CJES Volume 20 Issue 1 Pages 45-53-2
CJES Volume 20 Issue 1 Pages 45-53-2
INTRODUCTION
Increased wastewater discharge from industries that is polluted with hazardous heavy metals as a result of rapid
industrialization is a worldwide environmental matter (Razak et al. 2020; Rushdi et al. 2020). Toxic heavy metal
ion contamination of water is commonly seen in mining, electroplating, and metal processing industries, as well
as textile and battery manufacturing as heavy metals, such as copper, are released into water streams (Amarasinghe
& Williams 2007; Al-Sharify et al. 2018). Unintended absorption of excessive Cu (II) through copper-
contaminated water presents a multitude of health challenges in humans causing death in extreme cases or
vomiting, nausea, diarrhea and epigastric pain in others. Technologies currently used for the elimination of Cu
(II) from wastewaters are various and include conventional methods such as chemical precipitation (Hutchison
et al. 2008; Al-Qaisi et al. 2018), adsorption (Skinner et al. 2007), biological treatment, and membrane filtration
(Urgun-Demirtas et al. 2012; Al Jaaf et al. 2020). Adsorption is considered one of the more practicable techniques
because of its reproducibility, ease of operation, and sensitivity alongside economic benefits such as effectiveness
and economy. Comparatively, chemical precipitation necessitates a separation procedure, biological methods are
either inefficient or too time-consuming to treat because of the heavy metals and microbial activity inhibition.
Membrane filtration is also expensive. Underutilized resources such as natural materials in huge quantities or
agricultural waste can potentially be employed as inexpensive adsorbents because they are available widely and
are naturally beneficial (Deans & Dixon 1992). Several previous studies have examined the use of inexpensive
natural adsorbents such as waste by-products, agricultural products and carbonaceous substances (Nguyen & Do
2001; Singh et al. 2005; Abdel-Ghani et al. 2007; Lahieb et al. 2020; Almhana et al. 2020; Gadhban et al. 2020)
as possible alternatives to traditional techniques like precipitation. However, using raw wastes from plant as
adsorbents can cause various issues and are becoming a growing concern worldwide (Gallouze et al. 2021).
Increased COD, BOD and TOC levels from soluble organic components and their release often found in materials
from plants such as cellulose, pectin, tannin and lignin (Nakajima & Sakaguchi 1990; Misran et al. 2021) can
Caspian Journal of Environmental Sciences, Vol. 20 No. 1 pp. 45-53 Received: May 23, 2021 Revised: July 24, 2021 Accepted: Oct. 25, 2021
DOI: 10.22124/CJES.2022.5391 © The Author(s)
Publisher: University of Guilan, Iran
46 Removal of Cu (II) from…
deplete oxygen levels in the water, endangering aquatic life. So far, remedies such as treatments with chemicals
of solid adsorbents have been utilized as an approach for enhancing their chemical as well as physical
characteristics alongside boosting their capacity for adsorption to solve such difficulties (Reddy et al. 1997; Feng
et al. 2009; Mohammadi & Fataei 2019; Rzaij et al. 2020; Olasehinde et al. 2020; Amer Alshamri et al. 2021;
Aljeboori et al. 2021; Abdouni et al. 2021). Orange peel (OP) is an inexpensive, readily and abundantly available
agricultural byproduct of the orange juicing business. OP’s chemical makeup consists of limonene, chlorophyll
pigments, lignin, pectin, hemicellulose and cellulose. Numerous studies have examined the use of orange waste
in the preparation of an adsorbent as a precursor material by chemical treatment (Khormaei et al. 2007; Biswas et
al. 2007; Lahieb et al. 2020). This paper discusses and examines the results of an experimental work done on
preparing an adsorbent from OP while elaborating on its adsorption characteristics for copper (II) in aqueous
solutions. In evaluating the benefits of the sorbent material, changes in pH of solution, initial Cu (II)
concentrations, adsorbent doses as well as contact times on the process of adsorption were also explored.
where the quantity of adsorbed adsorbate per unit mass of activated carbon is denoted by qe (mg g-1) while the
adsorbate’s equilibrium concentration is abbreviated as Ce (mg L-1) and qe is the quantity of adsorbate adsorbed
per unit mass of activated carbon (mg g-1). The Langmuir constant and maximum uptake of Cu+2 per unit mass
of adsorbent b (mg g-1), and the Langmuir constant are both linked to the adsorption rate KL (L mg-1) and are
derived using (Ce/qe) vs Ce plots. The equilibrium parameter RL given by equation 2 is one more feature of the
Langmuir isotherm, defining the type of adsorption process that can be either irreversible (RL = 0), favorable (0
< RL < 1), linear (RL = 1) or unfavorable (RL > 1).
The Freundlich isotherm, that is related to the process of adsorption which occurs on surfaces that are
heterogonous (Gallouze et al. 2021), is an isotherm that describes heterogeneity on a surface and the exponential
Naser & Abdul-Hameed
47
distribution of active sites with their energies (Ayawei et al. 2015). The Freundlich isotherm in its non-linear form
is as follow (Fost & Aly 1981; Ruthven 1984):
qe = Kf 〖Ce〗^(1/n) (3)
where Freundlich constants Kf and n are found from the intercept and slope of the ln qe vs ln Ceq plots, with Kf
and n suggesting the adsorption capacity of the adsorbent and the favorableness (n > 1) of the adsorption process,
respectively.
3.2 Effects of pH
The reaction mixture’s initial pH affects the efficiency of metal ion removal (Abia et al. 2003). The effects of
initial pH were evaluated using pH values of 4, 6.5, and 11 for the removal of copper (II) from a solution of 75
mg L-1. For cations sorption, the increased pH brought about an elevated copper (II) uptake. The optimum removal
rate of 99.6% was obtained for a pH value of 6.5, thereafter, the removal efficiency declined as a result of the
competing OH- and copper (II) ions.
150
50
0
0 5 pH 10 15
Fig. 3. Effect of pH on copper (II) removal, dose = 0.5 g L-1, time = 180 min, Cu = 1 mg L-1.
3.3 Effects of adsorbent dose
Effects of adsorbent doses on the removal procedure were examined using varying values of OPAC (0.5, 1, 1.5
and 2 g L-1). It turns out that an elevation in the adsorbent dose, upraises the amount of copper removed. This
elevation can be linked to the large amount of active sites for OPAC that are available as dosage is increased. The
best removal value was obtained when the dose value for OPAC was 1 g L-1. Additional dosage did not lead to
improvement which can be attributed to the overlapping of particles.
102
Removal (%)
100
98
96
94
0 0.5 1 1.5 2 2.5
Dosage (g L-1)
Fig. 4. Effects of doses on copper (II) removal, pH = 6.5, time = 180 min, Cu = 1 mg L-1.
150
Removal (%)
100
50
0
0 100 200 300 400
RPM
Fig. 5. Effect of RPM on copper (II) removal, pH = 6.5, dose = 0.5 g L1, time = 180min, Cu = 1 mg L-1.
Naser & Abdul-Hameed
49
100
Removal (%) 50
0
0 20 40 60 80 100
Fig. 6. Effects of contact time on copper (II) removal, pH = 6.5, dose = 0.5 g L-1, Cu = 1 mg L-1.
150
Removal (%)
100
50
0
0 1 2 3
Initial concentration (mg L-1)
Fig. 7. Effects of initial concentration on removal of copper (II), dose = 0.5 g L-1, time = 180 min, pH = 6.5.
qexp
.(mg
qexp.(mg g-1)
Ce (mg L-1)
Fig. 8. Adsorption isotherms for Cu onto OP waste at 25 ºC.
50 Removal of Cu (II) from…
Table 2. Freundlich and Langmuir isotherm constants for Cu onto OP waste at 25 ºC.
Freundlich Langmuir
kf 1/n R q b R
0.163 6.87 0.895 0.1397 297.2 0.964
Pseudo-first-order
1.555
1.554
1.553
1.552
ln(qe-qt)
1.551
1.55
1.549
1.548
1.547
1.546
0 50 100
Time (min)
Fig. 9a. Experimental data and the fitted linear equations of pseudo 1 st order for Cu+2 adsorption on OPAC.
Pseudo-second-order
1000
900
800
700
600
qt/t
500
400
300
200
100
0
0 50 100
Time (min)
Fig. 9b. Experimental data and the fitted linear equations of pseudo 2 nd order for Cu+2 adsorption on OPAC.
Naser & Abdul-Hameed
51
First-order kinetic
0
0 20 40 60 80 100
-2
ln(Co/Ct)
-4
-6 y = -0.0634x - 0.1001
R² = 0.9651
-8
Time (min)
Fig. 9c. Experimental data and the fitted linear equations of 1st order kinetic for Cu+2 adsorption on OPAC.
Second-order kinetic
300 y = 2.6527x - 44.511
R² = 0.7218
200
1/C
100
0
0 20 40 60 80 100
-100
Time (min)
Fig. 9d. Experimental data and the fitted linear equations of 2nd order kinetics for Cu+2 adsorption on OPAC.
CONCLUSION
OP and chemically modified OP are both effective copper (II) biosorbents as compared to other bio-sorbents
discussed in earlier studies. This work's primary conclusions are as follows:
The uptake of copper (II) increased with a rise in the solution pH. Optimum removal rate of 99.6% was obtained
when pH value was 6.5.
The best removal value is obtained when the adsorbent dose concentration is 1g L-1.
Metal ion removal percent elevates as agitation speed is upraised. Removal rate peaks at 99.63% at 200 RPM,
afterward the removal rate starts to decline.
Metal ions uptake grows from 71.81% to 99.48% as contact time increases from 15 to 90 min. The best contact
time was 60 min.
Adsorption tests were performed at varying initial Cu2+ concentrations in the ranges of 0.5 to 2 mg L-1. The ratio
of ion removal elevates by a decreased initial ion concentration. The highest removal rate achieved was 99.63%
at 1 mg L-1.
Linked to the assumption of chemisorption, the 2nd order model is the rate limiting step. The Langmuir model has
a better fit for Cu+2 adsorption on OPAC (R2 > 0.964) than the Freundlich one. This suggests that adsorption
processes are monolayer adsorption ones. The equilibrium parameter RL suggests that the nature of adsorption is
favorable given 0 < RL < 1.
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