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IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 164
MULTIPLE ADSORPTION OF HEAVY METAL IONS IN AQUEOUS
SOLUTION USING ACTIVATED CARBON FROM NIGERIAN
BAMBOO
Ademiluyi F. T1
, Nze J.C2
1,2
Department of Chemical/Petrochemical Engineering. Faculty of Engineering, Rivers State University of Science and
Technology, Nkpolu, Port Harcourt, Nigeria
E-mail: ademuluyi@yahoo.com
Abstract
Batch adsorption of different heavy metal ions (Nickel, Copper, Zinc, Lead, Cadmium and Chromium) in aqueous solution using
activated carbon from Nigerian bamboo was studied. The bamboo was cut, washed and dried. It was carbonized between 3000
C -
4500
C, and activated at 8000
C using nitric acid. The bulk density, iodine number, Benzene adsorption, methylene adsorption, and
ash content of the activated carbon produced compared well with commercial carbons. Multiple adsorption of these metals in
same aqueous solution using bamboo carbon showed that adsorption capacity is in the order Pb>Cd>Cu>Zn>Ni>Cr which
showed that these metal ions can be adsorbed selectively by Nigerian bamboo activated carbon. The order of adsorption is related
to the maximum adsorption of lead, cadmium, copper on bamboo was found to be in the order of ionic radius of the heavy metals
used. Therefore this study demonstrates that bamboo can serve as a good source of activated carbon with multiple metal ions –
removing potentials and may serve as a better replacement for commercial activated carbons in applications that warrant their
use. However, it will also contribute to the search for less expensive adsorbents and their utilization possibilities for the
elimination of heavy metal ions from industrial waste water.
Key Words: multiple adsorption, heavy metals, Nigerian bamboo, Activated Carbon,
--------------------------------------------------------------------***----------------------------------------------------------------------
1. INTRODUCTION
In recent years, the need for safe and economical methods
for the elimination of heavy metals from refinery waste
waters necessitated research interest towards the production
of low cost commercially available activated carbon. Unlike
organic pollutants, the majority of which are susceptible to
biological degradation, heavy metal ions do not degrade into
harmless end products. Heavy metals such as Chromium,
Cadmium, lead, Copper, Zinc and Nickel often found in
refinery waste waters are carcinogenic or toxic to the
environment (Kocasoy and Sahin, 2007).
The low cost agricultural waste by-products such as
sugarcane bagasse, rice husk, sawdust, coconut husk, oil
palm shell, Neembark, Zeolite-based oil shale ash etc used
for the elimination of heavy metals from waste water have
been investigated by various researchers (Nasim et al., 2004,
Panida and Pisit, 2010, Wei-Wei et al., 2013, Ademiluyi and
Ujile 2013). Most of the previous works reported are on
single, double, and triple metal ion adsorption. Although
other works, carried out by Kermit, et al.,(2005) and
Myroslav et al., (2006), using activated carbon made from
peanut shells and; raw and pretreated clinoptilolite showed
that selective metal ion adsorption of copper, lead,
cadmium, zinc and nickel is possible in same aqueous
solution. Uzun and Guzel (2000) also observed that the rate
of uptake of Cu2+
, Mn2+
, Fe2+
and Ni2+
using three adsorbents
(Chitosan, Agar and a commercial carbon, Merck 2514) are
different and concluded that an adsorbent that adsorb one
adsorbate may not be able to adsorb another adsorbate
effectively . In the work of Bassam et al., (2012), the ad-
sorption capacity of Cd(II), Ni(II), Zn(II) onto geopolymers
decreases with competition in a similar manner to the
adsorption of metal ions onto zeolite. However, the
adsorption of Cu(II) onto geopolymers increases with
competition like adsorption of metal ions onto kaolinite
hence the need to study the multiple adsorption of these
metal ions often found in refinery waste water.
The review from previous works carried out on bamboo
activated carbon showed that equilibrium study on multiple
batch adsorption of different heavy metal ions from aqueous
solution using activated carbon from Nigerian Bamboo is
yet to be investigated for these six metals i.e. Chromium,
Cadmium, lead, Copper, Zinc and Nickel, often found in
refinery waste waters. Therefore, the objectives of this
research is to investigate the multiple and competitive
adsorption of these metals in aqueous solution using
activated carbon from Nigerian Bamboo and develop
empirical models that can be used to predict the sorption
process.
2. MATERIALS AND METHODS
2.1 Materials
The materials used for this study are as follows: Granular
activated carbon produced from Nigerian waste Bamboo,
distilled water, Nitric acid, metal salts of Nickel, Copper,
Zinc, Cadmium, Lead and Chromium, Methylene Blue,
Sodium Thiosulphate and Iodine solution (for
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 165
characterization of carbon). Refinery waste waters collected
after treatment to analyze heavy metal ions presence. Other
equipments and apparatus used for the research are: An
analytical weighing Balance, pyrolyzer with condenser,
Electric burner, Measuring cylinder, Heating mantle,
Desiccators, Crucibles, Funnels and filter paper, Digital
weighing Balance, Mortar and pestle, pH meter, Spatula,
Burette and retort stand, Beakers, conical flasks, stirrer
Muffle finance, Set of sieves (1.18mm, 600m, 300m,
150m, 75m), Cutting machine and oven, Atomic
Absorption Spectrophotometer (AAS).
2.2 Methods
2.2.1 Preparation of Nigerian Bamboo Samples
The Nigerian Bamboo was cut into small sizes of about 2cm
long with a cutting machine. After the cutting, pieces of
bamboo were washed thoroughly with distilled water to
remove all the adherent extraneous matter. The bamboo was
then dried in the oven.
2.2.2 Carbonization Process
2 kg of Bamboo pieces were weighed into a reactor. The
Bamboo was pyrolysed between (300 -450 o
C) in the
absence of air for two hours, 30 minutes (Ademiluyi et al.,
2007). The distillate formed during the pyrolysis was
collected by the receiver connected to a condenser. The
charred material was cooled at room temperature before
discharging it into container.
2.2.3 Chemical Activation
The carbonated material was crushed. The crushed sample
was screened using 1.18mm sieve in order to get a uniform
size of the particle. 100 g of carbonized bamboo was
carefully weighed and put in beaker containing 150cm3
of
Nitric acid. The solution was stirred until the mixture
formed a paste. The paste was allowed to pass through an
oven in order to reduce the moisture content. The crucible
was then transferred into a muffle furnace where it was
heated for 1hour at a temperature of 800 0
C in the absence
of air so as to increase the surface area to volume ratio of the
sample for proper adsorption. After heating, it was cooled at
room temperature and was washed with distilled water until
the pH value was approximately 7, showing no trace of
nitric acid. After washing, the activated carbon was then
dried and the final products are kept in an air tight
containers . The same procedure was repeated using with
different concentrations of Nitric acid (0.025M - 0.5M).
Nitric acid was found to be the best for metal ion adsorption
and so was used as previously reported by Ademiluyi and
David-West, 2012.
2.3 Characterization of Activated Carbon Produced
The characterization of the activated carbon involves the
determination of properties such as bulk density, pore
volume, percentage burnt off, moisture content, ash content,
particle size, benzene adsorption, methylene blue and iodine
number. (Ademiluyi et al.,2007).
2.4 Determination of Adsorption Capacity
Six metal ions (Cd2+
, Ni2+
, Pb2+
, Cr3+
,Cu2+
and Zn2+
) often
found in industrial waste waters especially refineries were
used for this study. Different concentrations of these heavy
metals ions in solution were prepared. Batch adsorption of
the six metal ions onto bamboo activated carbon was carried
out in the same aqueous solution for the different
concentrations of these heavy metals ions in solution i.e.
100ml of the six metal ions in solution : 1g of activated
carbon . each sample was stirred, and adsorption was carried
out for 30, 45, 90, 120, 240 and 990 minutes till
equilibration. After each time interval the sample was
filtered out with filter paper to remove any carbon particles.
This process was repeated for different concentrations of
these heavy metals ions in solution. 5 ml of the resulting
filtrate from each sample was diluted with 50ml of 2 %
nitric acid and metals ions in filtrate after digestion were
analyzed using Atomic Absorption Spectrophotometer
(AAS).
3.5 Metal Uptake
The amount of metal adsorbed per unit weight of adsorbent,
Qe (mg/g), was calculated from equation 1. (Kannan and
Veemaraj, 2009)
Qe =
M
V)C-(C eo
(1)
where;
Co = The initial metal concentration in liquid
phase (mgL-1
)
Ce = The liquid phase metal concentration at
equilibrium (mg L-1
)
V = The volume of metal solution used (L)
M = The mass of adsorbent used (g)
3. RESULTS AND DISCUSSION
3.1 Characterization of Activated Carbon from
Bamboo
The work of Ademiluyi and David-West (2012) on effect of
chemical activation on the adsorption of heavy metals using
activated carbon from waste materials revealed that waste
Bamboo activated with HN03 effectively remove metal ions
from waste streams and in different metal recovery
processes than other activating agent. Hence different
concentration of Nitric acid was initially prepared and used
for activation in this study. Iodine Number is a measure of
micro-porous structures of the activated carbon which shows
the degree of porosity of Bamboo carbon and Benzene
adsorption is a measure of meso-pore content of activated
carbon. The higher the Benzene adsorption capacity, the
higher the degree of adsorption hence these two parameters
were used to determine the best concentration of Nitric acid
to be used for activation. Fig. 1 shows a plot of Iodine
Number and Benzene adsorption capacity of the activated
carbon produced against concentration of activating agent .
The Iodine number of carbon produced was highest at 0.1 M
concentration of Nitric acid. Also Benzene adsorption
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 166
capacity plotted against different concentration of activating
agent in Figure 1, showed that as concentration of the
activating agent used to activate the carbon increased, the
amount of benzene adsorbed also increased to a maximum
value at 0.1 M of Nitric acid. Benzene adsorption capacity
decreased to a minimum value at Nitric acid concentration
of 0.025 M. Hence the activated carbon used for the
adsorption of the heavy metal ions in this study was
activated using 0.1M Nitric acid.
Table 1 shows the characterization of activated carbon of the
Nigerian Bamboo used for the batch adsorption of Nickel,
Copper, Zinc, Lead, Cadmium, and Chromium ions in
solution compared with reference activated carbon.
Moderate bulk density, favours better adsorption and from
Table 1, the bulk density falls within the reference standard.
The Methylene Blue adsorptive capacity which is a measure
of meso-pore content of the activated carbon also falls
within the reference standard. The higher the Iodine
Number, (a measure of activity level and the micro pore
content of the activated carbon; higher number indicates
higher degree of activation) the higher the degree of
adsorption. The ash content obtained after activation,
compares favourably with reference activated carbon.
Adsorption is more favored when ash content is neither too
high nor too low.
0
200
400
600
800
1000
1200
1400
0 0.1 0.2 0.3 0.4 0.5 0.6
concetration of activating agents (M)
IodineNumber
0
20
40
60
80
100
120
140
160
Benzeneadsorptioncapacity(mg/g
Iodine number
Benzene Adsorption
Fig. 4.1 Characterization of Activated Carbon from Bamboo
Showing Benzene adsorption Capacity and Iodine number
using different concentration of Nitric acid.
Table-1 Characterization of Activated Carbon from Bamboo
S/No. Parameters Units Locally made Bamboo activated
carbon
Reference Standards (Activated
Carbon)
1. Bulk Density g/cm3
0.458 0.2-0.6
Long and Criscione (2003)
2. Iodine number g of
Iodine/kg
of carbon
1,160 500-1200
Long and Criscione (2003)
3. Ash content % 3.900 < 8
Melcalf and Eddy (2003)
4. Methylene-Blue adsorptive
capacity
mg/g 941.325 900-1100
Wikipedia (2014)
5. Benzene adsorptive capacity mg/g 148.9 129
Ademiluyi et al. (2007)
3.2 Concentration of Metal ions (mg/l) in Refinery
Waste Water Before and After Adsorption
Compared with WHO Standard.
Refinery waste water used for this research was obtained
after the treatment plant of the refinery and still has a
conductivity of 82 S. Hence the metal ions in the waste
water from the refinery was analyzed before and after
treatment with bamboo activated carbon. In Fig 2, the
concentration of metal ions mg/L was plotted against metal
ions in refinery waste water before and after adsorption
along with the World Health Organization’s (WHO)
standard on the maximum allowable limit of these metal
ions in waste water.
Fig. 2 Concentration of metal ions mg/L in refinery waste
water before and after adsorption and WHO standards.
The concentration of these heavy metal ions was high before
adsorption from the treated refinery waste water as shown in
Figure 2. Lead, Nickel and Cadmium in refinery waste water
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 167
before adsorption was higher than the quantity required by
WHO while the concentrations of Chromium, Copper and
Zinc in refinery waste water before adsorption were below
the concentration required by World Health Organization.
The concentrations of metal ions after adsorption with
bamboo carbon reduced drastically. In fact Copper and
Chromium were adsorbed completely, which shows the
effectiveness of activated carbon from Nigerian Bamboo.
The result was compared with WHO standards as shown in
Fig. 2 and this result also showed that Bamboo activated
carbon adsorb metal ions in same aqueous solution
competitively or selectively. After adsorption with Bamboo
activated carbon, the amount of metal ions available was too
small to study the adsoprtion until equilibrium is reached
because the refinery wastewater was already treated. Hence
metallic salts containing these metal ions were used for the
study.
3.3 Quantity of Adsorbate adsorbed at equilibrium
against equilibrium concentration
Fig. 3 shows the quantity of adsorbate adsorbed at
equilibrium against equilibrium concentration. The quantity
of heavy metal ions adsorbed increased with increase in
concentration of adsorbate. Since the activated carbon used
is a micro porous adsorbent, heavy metals penetrate easily
into these pores as the concentration of these metal ions
increased. The amount adsorbed also increased until the
pores were saturated where the adsorbates can no longer be
adsorbed at the pores. Similar behavior was observed by
Zacaria, et al., (2002) during the study of the adsorption of
several metal ions onto a low-cost biosorbent. As shown in
Fig. 3 high amount of Lead, Cadmium, Copper and were
adsorbed at the same time than Nickel , Zinc, and
Chromium. This is an indication that Bamboo activated
carbon has more affinity for some metals than others.
Fig.3 Quantity of Adsorbate Adsorbed at Equilibrium
against Equilibrium Concentration
It was also observed that the rate of adsorption of Copper
and zinc were close , yet Bamboo activated carbon was
able to adsorb them separately in same aqueous solution.
3.4 Rate of Multiple Adsorption of Heavy Metal
ions using Activated Carbon from Bamboo in
aqueous solutions of Different Concentrations.
Fig. 4 shows the amount of heavy metal ions adsorbed (Qe)
in mg/g of carbon at different adsorption times for the
different metal ions in aqueous solution using 166 mg/L of
each metal ions from the metallic salts in aqueous solution.
The amount of heavy metal ions adsorbed differ for different
metal ions in solution. Each of the heavy metal ions
exhibited some level of desorption before attainment of
equilibrium at about 240 minutes. At the initial stage, the
rate of removal of the metal ions was higher, due to the
availability of more active sites on the surface of the carbon
and became slower at later stages of contact time, due to the
decreased or lesser number of active sites. Similar results
have been reported for the removal of dyes organic acids
and metal ions by (Kannan and Veemaraj, 2009).
Fig.4 Amount of heavy metal ion adsorbed in mg/g of
carbon at different adsorption times for the different metals
ions in aqueous solution (166 mg/L of each metal salt in
aqueous solution).
This is an indication that the multiple adsorption of heavy
metal ions is time dependent. The uptake rate is controlled
by the rate at which the adsorbate is transported from
exterior to the interior sites of the adsorbent particles. Fig 4
also shows how these metal ions are adsorbed selectively at
same time interval. The amount of metal ions adsorbed also
differs though the metallic salts added before adsorption
was the same. Using same concentration of adsorbate, Lead,
Cadmium and Copper are more adsorbed than Zinc, Nickel
and Chromiumi.e. Pb>Cd>Cu>Zn>Ni>Cr. This shows that
Bamboo can be employed effectively in batch adsorption of
different heavy metal ions in aqueous solution.
The work of Ingmar (2010) on hydrated metal ions in
aqueous solution shows that the M–O bonds are mainly of
electrostatic character, the coordination number of the
hydrated metal ions is expected to be determined by the
ratio of the ionic radius of the metal ion and the radius of the
water oxygen atom ; the size of the water oxygen atom at
coordination to metal ions has been determined to be 1.34
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 168
Å. It is therefore expected that metal ions with an ionic
radius smaller than
0.55 Å is expected to be tetrahedral, metal ions with an
ionic radius in the range 0.55–0.98 Å are expected to be
octahedral, while metal ions with an ionic radius larger than
0.98 Å are expected to be eight-coordinate or have an even
higher coordination number. This principle can be used to
explain why Lead and Cadmium ions were more adsorbed
by Bamboo activated carbon than other metals.
Table 2. Overview of Mean Bond Distance, Ionic Radius, of the Hydrated Metal Ions Adsorbed.
S/No Aqua complex
of metal ions
adsorbed
M–O distance* Ionic Radius
/Å*
Amount of metal ions in 166mg of
metallic salt/ liter of aqueous solution
before adsorption (mg/L) from present
study
1 Pb(H2O)2+
6 2.54 1.19 124.17
2 Cd(H2O)2+
6 2.30 0.95 89.83
3 Cu(H2O)2+
6 1.96-2.28 0.73 78.83
4 Zn(H2O)2+
6 2.08 0.74 67.50
5 Ni(H2O)2+
6 2.055 0.69 63.16
6 Cr(H2O)3+
6 1.96 0.615 54.66
*Ingumar (2010) where M-O is metal ions mean bond distance and O- oxygen in water
As reported by Ingmar (2010), the expected coordination
figure for four-coordination is therefore the tetrahedron, for
six-coordination the octahedron, for eight-coordination the
square anti - prism and for nine-coordination the tricapped
trigonal prism in which these metals ions used in theses
display in solution as shown in Figure 4. The porous nature
of Bamboo carbon make it easy for these competitive
adsorption and the structure of these metal ions in solution
makes bonding of these metals to the pores of bamboo
carbon easier.
Fig 5. Basic models for tetrahedron, octahedron, square
antiprism, and tricapped trigonal prism.
The work of Chen et al., (2010) while studying the
adsorption of aqueous Cd2+
, Pb2+
, Cu2+
ions by nano-
hydroxyapatite also similarly reported that the sorption
affinity of nano-HAP for Pb(II) is always higher than that
for Cu(II) and for Cd(II); the sorption maxima for the Cd,
Pb and Cu follow the order Pb2+
> Cu2+
> Cd2+
, which they
reported could be inversely proportional to the hydrated
ionic radii as Pb2+
(4.01 Å) > Cu2+
(4.19 Å) > Cd2+
(4.26 Å).
The amount of activated carbon adsorbed also increased
with time until equilibrium was attained when higher
metallic ion concentration of 500 mg/L of each metals salts
in solution was used for adsorption and also more surface
sites were covered as shown in Fig 6. It was observed that
heavy metal ions are being adsorbed according to this order
Pb>Cd>Cu>Zn>Ni>Cr. According to this order, chromium
(Cr) was the least adsorbed and Pb was the most adsorbed,
because the heavy metal whose complex is stable will be
present in the complex at higher levels and this will cause
the complex to be adsorbed more (Uzun & Guzel 2000). The
capacities of the adsorbent get exhausted due to non-
availability of active surface sites. It was also observed from
Fig 6, that the amount of metal ions adsorbed, rapidly
reached equilibrium from 120min before it became stable.
Using higher concentration of adsorbate, (500 mg/L) there
exist closeness in the amount of Copper and Cadmium
adsorbed as well as the amount of Chromium and Nickel
adsorbed. This difference can be attributed to the stability of
these metallic complexes at higher concentration as
compared with what happened at lower concentration in Fig.
4.
Fig. 6 shows the amount of metal ions adsorbed in mg/g of
carbon at different adsorption times for the different metal
ions in aqueous solution (500 mg/L of each metal salt in
aqueous solution).
IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
_______________________________________________________________________________________
Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 169
4. CONCLUSION
Multiple batch adsorption of different heavy metal ions in
aqueous solution using activated carbon from Nigerian
Bamboo has been investigated. The results obtained from
equilibrium study on batch adsorption of these heavy metal
ions showed that Bamboo activated carbon can effectively
be adopted in multiple adsorption of these heavy metal ions
when present in waste water. An increase in contact time
resulted in increase in the quantity of metal ions adsorbed
till equilibrium was reached . It can also be seen that heavy
metal ions are adsorbed in the following affinity order of
adsorption Pb>Cd>Cu>Zn>Ni>Cr. Lead ions was the most
adsorbed and Nickel ions the least adsorbed in the same
aqueous solution. The order of adsorption is related to the
maximum adsorption of lead, cadmium, copper on bamboo
was found to be in the order of ionic radius of the heavy
metals used. The high multiple adsorption intensity of
activated carbon from Bamboo and its high affinity for
metal ions of Nickel, Copper, Zinc, Lead, Cadmium, and
Chromium can help resolve many adsorption challenges in
the industry and in water purification processes. This
research work on multiple adsorption of different heavy
metal ions in an aqueous solution using activated carbon
from Nigerian Bamboo has also contributed to the search for
less expensive and easily available material for adsorption
and separation process.
REFERENCES
[1] Ademiluyi, F. T. & David-West, E. O. (2012). Effect of
Chemical Activation on the Adsorption of Heavy
Metals using Activated Carbons from Waste Materials,
ISRN Chemical Engineering: Retrieved from
http://www.hindawi.com/isrn/
Chemeng/2012/674209/[Accessed 8th
June 2013].
[2] Ademiluyi, T., Gumus, R., Adeniji S. M., & Jasem, O.
T. (2007). Effect of Process Condition on the
Characterization of Activated Carbon from Waste
Nigerian Bamboo. Journal of Nigerian Society of
Chemical Engineers. 24, (1-2), 83-94.
[3] Ademiluyi F. T & Nze J.C (2015) Multiple
Adsorption of Heavy Metal Ions in Aqueous Solution
Using Activated Carbon from Nigerian Bamboo. The
Thirtieth International Conference on Solid Waste
Technology And Management. Philadelphia, PA U.S.A.
March 15-18
[4] Ademiluyi, F.T., & Ujile, A . A., (2013). Kinetics of
Batch Adsorption of Iron 11 Ions from Aqueous
Solution Using Activated Carbon from Nigerian
Bamboo. International Journal of Engineering and
Technology 3 (6) 2849-3444.
[5] Bassam El-Eswed, Mazen Alshaaer, Rushdi
IbrahimYousef, Imad Hamadneh, & Fawwaz Khalili
(2012) Adsorption of Cu(II), Ni(II), Zn(II), Cd(II) and
Pb(II) onto Kaolin/Zeolite Based- Geopolymers,
Advances in Materials Physics and Chemistry, 2, 119-
125
[6] Chen S. B., Ma Y. B., L. Chen . L & Xian .K (2010)
Adsorption of aqueous Cd2+, Pb2+, Cu2+ ions
by nano-hydroxyapatite: Single- and multi-metal
competitive adsorption study, Geochemical Journal,
44, 233 -239
[7] Ingmar Persson (2010) Hydrated metal ions in aqueous
solution: How regular are their structures? Pure
Applied. Chemistry, 82, 10, 1901–1917
[8] Kannan, N. & Veemaraj, T. (2009). Removal of Lead
(II) Ions by Adsorption Onto Bamboo Dust and
Commercial Activated Carbons. E-Journal of
Chemistry 6(2), 247-256.
[9] Kermit,W., Hong, Y.,Chung W.S & Wayne, E. M.
(2006). Select Metal Adsorption by Activated Carbon
Made from Peanut Shells: Bio Resources Technology
97, 2266-2270.
[10]Kocasoy, G. & Sahin, V. (2007). Heavy Metal Removal
from Industrial Wastewater by Clinoptilolite. Journal
Environmental Science and Health Part A. 42, 2139-
2146.
[11]Long, J. C. & Criscione, J. M. (2003). Activated
Carbon and its Properties, Chemical Encyclopedia
4,741-757.
[12]Metcalf & Eddy (2003). Wastewater Engineering
Treatment and Re-use.6th
Edition John Wiley.
[13]Myroslav .S., Boguslaw . B., Artur .P.T., & Jacek .N.,
(2006) Study of the selection mechanism of heavy
metals (Pb2+
, Cu2+
, Ni2+
, and Cd2+
) adsorption on
clinoptilolite Journal of Colloid and Interface Science
304 (1) , 21-28
[14]Nasim, A.K., Shaliza, I., & Piarapakaram, S. (2004).
Elimination of Heavy Metals from Wastewater Using
Agricultural Wastes as Adsorbent. Malaysian Journal
of Science 23, 43-51.
[15]Panida, S. & Pisit, C. (2010). Equilibrium Isotherm
Thermodynamic and Kinetic Studies of Lead
Adsorption onto Pineapple and Paper waste Sludges.
International Journal of Energy and Environment. 3(4)
88-97.
[16]Uzun, . I. & Guzel, . F. (2000) Adsorption of some
metal ions from aqueous solution by activated carbon
and comparison of percentage adsorption results of
activated carbon with those of some other adsorbents
Turkey Journal of chemistry 24, 291-297.
[17]Wei-wei, B., Hai-feng, Z., Shu-cai, G., Xue-chun, X.,
Gui, J., & Keyan, G. (2013). Kinetic and Equilibrium
Studies on the Adsorption of Heavy Metal ions from
Aqueous Solution by Zeolite Based Oil Shale Ash.
Journal of Chemical Research 29 (126-131)
[18]Wikipedia (2014) Activated Carbon- Retrieved from:
http://en.wikipedia.org/wiki/activated [Accessed 28th
July, 2014].
[19]Zacaria, R., Claire, G., Yves A. & Pierrele, C. (2002).
Adsorption of Several Metal Ions Onto a Low-cost
Biosorbent . Journal of Environmental Science, 36(9),
2067-2073.

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Multiple adsorption of heavy metal ions in aqueous solution using activated carbon from nigerian bamboo

  • 1. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 164 MULTIPLE ADSORPTION OF HEAVY METAL IONS IN AQUEOUS SOLUTION USING ACTIVATED CARBON FROM NIGERIAN BAMBOO Ademiluyi F. T1 , Nze J.C2 1,2 Department of Chemical/Petrochemical Engineering. Faculty of Engineering, Rivers State University of Science and Technology, Nkpolu, Port Harcourt, Nigeria E-mail: ademuluyi@yahoo.com Abstract Batch adsorption of different heavy metal ions (Nickel, Copper, Zinc, Lead, Cadmium and Chromium) in aqueous solution using activated carbon from Nigerian bamboo was studied. The bamboo was cut, washed and dried. It was carbonized between 3000 C - 4500 C, and activated at 8000 C using nitric acid. The bulk density, iodine number, Benzene adsorption, methylene adsorption, and ash content of the activated carbon produced compared well with commercial carbons. Multiple adsorption of these metals in same aqueous solution using bamboo carbon showed that adsorption capacity is in the order Pb>Cd>Cu>Zn>Ni>Cr which showed that these metal ions can be adsorbed selectively by Nigerian bamboo activated carbon. The order of adsorption is related to the maximum adsorption of lead, cadmium, copper on bamboo was found to be in the order of ionic radius of the heavy metals used. Therefore this study demonstrates that bamboo can serve as a good source of activated carbon with multiple metal ions – removing potentials and may serve as a better replacement for commercial activated carbons in applications that warrant their use. However, it will also contribute to the search for less expensive adsorbents and their utilization possibilities for the elimination of heavy metal ions from industrial waste water. Key Words: multiple adsorption, heavy metals, Nigerian bamboo, Activated Carbon, --------------------------------------------------------------------***---------------------------------------------------------------------- 1. INTRODUCTION In recent years, the need for safe and economical methods for the elimination of heavy metals from refinery waste waters necessitated research interest towards the production of low cost commercially available activated carbon. Unlike organic pollutants, the majority of which are susceptible to biological degradation, heavy metal ions do not degrade into harmless end products. Heavy metals such as Chromium, Cadmium, lead, Copper, Zinc and Nickel often found in refinery waste waters are carcinogenic or toxic to the environment (Kocasoy and Sahin, 2007). The low cost agricultural waste by-products such as sugarcane bagasse, rice husk, sawdust, coconut husk, oil palm shell, Neembark, Zeolite-based oil shale ash etc used for the elimination of heavy metals from waste water have been investigated by various researchers (Nasim et al., 2004, Panida and Pisit, 2010, Wei-Wei et al., 2013, Ademiluyi and Ujile 2013). Most of the previous works reported are on single, double, and triple metal ion adsorption. Although other works, carried out by Kermit, et al.,(2005) and Myroslav et al., (2006), using activated carbon made from peanut shells and; raw and pretreated clinoptilolite showed that selective metal ion adsorption of copper, lead, cadmium, zinc and nickel is possible in same aqueous solution. Uzun and Guzel (2000) also observed that the rate of uptake of Cu2+ , Mn2+ , Fe2+ and Ni2+ using three adsorbents (Chitosan, Agar and a commercial carbon, Merck 2514) are different and concluded that an adsorbent that adsorb one adsorbate may not be able to adsorb another adsorbate effectively . In the work of Bassam et al., (2012), the ad- sorption capacity of Cd(II), Ni(II), Zn(II) onto geopolymers decreases with competition in a similar manner to the adsorption of metal ions onto zeolite. However, the adsorption of Cu(II) onto geopolymers increases with competition like adsorption of metal ions onto kaolinite hence the need to study the multiple adsorption of these metal ions often found in refinery waste water. The review from previous works carried out on bamboo activated carbon showed that equilibrium study on multiple batch adsorption of different heavy metal ions from aqueous solution using activated carbon from Nigerian Bamboo is yet to be investigated for these six metals i.e. Chromium, Cadmium, lead, Copper, Zinc and Nickel, often found in refinery waste waters. Therefore, the objectives of this research is to investigate the multiple and competitive adsorption of these metals in aqueous solution using activated carbon from Nigerian Bamboo and develop empirical models that can be used to predict the sorption process. 2. MATERIALS AND METHODS 2.1 Materials The materials used for this study are as follows: Granular activated carbon produced from Nigerian waste Bamboo, distilled water, Nitric acid, metal salts of Nickel, Copper, Zinc, Cadmium, Lead and Chromium, Methylene Blue, Sodium Thiosulphate and Iodine solution (for
  • 2. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 165 characterization of carbon). Refinery waste waters collected after treatment to analyze heavy metal ions presence. Other equipments and apparatus used for the research are: An analytical weighing Balance, pyrolyzer with condenser, Electric burner, Measuring cylinder, Heating mantle, Desiccators, Crucibles, Funnels and filter paper, Digital weighing Balance, Mortar and pestle, pH meter, Spatula, Burette and retort stand, Beakers, conical flasks, stirrer Muffle finance, Set of sieves (1.18mm, 600m, 300m, 150m, 75m), Cutting machine and oven, Atomic Absorption Spectrophotometer (AAS). 2.2 Methods 2.2.1 Preparation of Nigerian Bamboo Samples The Nigerian Bamboo was cut into small sizes of about 2cm long with a cutting machine. After the cutting, pieces of bamboo were washed thoroughly with distilled water to remove all the adherent extraneous matter. The bamboo was then dried in the oven. 2.2.2 Carbonization Process 2 kg of Bamboo pieces were weighed into a reactor. The Bamboo was pyrolysed between (300 -450 o C) in the absence of air for two hours, 30 minutes (Ademiluyi et al., 2007). The distillate formed during the pyrolysis was collected by the receiver connected to a condenser. The charred material was cooled at room temperature before discharging it into container. 2.2.3 Chemical Activation The carbonated material was crushed. The crushed sample was screened using 1.18mm sieve in order to get a uniform size of the particle. 100 g of carbonized bamboo was carefully weighed and put in beaker containing 150cm3 of Nitric acid. The solution was stirred until the mixture formed a paste. The paste was allowed to pass through an oven in order to reduce the moisture content. The crucible was then transferred into a muffle furnace where it was heated for 1hour at a temperature of 800 0 C in the absence of air so as to increase the surface area to volume ratio of the sample for proper adsorption. After heating, it was cooled at room temperature and was washed with distilled water until the pH value was approximately 7, showing no trace of nitric acid. After washing, the activated carbon was then dried and the final products are kept in an air tight containers . The same procedure was repeated using with different concentrations of Nitric acid (0.025M - 0.5M). Nitric acid was found to be the best for metal ion adsorption and so was used as previously reported by Ademiluyi and David-West, 2012. 2.3 Characterization of Activated Carbon Produced The characterization of the activated carbon involves the determination of properties such as bulk density, pore volume, percentage burnt off, moisture content, ash content, particle size, benzene adsorption, methylene blue and iodine number. (Ademiluyi et al.,2007). 2.4 Determination of Adsorption Capacity Six metal ions (Cd2+ , Ni2+ , Pb2+ , Cr3+ ,Cu2+ and Zn2+ ) often found in industrial waste waters especially refineries were used for this study. Different concentrations of these heavy metals ions in solution were prepared. Batch adsorption of the six metal ions onto bamboo activated carbon was carried out in the same aqueous solution for the different concentrations of these heavy metals ions in solution i.e. 100ml of the six metal ions in solution : 1g of activated carbon . each sample was stirred, and adsorption was carried out for 30, 45, 90, 120, 240 and 990 minutes till equilibration. After each time interval the sample was filtered out with filter paper to remove any carbon particles. This process was repeated for different concentrations of these heavy metals ions in solution. 5 ml of the resulting filtrate from each sample was diluted with 50ml of 2 % nitric acid and metals ions in filtrate after digestion were analyzed using Atomic Absorption Spectrophotometer (AAS). 3.5 Metal Uptake The amount of metal adsorbed per unit weight of adsorbent, Qe (mg/g), was calculated from equation 1. (Kannan and Veemaraj, 2009) Qe = M V)C-(C eo (1) where; Co = The initial metal concentration in liquid phase (mgL-1 ) Ce = The liquid phase metal concentration at equilibrium (mg L-1 ) V = The volume of metal solution used (L) M = The mass of adsorbent used (g) 3. RESULTS AND DISCUSSION 3.1 Characterization of Activated Carbon from Bamboo The work of Ademiluyi and David-West (2012) on effect of chemical activation on the adsorption of heavy metals using activated carbon from waste materials revealed that waste Bamboo activated with HN03 effectively remove metal ions from waste streams and in different metal recovery processes than other activating agent. Hence different concentration of Nitric acid was initially prepared and used for activation in this study. Iodine Number is a measure of micro-porous structures of the activated carbon which shows the degree of porosity of Bamboo carbon and Benzene adsorption is a measure of meso-pore content of activated carbon. The higher the Benzene adsorption capacity, the higher the degree of adsorption hence these two parameters were used to determine the best concentration of Nitric acid to be used for activation. Fig. 1 shows a plot of Iodine Number and Benzene adsorption capacity of the activated carbon produced against concentration of activating agent . The Iodine number of carbon produced was highest at 0.1 M concentration of Nitric acid. Also Benzene adsorption
  • 3. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 166 capacity plotted against different concentration of activating agent in Figure 1, showed that as concentration of the activating agent used to activate the carbon increased, the amount of benzene adsorbed also increased to a maximum value at 0.1 M of Nitric acid. Benzene adsorption capacity decreased to a minimum value at Nitric acid concentration of 0.025 M. Hence the activated carbon used for the adsorption of the heavy metal ions in this study was activated using 0.1M Nitric acid. Table 1 shows the characterization of activated carbon of the Nigerian Bamboo used for the batch adsorption of Nickel, Copper, Zinc, Lead, Cadmium, and Chromium ions in solution compared with reference activated carbon. Moderate bulk density, favours better adsorption and from Table 1, the bulk density falls within the reference standard. The Methylene Blue adsorptive capacity which is a measure of meso-pore content of the activated carbon also falls within the reference standard. The higher the Iodine Number, (a measure of activity level and the micro pore content of the activated carbon; higher number indicates higher degree of activation) the higher the degree of adsorption. The ash content obtained after activation, compares favourably with reference activated carbon. Adsorption is more favored when ash content is neither too high nor too low. 0 200 400 600 800 1000 1200 1400 0 0.1 0.2 0.3 0.4 0.5 0.6 concetration of activating agents (M) IodineNumber 0 20 40 60 80 100 120 140 160 Benzeneadsorptioncapacity(mg/g Iodine number Benzene Adsorption Fig. 4.1 Characterization of Activated Carbon from Bamboo Showing Benzene adsorption Capacity and Iodine number using different concentration of Nitric acid. Table-1 Characterization of Activated Carbon from Bamboo S/No. Parameters Units Locally made Bamboo activated carbon Reference Standards (Activated Carbon) 1. Bulk Density g/cm3 0.458 0.2-0.6 Long and Criscione (2003) 2. Iodine number g of Iodine/kg of carbon 1,160 500-1200 Long and Criscione (2003) 3. Ash content % 3.900 < 8 Melcalf and Eddy (2003) 4. Methylene-Blue adsorptive capacity mg/g 941.325 900-1100 Wikipedia (2014) 5. Benzene adsorptive capacity mg/g 148.9 129 Ademiluyi et al. (2007) 3.2 Concentration of Metal ions (mg/l) in Refinery Waste Water Before and After Adsorption Compared with WHO Standard. Refinery waste water used for this research was obtained after the treatment plant of the refinery and still has a conductivity of 82 S. Hence the metal ions in the waste water from the refinery was analyzed before and after treatment with bamboo activated carbon. In Fig 2, the concentration of metal ions mg/L was plotted against metal ions in refinery waste water before and after adsorption along with the World Health Organization’s (WHO) standard on the maximum allowable limit of these metal ions in waste water. Fig. 2 Concentration of metal ions mg/L in refinery waste water before and after adsorption and WHO standards. The concentration of these heavy metal ions was high before adsorption from the treated refinery waste water as shown in Figure 2. Lead, Nickel and Cadmium in refinery waste water
  • 4. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 167 before adsorption was higher than the quantity required by WHO while the concentrations of Chromium, Copper and Zinc in refinery waste water before adsorption were below the concentration required by World Health Organization. The concentrations of metal ions after adsorption with bamboo carbon reduced drastically. In fact Copper and Chromium were adsorbed completely, which shows the effectiveness of activated carbon from Nigerian Bamboo. The result was compared with WHO standards as shown in Fig. 2 and this result also showed that Bamboo activated carbon adsorb metal ions in same aqueous solution competitively or selectively. After adsorption with Bamboo activated carbon, the amount of metal ions available was too small to study the adsoprtion until equilibrium is reached because the refinery wastewater was already treated. Hence metallic salts containing these metal ions were used for the study. 3.3 Quantity of Adsorbate adsorbed at equilibrium against equilibrium concentration Fig. 3 shows the quantity of adsorbate adsorbed at equilibrium against equilibrium concentration. The quantity of heavy metal ions adsorbed increased with increase in concentration of adsorbate. Since the activated carbon used is a micro porous adsorbent, heavy metals penetrate easily into these pores as the concentration of these metal ions increased. The amount adsorbed also increased until the pores were saturated where the adsorbates can no longer be adsorbed at the pores. Similar behavior was observed by Zacaria, et al., (2002) during the study of the adsorption of several metal ions onto a low-cost biosorbent. As shown in Fig. 3 high amount of Lead, Cadmium, Copper and were adsorbed at the same time than Nickel , Zinc, and Chromium. This is an indication that Bamboo activated carbon has more affinity for some metals than others. Fig.3 Quantity of Adsorbate Adsorbed at Equilibrium against Equilibrium Concentration It was also observed that the rate of adsorption of Copper and zinc were close , yet Bamboo activated carbon was able to adsorb them separately in same aqueous solution. 3.4 Rate of Multiple Adsorption of Heavy Metal ions using Activated Carbon from Bamboo in aqueous solutions of Different Concentrations. Fig. 4 shows the amount of heavy metal ions adsorbed (Qe) in mg/g of carbon at different adsorption times for the different metal ions in aqueous solution using 166 mg/L of each metal ions from the metallic salts in aqueous solution. The amount of heavy metal ions adsorbed differ for different metal ions in solution. Each of the heavy metal ions exhibited some level of desorption before attainment of equilibrium at about 240 minutes. At the initial stage, the rate of removal of the metal ions was higher, due to the availability of more active sites on the surface of the carbon and became slower at later stages of contact time, due to the decreased or lesser number of active sites. Similar results have been reported for the removal of dyes organic acids and metal ions by (Kannan and Veemaraj, 2009). Fig.4 Amount of heavy metal ion adsorbed in mg/g of carbon at different adsorption times for the different metals ions in aqueous solution (166 mg/L of each metal salt in aqueous solution). This is an indication that the multiple adsorption of heavy metal ions is time dependent. The uptake rate is controlled by the rate at which the adsorbate is transported from exterior to the interior sites of the adsorbent particles. Fig 4 also shows how these metal ions are adsorbed selectively at same time interval. The amount of metal ions adsorbed also differs though the metallic salts added before adsorption was the same. Using same concentration of adsorbate, Lead, Cadmium and Copper are more adsorbed than Zinc, Nickel and Chromiumi.e. Pb>Cd>Cu>Zn>Ni>Cr. This shows that Bamboo can be employed effectively in batch adsorption of different heavy metal ions in aqueous solution. The work of Ingmar (2010) on hydrated metal ions in aqueous solution shows that the M–O bonds are mainly of electrostatic character, the coordination number of the hydrated metal ions is expected to be determined by the ratio of the ionic radius of the metal ion and the radius of the water oxygen atom ; the size of the water oxygen atom at coordination to metal ions has been determined to be 1.34
  • 5. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 168 Å. It is therefore expected that metal ions with an ionic radius smaller than 0.55 Å is expected to be tetrahedral, metal ions with an ionic radius in the range 0.55–0.98 Å are expected to be octahedral, while metal ions with an ionic radius larger than 0.98 Å are expected to be eight-coordinate or have an even higher coordination number. This principle can be used to explain why Lead and Cadmium ions were more adsorbed by Bamboo activated carbon than other metals. Table 2. Overview of Mean Bond Distance, Ionic Radius, of the Hydrated Metal Ions Adsorbed. S/No Aqua complex of metal ions adsorbed M–O distance* Ionic Radius /Å* Amount of metal ions in 166mg of metallic salt/ liter of aqueous solution before adsorption (mg/L) from present study 1 Pb(H2O)2+ 6 2.54 1.19 124.17 2 Cd(H2O)2+ 6 2.30 0.95 89.83 3 Cu(H2O)2+ 6 1.96-2.28 0.73 78.83 4 Zn(H2O)2+ 6 2.08 0.74 67.50 5 Ni(H2O)2+ 6 2.055 0.69 63.16 6 Cr(H2O)3+ 6 1.96 0.615 54.66 *Ingumar (2010) where M-O is metal ions mean bond distance and O- oxygen in water As reported by Ingmar (2010), the expected coordination figure for four-coordination is therefore the tetrahedron, for six-coordination the octahedron, for eight-coordination the square anti - prism and for nine-coordination the tricapped trigonal prism in which these metals ions used in theses display in solution as shown in Figure 4. The porous nature of Bamboo carbon make it easy for these competitive adsorption and the structure of these metal ions in solution makes bonding of these metals to the pores of bamboo carbon easier. Fig 5. Basic models for tetrahedron, octahedron, square antiprism, and tricapped trigonal prism. The work of Chen et al., (2010) while studying the adsorption of aqueous Cd2+ , Pb2+ , Cu2+ ions by nano- hydroxyapatite also similarly reported that the sorption affinity of nano-HAP for Pb(II) is always higher than that for Cu(II) and for Cd(II); the sorption maxima for the Cd, Pb and Cu follow the order Pb2+ > Cu2+ > Cd2+ , which they reported could be inversely proportional to the hydrated ionic radii as Pb2+ (4.01 Å) > Cu2+ (4.19 Å) > Cd2+ (4.26 Å). The amount of activated carbon adsorbed also increased with time until equilibrium was attained when higher metallic ion concentration of 500 mg/L of each metals salts in solution was used for adsorption and also more surface sites were covered as shown in Fig 6. It was observed that heavy metal ions are being adsorbed according to this order Pb>Cd>Cu>Zn>Ni>Cr. According to this order, chromium (Cr) was the least adsorbed and Pb was the most adsorbed, because the heavy metal whose complex is stable will be present in the complex at higher levels and this will cause the complex to be adsorbed more (Uzun & Guzel 2000). The capacities of the adsorbent get exhausted due to non- availability of active surface sites. It was also observed from Fig 6, that the amount of metal ions adsorbed, rapidly reached equilibrium from 120min before it became stable. Using higher concentration of adsorbate, (500 mg/L) there exist closeness in the amount of Copper and Cadmium adsorbed as well as the amount of Chromium and Nickel adsorbed. This difference can be attributed to the stability of these metallic complexes at higher concentration as compared with what happened at lower concentration in Fig. 4. Fig. 6 shows the amount of metal ions adsorbed in mg/g of carbon at different adsorption times for the different metal ions in aqueous solution (500 mg/L of each metal salt in aqueous solution).
  • 6. IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308 _______________________________________________________________________________________ Volume: 05 Issue: 01 | Jan-2016, Available @ http://www.ijret.org 169 4. CONCLUSION Multiple batch adsorption of different heavy metal ions in aqueous solution using activated carbon from Nigerian Bamboo has been investigated. The results obtained from equilibrium study on batch adsorption of these heavy metal ions showed that Bamboo activated carbon can effectively be adopted in multiple adsorption of these heavy metal ions when present in waste water. An increase in contact time resulted in increase in the quantity of metal ions adsorbed till equilibrium was reached . It can also be seen that heavy metal ions are adsorbed in the following affinity order of adsorption Pb>Cd>Cu>Zn>Ni>Cr. Lead ions was the most adsorbed and Nickel ions the least adsorbed in the same aqueous solution. The order of adsorption is related to the maximum adsorption of lead, cadmium, copper on bamboo was found to be in the order of ionic radius of the heavy metals used. The high multiple adsorption intensity of activated carbon from Bamboo and its high affinity for metal ions of Nickel, Copper, Zinc, Lead, Cadmium, and Chromium can help resolve many adsorption challenges in the industry and in water purification processes. This research work on multiple adsorption of different heavy metal ions in an aqueous solution using activated carbon from Nigerian Bamboo has also contributed to the search for less expensive and easily available material for adsorption and separation process. REFERENCES [1] Ademiluyi, F. T. & David-West, E. O. (2012). Effect of Chemical Activation on the Adsorption of Heavy Metals using Activated Carbons from Waste Materials, ISRN Chemical Engineering: Retrieved from http://www.hindawi.com/isrn/ Chemeng/2012/674209/[Accessed 8th June 2013]. 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