parameters in the adsorption process
because it determines the capacity of an adsorbent for a given initial concentration of the
adsorbate under a given set of operational conditions.
100 –
95 – Coconut shell
90 – Groundnut shell
85 –
80 –
75 –
70 –
65 –
60 –
55 –
50 –
0 0.5 1 1.5
Adsorbent weight (g)
Fig. 3: Effect of adsorbent weight on Pb(II) ion adsorption
Figure 3 shows the influence of the weight of the adsorbent on the adsorption of the Pb (II) ion.
The experimental result showed an increase in both percentages adsorbed (85.8% and 90.2%;
77.25% and 80.33% for coconut shell and groundnut shell respectively) and the amount
adsorbed with an increase in the adsorbent mass from 0.2g to 0.5g. However, the percentage of
the metal ion adsorbed decreases (88.93% and 76.9% respectively for coconut shells and
groundnut shells) with a further increase in mass from 0.5g to 1g. It can be said that the initial
increase in the percentage of the metal ion adsorbed as a result of the increase in adsorbent
mass may be because more adsorbent surfaces are available for adsorption of the metal ion
[29]. Also, the eventual decrease in the rate of adsorption with a further increase in the mass of
adsorbents may be attributed to the increased mass of adsorbents preventing effective contact
between the adsorbents and the metal ions [30]. Therefore, the adsorbent mass of 0.5g was
used in all subsequent experiments.
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Effect of temperature % of Pb(II) ion adsorbed
100
95 Coconut shell
90 Groundnut
shell
85
80
75
70
65
60
20 30 40 50 60 70
Temperature (oC)
Fig. 5: Effect of temperature on Pb(II) ion adsorbed
The effect of temperature on the adsorption rate of lead and cadmium can be seen as presented
in Figures 5 and 6 respectively.
Figure 5 shows that temperature can affect the adsorption behaviour of Pb(II). Thus, the
removal of Pb(II) from aqueous solution by these adsorbents was temperature-dependent. An
increase in temperature from 35°C to 65°C was found to result in a steady increase in the
percentage (from 90.2% to 96.55% and 80.33% to 90.68% respectively for coconut shell and
groundnut shell of the metal ion adsorbed. This is probably due to the temperature effect on
the interaction between the shells and the metal ions in the solution [31, 32].
Increase in temperature from 35°C to 65°C was found to result in a steady increase in the
percentage from 90.2 to 96.55 and 80.33 to 90.68 respectively for coconut shell and groundnut
shell of the metal ion adsorbed.
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Fig. 3.7: Effect of initial concentration on Pb(II) ion adsorption
Figure 7 indicates that the percentage of Pb(II) ion adsorbed decreased from 90.2 to 78.95%
and 80.30 to 65.23% respectively for coconut shell and groundnut shell, with an increase in
initial concentration of the metal ion from 100 to 160 mg/dm3. Figure 8 indicates that the
percentage of the Cd(II) ion metal adsorbed decreased (from 83.50 to 72.18% and 78.20 to
66.58% respectively for coconut shell and groundnut shell) with an increase in initial
concentration of the metal ion from 100 to 160 mg/dm3.
The decrease in the initial metal ion concentration of both adsorbents was due to the fact, that
at higher concentrations of the metal ions, the available adsorption sites of the adsorbents
became less, and hence the percentage removal decreases [14]. % of Pb(II) Ion Adsorbed
95-
90- Coconut shell
85- Groundnut shell
80-
75-
70-
65-
60-
55-
80 100 120 140 160 180
Initial Conc. of Pb(II) Ion (mg/dm3)
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Fig. 9: Effect of contact time on Pb(II) ion adsorption
% of Cd(II) Ion Adsorbed
100 –
95 – Coconut shell
90 – Groundnut shell
85 –
80 –
75 –
70 –
65 –
60 –
55 –
50
0 10 20 30 40 50
Time (min)
Fig. 10: Effect of contact time on Cd(II) ion adsorption
Figure 10 shows that a contact time of 30 min was sufficient to achieve equilibrium and that the
adsorption does not change significantly with a further increase in contact time. Therefore, an
equilibrium time of 30 min was used in all subsequent experiments. Ranking the adsorption
rate of the adsorbents, it can be seen that the coconut shell has the highest value of adsorption
efficiency followed by the groundnut shell. Generally, the experimental results obtained for the % of Pb(II) Ion Adsorbed
100 –
95 – Coconut shell
90 – Groundnut shell
85 –
80 –
75 –
70 –
65 –
60 –
55 –
50
0 10 20 30 40 50
Time (min)
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Ochiagha, K. E., Eboagu, N. C., Eze, U. G., Odidika, C. C., & Aralu, C. C. (2022). Comparative Study of the Adsorption Effects of Activated Carbons
from Coconut Shell and Groundnut Shell as Absorbents for Metal Ions. European Journal of Applied Sciences, 10(4). 492-507.
URL: http://dx.doi.org/10.14738/aivp.104.12764
metal ion adsorption reveal that the value obtained for cadmium adsorption is less than those
obtained in the adsorption of lead.
CONCLUSION
The study indicated the suitability of activated carbons derived from coconut shells and
groundnut shells for the removal of Pb(II) and Cd(II) in an aqueous solution through batch
adsorption studies. The experimental data showed that the adsorption rate of heavy metal ions
depends to a large extent on the initial concentrations of the metal ions, temperature, adsorbent
mass, pH of the solution, and contact time. It was also seen in the study that an optimum contact
time of 30 minutes, the adsorbent mass of 0.5g, adsorbate pH of 6, and initial metals (Pb and
Cd) ion concentration of 100 mg/dm3 were required for the maximum removal of the lead and
cadmium by the adsorbents. Under the conditions used for this study, the selectivity order of
the adsorbents for the adsorption of lead and cadmium ions was coconut shell>groundnut shell.
Again, adsorption decreases with an increased initial concentration of the metal ions. Also,
adsorption increases at higher temperatures thereby suggesting that the adsorption process is
endothermic in nature.
It can therefore be concluded agricultural by-products which are inexpensive, readily available,
and effective metal ion adsorbents can be carbonized, activated, and used effectively as
prepared from coconut shells and groundnut shells for the removal of toxic lead and cadmium
and possibly other metals from the wastewater being discharged into the environment. The
capacity of the prepared activated carbons and their efficiency for the removal of Pb(II) ion and
Cd(II) ion from aqueous solution was found to be adequate and therefore suitable for use in
place of the costly commercial activated carbons.
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