Accepted Manuscript

Title: Adsorption of cyanide from aqueous solution using

calcinated eggshells: Equilibrium and optimisation studies

Author: O.A.A. Eletta O.A. Ajayi O.O. Ogunleye I.C. Akpan

PII: S2213-3437(16)30020-3
DOI: http://dx.doi.org/doi:10.1016/j.jece.2016.01.020
Reference: JECE 943

To appear in:

Received date: 23-6-2015

Revised date: 13-1-2016
Accepted date: 15-1-2016

Please cite this article as: O.A.A.Eletta, O.A.Ajayi, O.O.Ogunleye, I.C.Akpan,

Adsorption of cyanide from aqueous solution using calcinated eggshells:
Equilibrium and optimisation studies, Journal of Environmental Chemical Engineering
http://dx.doi.org/10.1016/j.jece.2016.01.020

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Adsorption of Cyanide from Aqueous Solution Using Calcinated Eggshells:
Equilibrium and Optimisation Studies

O.A.A. Eletta1, O.A. Ajayi2* modeletta@unilorin.edu.ng, O.O. Ogunleye3, I.C. Akpan1

1
Department of Chemical Engineering, University of Ilorin, Ilorin. Nigeria.
2
Department of Chemical Engineering, Ahmadu Bello University, Zaria. Nigeria.
3
Department of Chemical Engineering, Ladoke Akintola University of Technology,
Ogbomoso. Nigeria

*Corresponding author. Tel.: +2348035817674.

1
Abstract
Eggshells were calcined and used to adsorb cyanide from its aqueous solution. X –
Ray diffraction (XRD), X – Ray fluorescence (XRF), Fourier Transform Infra-red
(FTIR) and Scanning Electron Microscope (SEM) were used to characterize both
raw and calcined eggshell (CE) while UV spectrophotometer was used to monitor
the cyanide concentration. The XRD and FTIR showed the conversion of CaCO3 to
CaO. Batch adsorption experiments were carried out using 10 ml each of 0.01
mol/L to 0.05 mol/L cyanide solutions at different contact times, and adsorbent
dosages. To establish optimum adsorption conditions, Central Composite Design
(CCD) in Response Surface Methodology (RSM) was employed using the time,
concentration and adsorbent dosages as variables at a fixed pH of 7. Adsorption
efficiency of 84.53 % was obtained with 0.01 mol/L, 8.98 g of calcined eggshell at
26.58 min contact time using RSM. Pseudo second order kinetic model best fitted
the experiment. The coefficients of determination of Langmuir and Freundlich
isotherms were 0.988 and 0.650 respectively, with Langmuir isotherm giving a
better fit for the adsorption. The maximum monolayer adsorption capacity from
Langmuir isotherm was 3.27 mg/g at pH 7 and a temperature of 30

Keywords: cyanide; eggshell; cassava; adsorption isotherm.

2
Introduction
Wastes are generated in every facet of life including the industrial activities of man
[1]. Wastes emanating from local food processing industries are becoming
challenging, especially in developing countries where such activities are
encouraged to alleviate poverty and provide food for the populace. The disposal of
the wastes has followed varied routes from proper disposal to designated landfills
and incinerators to indiscriminate disposal on streets, drainages and water bodies.
Cassava (manihot esculenta crantz) is a very important food crop in tropical
countries and it is one of the most widely distributed food crops having high
content of cyanogenic glucosides [2]. According to Food and Agriculture
Organization of the United Nations
[3], cassava production in Nigeria is the largest in the World; it is a third more
than the production in Brazil; it doubles that of Thailand and Indonesia and it feeds
about 200 million people. Cassava is often processed into wet chips, cassava
noodles, cassava flour, garri and fufu, in order to preserve, reduce its toxicity and
add value to its derivable products. The poisonous chemical substance present in
high deadly concentration in raw cassava tuber is hydrocyanic acid or cyanide. The
process of cassava generates not only solid but, liquid wastes which could be
hazardous to the environment [4, 5].
Cyanide in wastewaters can be treated using physical, chemical and
biological methods either separately or simultaneously. These approaches include,
anodic oxidation, electrical attenuation, biodegradation, adsorption, among others.
Of all these, adsorption is the most versatile and widely used method for the
removal of these pollutants due to its high removal capacity, ease and cost of
operation [6-8].
Activated carbon has been a versatile adsorbent for the removal of various
compounds from aqueous solutions [9]. However, the high cost and availability has
restricted its application and prompted increased research interest into the
preparation and development of low – cost, readily available alternatives. These
low cost alternatives include natural materials, biosorbents and waste materials
resulting from industry and agricultural activities [10]. Zeolites of different types
are low cost natural minerals that have been employed as adsorbents for inductive
waste water effluent treatment [11-15]. Biosorbents have also been developed

3
from agro wastes like coconut shell [16], maize husk [17], banana peels [18] and
eggshells [19].
Eggs are produced and used for food and cosmetics in large quantities
worldwide. Eggshell has been explored for various uses ranging from abrasives, to
adsorbent, for many metal ions. It has been established that it contains a high level
of calcium carbonate and may be used as fertilizer and food additives for livestock
[19-22]. The utilization of eggshell and the by-products started with the
development of studies targeted at calcium supplement from the albumin,
processed membrane and matrix of eggshell for animal feedstock. However, if
these eggshells are not properly disposed or reused, they can serve as medium for
microbial growth, causing yet another environmental problem.
Studies have been conducted to determine the suitability of the eggshell and
membrane as adsorbents for iron [23], cadmium [24-25], chromium [20, 24, 26],
Cu (II) [25, 27], reactive dyes [28], Pb (II) [29], lignosulphate compound [30],
among many others. Others have also reported the catalytic property of activated
eggshell in biodiesel production [31]. The structure, adsorption behavior,
application and utilization of waste eggshell materials for the removal of organic
dyes and inorganic ions have been reviewed [22]. Previous researches on the
adsorption of cyanide from aqueous solution are presented in Table 1.
This study is aimed at investigating the adsorption of cyanide from
synthesized wastewater using activated waste eggshell and optimized using
Central Composite Design (CCD) in Response Surface Methodology (RSM). High
concentrations are used to mimic real time situation as CN in the waste waters are
available in high concentrations [3]. The effective use of the eggshell as an
adsorbent will not only help to properly manage the waste, it will give economic
value to the waste and provide a low cost adsorbent for use in small to medium
scale industries.

Materials and Methods

Eggshell preparation
Chicken eggshells used in this study were collected from restaurants in
Ilorin, Nigeria. The eggshells were soaked in warm water to remove the
membrane, washed in distilled water and sun dried for 48 hours. The eggshells

4
were crushed using ball mill to desired particle size, washed continuously until the
turbidity of the used water became negligible. The powder was dried in an oven at
120 oC for 6 hours to remove physical water before calcination at 900 oC for 4
hours. The Calcined Eggshell (CE) was later subjected to hydration and
dehydration prior to re-calcination at 600 oC for 4 hours.

Characterization of calcined eggshell

X-Ray Diffraction (XRD) analysis was carried out to observe microstructural
transformation of the eggshell as shown on Fig 1. X-Ray Fluorescence (XRF)
analysis was conducted on the sample to identify all the metallic oxides in the
eggshells before and after activation (Table 2). Scan Electron Microscopic (SEM)
analysis was carried out to establish the morphology of the samples (Fig 2).
Fourier Transform Infrared (FTIR) spectroscopic analysis was also employed to
establish phase conversions in the eggshells as well as the surface functional
groups (Fig 3).
Determination of pH of point zero of charge
Point of zero charge (PZC) of an adsorbent is important because it
indicates the net surface charge of the ion in solution. The pH at point of zero
charge (pHPZC ) is the pH value at which the net external and internal surface of the
ion is at zero [41- 43]. The pHPZC is the point where the curve of (pHinitial - pHfinal)
against pHinitial intersect the abscissa and then pH initial = pH final (Fig 4). In order to
determine the pH of point zero charge, 0.2 g of the CE was transferred into a 100
ml conical flask containing 50 ml of 0.01 mol/L NaCl. The pH initial was adjusted to
between 2 and 10 by the addition of 0.1 mol/L HCl or 0.1 mol/L NaOH for the CE.
The conical flask was sealed and placed in a shaker for 48hrs under atmospheric
condition. The content of the flask was filtered and the final pH was then measured
using a pH meter.

Preparation of cyanide solution and calibration of UV spectrophotometer

Cyanide solution of 0.5 mol/L was prepared by dissolving appropriate
quantity of KCN in deionized water in a 250 ml standard flask. Five different
standard solutions from 0.01 mol/L to 0.05 mol/L in steps of 0.01 mol/L were
prepared from the 0.5 mol/L KCN stock solution by serial dilution. Calibration

5
linearity curve was generated using the five prepared solution including a blank
using Perkin Elmer LAMBDA XLS spectrophotometer with single beam sample
compartment set at 575nm. The Linear Beer – Lambert relationship between
absorbance and cyanide concentration for the calibration curve was established by
plotting these parameters and observing the regression. The model developed was
useful for subsequent determination of unknown cyanide concentrations.

Batch equilibrium studies of cyanide adsorption

Batch adsorption experiment was conducted by contacting CE powder (5 g,
7 g and 9 g) each with, 10 ml solution (0.01, 0.03 and 0.05 mol/L KCN) in a 250 ml
batch reactor set at pH 7, temperature of 30 oC and stirring speed of 350 rpm. The
concentration of cyanide solution before and after adsorption was determined
using UV spectrophotometer. The amount of adsorbed cyanide (qt in mg/g) at time
t, was calculated using equation 1:

qt  C0  Ct 
V
1
m
Where C0 and Ct (mg/L) are the initial and final concentration of cyanide,
respectively; V is the volume of cyanide solution (L) and m is the mass of
adsorbent used (g).
The adsorption at equilibrium qe (mg/g) was calculated using equation 2 :

qe  C0  Ce 
V
2
m
Where Co and Ce are the initial and equilibrium cyanide concentration (mg/L);
respectively, V is the volume of solution (L), m is the mass of dry adsorbent used
(g).The adsorption efficiency or CN removal percentage is calculated using
equation 3 adopted from Foo and Hameed [44]
( )
3

Optimization studies
Central Composite Design (CCD) of Response Surface Methodology (RSM) in
Design Expert 6.8.0 was used to design three factors (concentration, time and
adsorbent dose) at three levels to estimate the optimum adsorption conditions.

6
Results and Discussions
Characterization of the eggshell
The XRD results, in Figure 1a, revealed that the raw eggshell consists mainly
of CaCO3 with the absence of CaO peak. Upon thermal treatment, the CaCO3
disappeared with the appearance of highly crystalline peaks attributed to CaO as
depicted in Figure 1b.
The extent of beneficiation of the eggshell is depicted in Table 2. It could be
inferred from the XRF analysis that, the CaO captured by the XRF machine was in
reality CaCO3 and, the percentage of this was lower in the raw eggshell. The
increase in CaO content was attributed to the liberation of CO2 at higher
temperature of calcination. This observation is in line with the works reported by
Busari et al [45]. The high Loss on Ignition (LOI) in the raw sample is attributed to
its inherent fibrous materials and water content [46].
The morphology of the raw eggshells, eggshells calcined at 900 oC and
washed, re-calcined eggshells at 600 oC are shown in Fig 2. The morphology of the
raw eggshells (Fig 2a) was observed to have irregular shapes and sizes, with more
coarse grains and little pores for metal attachment. This was found to conform to
the works reported by Niju et al [31]. Calcination of the eggshells led to sintering
which modified the surface area as seen in the SEM in fig. 2b. Washing and
recalcining brought about an increase in surface area as evident in fig. 2c giving
room for increase in mass transfer of the ions to the eggshells; this was used for
this adsorption study.
Adsorption bands noticed for raw eggshell in Fig 3a at 1436, 866 and 688
cm-1 corresponds to C-O asymmetric stretch, out-of-plane bend and in-plane bend
vibration models respectively for CaCO3 [47]. For calcined eggshell, shown in
Figure 3b, bands at 3637 and 2355 cm-1 depicted the existence of OH in Ca(OH)2,
suggested to have resulted from water adsorbed [48]. Appearance of peaks around
1410, 1062, 657 cm-1 are attributed to conversion of carbonate to CaO.

pH of CE at point of zero
The adsorption of ions from the solution depends to a large extent on the pH of the
solution which affects the surface charge of the adsorbents and the degree of
ionisation and speciation [34, 49-50]. In this study, the pHPZC of CE was 8.6 as

7
shown on Fig. 4. This implies that at pH < pHPZC = 8.6, the CE surface has a positive
charge and negative charge at pH > pHPZC = 8.6. Oxygen functional groups are
important characteristics of adsorbents because they determine their surface
properties. The contents of oxygen-containing functional groups with various basic
group content (CaO) is observed to be higher than the acidic group content as
shown in Table 2. This is consistent with a value of pHpzc 8.6 and the findings of
Zulfikar and Setoyanto [51], showing the dominance of basic groups. The cyanide
(KCN) is hydrolyzed in aqueous solution to form hydrocyanic acid that has a pKa
value of 9.4. At pH < 9.4, cyanide exists as HCN while at pH > 9.4, HCN dissociates
to CN− ions [34, 50]. Therefore, due to nucleophilic characteristic of CN- that
resulted in an increased electrostatic attraction at solution pH > 9.0, many
researchers have reported higher adsorption of cyanides at pH values 9 – 11 [37,
39, 49-50]. However, Dash et al [6] reported that inorganic cyanides such as NaCN
and KCN which are weak acids readily dissociate to form CN- and HCN at neutral
pH 7. At this pH, given the very low boiling point of HCN (25.6 - 26.6 oC), most of
the formed HCN would have evaporated out of the solution. This might have
formed the basis for other previous researches on higher adsorption of cyanides at
pH < 9 such as Gupta et al [52] at pH 7; Adams [53] at pH 7; Dash et al. [54] at pH
6-7 and, Saxena et al [34] at pH 7 where the adsorption of molecule of HCN onto
adsorbent has been hinged on the interaction with Lewis acid sites. Therefore, this
study was carried out at a pH 7.

Effect of Contact time on cyanide adsorption onto CE

The effect of the contact time on the adsorption efficiency of CN onto CE using
various concentrations at pH of 7 and temperature of 30 oC is as shown on Fig 5. It
was noticed that cyanide adsorption onto CE increased spontaneously with contact
time for the first 10 min reaching an equilibrium at around 40 min. The adsorption
process was rapid initially due to availability of active binding site on the
adsorbent surface which is controlled by diffusion process from the bulk to the
surface. However, during the last stages, adsorption was an attachment-controlled
process due to reduction in the available active sites. Comparatively, 0.01 mol/L
initial concentration has the highest cyanide removal at equilibrium (86 %),
followed by 0.03 mol/L (80 %) and the least being 0.05 mol/L (62 %). Generally,

8
the percentage of removal reduced with increasing initial concentration. This is
attributed to the saturation of all binding sites with ions in solution and,
establishment of equilibrium between adsorbate and adsorbent. This result is
similar to other research findings [55-57]
Effect of adsorbent dose and initial concentration on cyanide adsorption onto CE
The effect of adsorbent dose on percentage cyanide removal is as shown on
Fig 6. The percentage removal increased with increase in adsorbent dose for all the
initial concentration of cyanide considered. The highest percentage of cyanide
removal was 78 % for 0.01 mol/L using 9 g adsorbent dose followed by 67 % and
60 % for 7 and 5 g, respectively. This indicates that the quantity of adsorbent
provided enough active adsorptive site for cyanide occupation. With increase in
the initial concentration to 0.03 mol/L, a rapid drop in efficiency was noticed for 9,
7 and 5 g. This is due to less available sites resulting from the saturation of binding
sites by the ions in solution. This drop in removal efficiency was almost halved for
0.05 mol/L. This trend is in agreement with the findings of Agarry et al [56].

Adsorption Kinetics
The pseudo- first order kinetic model
The pseudo-first order equation is generally expressed as the integrated
form of Lagergren model [58] as presented in equation 4:
( ) ( ) 4
Where qe and qt are the adsorption capacities at equilibrium and at time t,
respectively in (mg/g), k1 is the rate constant for pseudo first order adsorption
(min-1). The plot of ( ) against t at various initial CN concentrations (Fig
7), resulted in linear graphs with negative slopes.
The values of k1 and qe were calculated from the slopes and intercepts,
respectively, as shown in Table 3. Despite the high correlation coefficient values
noted, the discrepancy between qe (calculated) and qe (experimental) implies that
the adsorption of CN onto CE does not perfectly fit the pseudo first order kinetics.

The pseudo- second order kinetic model

The adsorption kinetics may also be described by a pseudo-second order
equation [59]. The differential model is expressed by equation 5

9
 ( ) 5

Integrating equation 5 and applying boundary conditions (qt = 0 when t = 0; and qt

= qt at t = t gives equation 6:
6

Plots of t/qt versus t in equation 6 gave straight lines depicted in Fig 8 from
which qe, and k2 were determined. The computed results obtained from pseudo
second order kinetic model are as shown in Table 3. The correlation coefficients
obtained were greater than 0.99 for all initial concentrations studied and there
was good agreement between qe cal and qe exp. The good agreement indicates that
the pseudo-second-order kinetic model fits the adsorption system studied.

Adsorption isotherm
Langmuir isotherm is represented by the equation 7.

q m bCe
qe  7
1  bCe
where qe and qm represent the amount adsorbed at equilibrium and maximum adsorbed
in mg/g, respectively. Ce is the equilibrium concentration (mg/L) and b is the Langmuir
isotherm constant (L/mg). The plot of qe vs Ce is shown in Fig 9. Values of Langmuir
constants are tabulated in Table 4. From Figure 8, the adsorption curves were single,
smooth, plateau, continuous, leading to saturation, and this indicates the possible
monolayer coverage on the surface of the adsorbent. From the linearization plot of the
Langmuir isotherm model, the value of q m in the experiment was found to be 3.27
mg/g.

The essential features of the Langmuir isotherm can be expressed in terms of a

dimensionless constant separation factor or equilibrium parameter RL as presented in
equation 8.
1
RL 
1  bC o
8
Where b is Langmuir constant and Co is initial CN concentration (mg/L). The RL value
indicates the isotherm shape and, RL > 1 (unfavourable), RL = 1 (linear adsorption), RL =

10
0 (irreversible) and 0 < R L< 1 (favourable) [60 - 61]. The value of RL in this study was
found to be 5.73x 10-3, suggesting that adsorption of CN by powdered CE is favourable.

The Freundlich isotherm

The Freundlich isotherm was also applied for the adsorption of CN onto CE by using
the
Equation 9:
1
qe  K f Ce n 9

where Ce is the equilibrium concentration (mg/L), q is the amount of CN adsorbed per

unit mass of absorbent (mg/g), Kf and n are Freundlich constants. Plots of qe against Ce
for the CN show that the adsorption could not be fitted by this model (Fig 9) and hence
the adsorption does not follow the Freundlich isotherm at these concentrations.
Values of Kf and n are presented in Table 4.

Optimization study
The percentage removals obtained from experiments conducted were
inputted as response to the table generated from DOE. Then RSM methodology was
applied to analyse these values, leading to the model equation 10:
Cyanide Removal (%) = 47.16 - 18.304A + 13.93B + 3.97C + 7.96B2 + 3AB
10
Where A = concentration of cyanide, B = Adsorbent dosage, C = contact
time.
The estimated coefficient of equation 10 and its functional significance are
as presented in Table 5 while Analysis of Variance (ANOVA) of the model is as
presented in Table 6 in which the significant values of the F-values indicated the
adequacy of the model.
The square of the coefficient of regression of the model is 0.98, suggesting that, the
model is significantly high. The model also shows that absorbent dosage is most
relevant to cyanide removal, confirming the result depicted in Fig 9. Any
increment in the initial concentration has a negative effect on the percentage
removal while those of the dosage and time increase the percentage

11
The 3D plot along with the contour to estimate optimum value for the three factors
considered are shown in Fig 10. Fig 10 a shows the combined effect of absorbent
dose and initial concentration on percentage removal. It could be inferred from it
that to obtain 85.58 %, 0.01 mol/L of initial cyanide concentration will be treated
with 9 g eggshell. Fig 10b shows the combined effect of contact time and
concentration which pointed to a percentage removal of 89.933 for contact time of
around 30 min and 0.01 mol/L initial cyanide concentration. Fig 10c depicted
combined effect of contact time and absorbent dose which gave a lower percentage
removal of 63.3 % at almost 9 g dose for contact time between 27 and 30 min. The
DOE gave an optimization point of 84.53 % cyanide removal attainable with 0.01
mol /L, 8.98 g of egg shell at 26.58 min contact time.

Conclusion
Eggshell considered to be waste was beneficiated and thermally treated to
improve its property needed for cyanide adsorption. The various characterizations
done on the eggshells proves the potential of its applicability. The eggshell was
able to adsorb cyanide from synthesized wastewater and the adsorption isotherms
models used fitted satisfactorily. RSM was used to determine the optimal
adsorptive efficiency at operating conditions, namely concentration of cyanide,
dosage of calcined eggshell and contact time.

12
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20
 Figure Captions

Fig 1: XRD diffractograph for (a) raw eggshells (b) Calcined Eggshells

21
 (a) (b) (c)
Fig 2: SEM Morphological images for: (a) raw eggshell (b) calcinated eggshell
(c) washed and recalcined (CE)

22
Fig 3: FTIR for (a) raw eggshell (b) CE

23
 3

2.5

1.5
pH

1
pHo
0.5

0
0 2 4 6 8 10 12
-0.5

-1

Fig 4: pH of point of zero charge of CE

24
 Percentage Cyanide Removal (%) 100
90
80
70
60
50 0.01 mol/L
40 0.03 mol/L
30 0.05 mol/L
20
10
0
0 10 20 30 40 50 60
Contact Tme (Minutes)

Fig 5: Effect of Contact Time and Initial Concentration on Cyanide Removal

25
 90

80

70
Cyanide Removal (%)

60

50
5g
40
7g
30 9g
20

10

0
0.01 0.03 0.05
Initial Concentrations of Cyanide Solution (mol/L)

Fig 6: Effects of adsorbent doses and initial concentrations on cyanide

removal

26
 4.5
4
3.5
3
ln(qe-qt)

2.5
0.01 mol/L
2
0.03 mol/L
1.5
0.05 mol/L
1
0.5
0
0 10 20 30 40
Time (Minutes)

Fig 7 Pseudo-first-order kinetic model fitted to the batch kinetic data of CN

adsorption by CE at different initial concentrations

27
 3.5

3.0

2.5
t/qt (min.g/mg)

2.0
0.01mol/L
1.5
0.03 mol/L
1.0 0.05 mol/ L

0.5

0.0
0 10 20 30 40 50 60
Time (Minutes)

Fig 8 : Pseudo-second-order kinetic model fitted to the batch kinetic data of

CN adsorption by CE at different initial concentrations

28
 4.0000
3.5000
3.0000
2.5000
qe (mg/g)

2.0000 Experimental

1.5000 Langmuir
Freundlich
1.0000
0.5000
0.0000
0 1000 2000 3000 4000
Ce (mg/L)

Fig 9 Non-linear isotherm of CN adsorption onto CE

29
 86.933

85.5777
77.2995

69.4612
67.666
86.1822
53.3447
58.0325

% Removal
78.5586
37.2282
% Removal

48.399
70.9349
21.1117

63.3113

% Removal
55.6877

30.00
9.00
0.05
0.05 25.00
8.00
0.04
0.04
20.00 30.00
7.00 0.03
0.03 9.00
C: Contact Time 15.00 25.00
B: Adsorbent Dose 6.00 0.02
0.02 8.00
A: Concentration
A: Concentration
10.00 0.01 20.00
5.00 0.01 7.00

C: Contact Time 15.00

6.00
B: Adsorbent Dose
10.00 5.00

(a) (b) (c)

Figure 10: Effects of combination of factors on the percentage cyanide
removal (a) Concentration vs Adsorbent dose (b) Concentration vs Time (c)
Time vs Adsorbent dose

30
Tables
Table 1: Previous adsorption studies on cyanide
Adsorbent Adsorption conditions Adsorption References
capacity mg/g
Gold electrodeposits Adsorption of cyanide – containing [32]
species on gold electrodeposits from
alkaline solution of potassium
cyanide.
Silver Adsorption of cyanide ions on silver.The 15.4 [33]
concentration was varied from
constant
temperature and pH of 12.3.
Pyrophyllite surface The adsorption of cyanide onto 40 % in 10 mg/l [34]
pyrophyllite mineral surface was solution to 99 %
investigated at pH 7. in 0.1 mg/L
solution.
Activated carbon Effects of modifying activated 29.2 [1]
modified with carbon with TBAI and SDDC were (  5 times that of
tetrabutyl investigated on the removal of CN in plain carbon)
ammonium iodide solution.
and sodium diethyl
dithiocarbarmate
Metal impregnated Effect of metal impregnation, 2.95 [35]
granular activated aeration, concentration of adsorbent
carbon and cyanide on the rate and extent of
removal of cyanide was studied at
pH between 10 and 11
Nutshell and Rice Nutshell and rice husk activated 4.32 [36]
Husk Activated carbon was used to adsorb cyanide at
Carbon a pH of 11 using batch and column
contact pattern.
Pitstachio Hull Pistachio hull waste was used for the Not available [37]
Waste removal of cyanide from wastewater.
99 % removal of cyanide was
attained at an optimum pH of 10,
adsorbent dose of 1.5 g/L, time of 60
min and temperature of 24 .
Granular Activated Co – adsorptive removal of phenol The monolayer [38]
Carbon and cyanide from binary solution adsorption
using granular activated carbon was capacity of GAC
carried out at optimum pH of 8 and was found to be
30 oC temperature. The adsorption 269.7 and 1.95
followed pseudo – second order mg/g for Phenol
kinetics. and Cyanide,
respectively.
Polymeric complex Batch adsorption studies on cyanide 101.53 mg/g [39]
adsorbent were carried out while varying pH,
temperature, adsorbent dosage and
agitation time.Maximum adsorption
occurred between pH 9 -10 and
temperature of 298 K
Copper/ Active Electrochemical destruction of Cyanide removal [40]
Carbon Fiber cyanide with Cu/active carbon fiber efficiency less
Cathode composite cathode and than 20 %
dimensionless stable anode under
alkaline conditions was investigated

31
Table 2: XRF results for the eggshells before and after activation
Components Percentage Compositions of Eggshell
Natural Calcined
CaO 70.7 89.8
SiO2 0.12 0.1
Al2O3 0.04 0.32
MgO 0.01 0.01
Fe2O3 0.03 0.03
Na2O 0.23 0.21
P2O5 0.24 0.26
SO3 0.63 0.63
*LOI 28.2 11.5
*LOI refers to oxide loss on ignition

32
Table 3: Pseudo first order and pseudo second order kinetic parameter and
correlation coefficient obtained for adsorption of CN onto CE at different
concentration
Model Initial CN Concentrations (mol/L)
0.01 0.03 0.05
Pseudo first order
qe (exp.) ( mg/g ) 0.63 1.75 2.26
k1 (min-1) 0 .052 0.020 0.018
qe (cal.) (mg/g) 0.32 1.45 1.94
R2 0.981 0.962 0.955
Pseudo second order
k2 (g.mg-1 min-1) 0.0053 0.0043 0.0011
qe (cal.) (mg/g) 0.64 1.74 2.24
R2 0.998 0.999 0 .998

33
Table 4 Comparison of the isotherms for the adsorption of Cyanides.
Model Temperature (303 K)
Langmuir isotherm
qm (mg/g ) 3.27
B (L/mg) 0.263
R2 0.998
RL 5.78 x 10-3
Freudlich isotherm
Kf 0.76
N 4.76
R2 0.65

34
Table 5: Statistical parameters for the percentage cyanide removal model
Source Coefficients F- Value p-value
Intercept 47.16 75.84 0.0001*
A -18.30 398.35 0.0001*
B 13.93 230.91 0.0001*
C 3.97 18.72 0.0075*
A2 -1.20 0.44 0.5356
B 2 7.96 19.39 0.0070*
C2 -0.54 0.088 0.7783
AB 3.00 8.56 0.0328*
AC 2.00 3.81 0.1085
BC 0.75 0.54 0.4972
R = 0.98
2

*Significant at p<0.05

35
Table 6: Analysis of variance for the percentage cyanide removal
Source DF Sum of Mean F- Ratio p-Value
Square Square
Model 9 5737.98 637.55 75.84 0.0001
Linear 3 5447.55 1815.85 647.98 0.0001
Square 3 167.50 55.83 19.92 0.0001
Interaction 3 108.5 36.17 12.91 0.0003
Residual 5 42.03 8.41
Cor Total 14 5780.01

36