IRJCCS

International Research Journal of Chemistry and Chemical Sciences

Vol. 4(1), pp. 043-048, July, 2017. www.premierpublishers.org. ISSN: XXXX-XXXX

Research Article

SYNTHESIS AND CHARACTERIZATION OF KAOLINITE

COATED WITH CU-OXIDE AND ITS EFFECT ON THE
REMOVAL OF AQUEOUS MERCURY(II) IONS: PART II
Davidson E. Egirani*1, Mohamed. T. Latif2, Nanfe R. Poyi3, Napoleon Wessey4, Shukla Acharjee5
1Faculty of Science, Niger Delta University, Wilberforce Island, Nigeria.
2School of Environmental and Natural Sciences, National University, Malaysia.
3Nigerian Institute of Mining and Geosciences, Jos, Nigeria.
4Faculty of Science, Niger Delta University, Wilberforce Island, Nigeria.
5Centre for Studies in Geography, Dibrugarh University, Assam, India.

In this paper, the effect of copper oxide coated kaolinite on mercury (II) removal based on initial
metal concentration, particle concentration, and prolonged residence time have been
investigated. Experimental methods involved batch mode techniques at ambient temperature. The
content was analysed for Hg(II) adsorbed, using standard laboratory procedures. Here, using
empirical models derived from Freundlich isotherm, adsorption capacity increased from 300 to
400 mg/kg over the range of initial metal concentration investigated. The complex behavior of
existing reactive sites and the generation of new active sites accounted for these changes in
adsorption capacity. Increase in particle concentration led to decrease in adsorption. This was
over the range of 2, 4, 6, 8 and 10 gL-1 solid concentration. Higher Cp reduced the specific surface
area for adsorption. Hg(II) ions removal increased with increase in residence time. The most
efficient ratio of Cu-Oxide coated kaolinite was at 0.002kgL-1 at 40mgL-1 mercury concentration.
Values of between 600 to 900 mg/kg for Cu-Oxide coated kaolinite was higher when compared
with the uncoated kaolinite. As ageing was increased, hydroxylation probably increased thus
leading to the formation of new reactive sites.

Keywords: kaolinite, Cu-Oxide, initial metal concentration, particle concentration, ageing

INTRODUCTION

Reliable systems of minerals and solution chemistry are
required for effective removal of mercury ions at low
concentrations. Studies have revealed that mercury(II)
ions easily dissolve in solution and a combination of factors
regulate its removal from contaminated water (Gsior and
Tic,2016; Herrero et al., 2005: 3199-3210).
Water bodies as recipient of mercury ions is increasing,
thus levels above recommended standards (1g/L) are
found in the aquatic environment (Egirani et al., 2013a: 73-
81). Severe chronic diseases are caused by mercury
poisoning. In addition, mercury in its elemental form bio-
accumulates in the environment and creates neurological
health impact (Egirani et al., 2014: 1006-1017). Methyl
mercury induced by microbial biomethylation of Hg(II) ions
SYNTHESIS AND CHARACTERIZATION OF KAOLINITE COATED WITH CU-OXIDE AND ITS EFFECT ON THE REMOVAL OF AQUEOUS MERCURY(II) IONS: PART II
can accumulate in the body and can cause brain damage
and other chronic diseases (Egirani et al., 2016: 188-194).
Testing the removal of Hg(II) ions using standard
laboratory procedures mimics its removal from natural
bodies of water. This remains a current and relevant
research topic.
The hydrolysis performance of mercury ions and the
solubility of its species are controlled by pH. Increase in
concentration of particles and particle sizes may attenuate
mercury removal from aqueous solution (Deshicar et al.,
1990: 1011-1016), (Zhu et al., 2009: 2014-2025).
*Corresponding author: Dr. Davidson Egirani, Faculty of
Science, Niger Delta University, Wilberforce Island,
Nigeria. Email: eenonidavidson@yahoo.com
Egirani et al. 044
Figure 1: X-ray diffraction of kaolinite
The latter depicts outer sphere complexation. In some
cases, increase in particle size and particle concentration
does not necessarily lead to an increase in mercury uptake
(Eze et al., 2013: 852-860). Presence of surface area and
surface-active sites control mercury uptake (Franois et
al., 2012: 803-818), (Mishra et al., 2013: 175-184).
Increasing the residence time of solid mineral phase in
aqueous solution could results in much mineral surface
reorganization (Bonnissel-Gissinger et al., 1999: 313-322).
Increase in metal concentration led to initial decrease in
adsorption capacity (Akpomie et al., 2015: 757-767).
Here, the effect of solution composition and ageing on the
removal of mercury (II) ions from solution has received
limited attention. Previous studies centered on the use of
untreated kaolinite in removing Hg(II) ions from aqueous
solution (Egirani et al., 2013b: 49-55; 2016: 188-194).
Others have reported the use of modified activated carbon
and polyzwitterionic resin in mercury removal (Saleh et al.,
2017a: 1079-1088, b: 230-238, Vandervennet et al., 2012:
157-170). The aim of this study was to determine the role
of Cu-Oxide coated kaolinite in mercury removal in relation
to solution composition and ageing. Batch mode
experiments were conducted based on solution
composition, initial metal concentration and prolonged
residence time.
MATERIALS AND EXPERIMENTAL METHODS
All reagents used were of analytical grade. Kaolinite was
provided by Richard Baker Harrison Company of the
United Kingdom. This is known as RBH kaolinite. Merck
(Canada). provided the mercuric chloride used for the
sourcing of Hg(II) ions. Mercuric chloride dissolved in
double distilled water was used in the preparation of
different concentrations of Hg(II) ions.
Characterization
RBH kaolinite contained 47.00% SiO2,38.00% Al2O3,
SYNTHESIS AND CHARACTERIZATION OF KAOLINITE COATED WITH CU-OXIDE AND ITS EFFECT ON THE REMOVAL OF AQUEOUS MERCURY(II) IONS: PART II
1.50% moisture content as provided by the company. In
this study, particle size range was 0.6.00-20 m, cation
exchange capacity(mmols/kg) was 170, surface area
(m2/g) was 47.01 and point of zero salt effect was 7.
pH of RBH kaolinite suspensions and reacting solutions
were determined using the Model 3340 Jenway ion meter.
The cation exchange capacity (CEC) was determined by
Na saturation method. The external surface area of the
RBH kaolinite was measured using the standard
volumetric Brunauer, Emmett and Teller (BET) method
(Brunauer et al., 1938: 309319). Spectral analysis was
done using a JEOL JSM 5900 LVSEM with Oxford INCA
EDS (Table 1 and Figure 1).
Synthesis of Cu-Oxide Coated Kaolinite
Setting of Cu-oxide-coated kaolinite was by precipitating
the copper ions on the RBH kaolinite surface. Sodium
hydroxide addition tracked by thermal treatment was
conducted (Eren, 2009).
Cu-oxide-coated kaolinite was set by precipitating the
copper ions on the surface of the RBH kaolinite. This was
done using sodium hydroxide tracked by thermal treatment
(Phiwdanga et al., 2013: 740 745), (Eren, 2009).
20 g of RBH was mixed with 100 mL 1M Cu(NO3)2 solution
and 180 mL of 2 M NaOH solution. These were freshly
prepared. The mixture of the reaction was maintained at
90 C for 48 h. The RBH activated with the NaOH solution
was dispersed into 150 mL of 0.10 M Cu(NO3)2 solution.
0.10 M NaOH aqueous solution amounting to three
hundred microliters was added dropwise at the rate of 1
mL/h. To minimize the formation of carbonate salts, the
titration was carried out under nitrogen flow condition
(Maruthupandy et al., 2017: 167174), (Wang et al., 2016:
328334). Centrifugation and washing of the precipitate
was carried out to free the content from NO3 ions. Heating
the solid for 4 h in air at 700 K led to the formation of Cu-
Oxide kaolinite. RBH kaolinite was verified from the X-ray
diffraction (XRD) patterns of the product.
 Int. Res. J. Chem. Chem. Sci. 045

Table 1: Summary of system characterisation

Components of Characterisation Values

SiO2 (%) 47.00
Al2O3 (%) 38.00
Moisture content (%) 1.50
Specific gravity 2.60
Water soluble salt (%) 0.20
CEC (mmols/kg) 170.00
% (<1000 nm) colloid 3.00
Components of Characterisation Values
Particle size range (m) 0.60-20.010.5
pH 6.050.05
Surface Area(SSA) (m2/g) 47.01 0.24
Point of Zero Salt Effect (PZSE) 7.00

Table 2: Statistical presentation of proton coefficient

Equation Y=a+b*x
Proton coefficient 0.891
Residual Sum of 0.019
Squares
Pearsons r 0.939
Adj. R-Square 0.843
Value Standard Error
Log Kd(L/kg) Intercept 1.946 0.755
Slope 0.605 0.127

Table 3: Mass transfer rates for Hg(II) sorbed on Cu-Oxide coated kaolinite
Slope I(hr-1) SlopeII(hr-1) Exposed Surface KfI (cmhr-1) KfII (cmhr-1)
Area (cm-1)
0.935 0.074 4700 1.990e-4 1.590e-5

Batch Mode Experiments

To determine the effect of initial metal concentration,
10ppm, 15ppm, 20ppm and 40ppm of Hg(II) solutions
were reacted with 1% each of Cu-Oxide coated kaolinite
suspension. This was made up to 50mL solution and
equilibrated for 24h at pH =4 below the point of zero salt
effect. This was used to determine the effect of initial metal
concentration.
Here, Co denotes the initial metal concentration (mgL-1) at
time t=0; Ct denotes the concentration (mgL-1) at time t; V
denotes the total Cu-Oxide coated kaolinite suspension
volume and m is the weight of the sorbent (kg) (Egirani et
al., 2013a: 73-81), (Vijayakumar et al., 2012: 157-170).
RESULTS AND DISCUSSION

To determine particle concentration effect (Cp), solid Results

concentrations of Cu-Oxide kaolinite of 2, 4, 6, 8 and 10
gL-1 made unto 50mLwere reacted with solutions Cu-Oxide Coated Kaolinite and Initial Metal
containing 10ppm, 15ppm, 20ppm and 40ppm of Hg(II) Concentration
ions and equilibrated for 24h at pH=4.
Initial metal concentration affected the proton coefficient
To determine the effect of ageing,10ppm, 15ppm, 20ppm and the mass transfer rates. These were based on 10mgL-
and 40ppm mercury concentrations were reacted with 1% 1 initial metal concentration (Table 2 and Table 3).

Cu-Oxide coated kaolinite at pH=4.In each case the
content was equilibrated, made unto50mL and aged from
24 to 720h. All experiments were conducted at room
temperature.
Here, amount of metal adsorbed (Qt) on a mineral at time
t, is provided in Equation (1):
Qt(mg/kg) = [Co-Ct] V/m (1)
SYNTHESIS AND CHARACTERIZATION OF KAOLINITE COATED WITH CU-OXIDE AND ITS EFFECT ON THE REMOVAL OF AQUEOUS MERCURY(II) IONS: PART II
Adsorption capacity increased from 300 to 400 mg/kg over
the range of metal concentration investigated (Figure 2).
Cu-Oxide Coated Kaolinite and Particle Concentration
(Cp) Effect
There was a decrease in sorption capacity as particle
concentration was increased (Figure 3).
Egirani et al. 046

Figure 2: Plot of adsorption capacity versus initial metal Figure 3: Plot of sorption capacity versus Cp for Cu-Oxide coated kaolinite at
concentration at pH=4. pH=4.

Figure 4: Plot of sorption capacity versus residence time ageing for mineral
systems at 10mgL-1 metal concentration

Cu-Oxide Coated Kaolinite and Ageing Effect.
The rate of removal of Hg(II) ions increased from 600 to
900 mg/kg over the range of residence time investigated
(Figure 4).
investigated. Also, uncoated kaolinite provided an
increase in Hg(II) adsorption as particle concentration was
increased. Furthermore, uncoated kaolinite revealed a
decrease in Hg(II) adsorption over the range of ageing
investigated (Egirani et al., 2016:188-194; 2013a:73-81;
2014:1006-1017).

DISCUSSION Here, the overall adsorption capacity decreased with

increase in initial metal concentration. This decrease is
The range of increase in adsorption capacity as initial ascribed to the fact that Cu-Oxide coated kaolinite
metal concentration was increased, was higher than those possesses a constant number of active and reactive sites.
of uncoated kaolinite These reports provided a linear As the metal concentration was increased, the reactive
decrease in Hg(II) adsorption as initial metal sites became saturated. For particle concentration effect,
concentration, over the range of initial metal concentration the values for coated kaolinite were higher when
SYNTHESIS AND CHARACTERIZATION OF KAOLINITE COATED WITH CU-OXIDE AND ITS EFFECT ON THE REMOVAL OF AQUEOUS MERCURY(II) IONS: PART II

compared with uncoated kaolinite. Here, the most efficient
ratio of Cu-Oxide coated kaolinite was at 0.002kgL-1 at
40mgL-1 mercury concentration. The lower sorption
capacity as Cp was increased could be assigned to the
fact that higher Cp reduced the specific surface area for
adsorption. Increase in Cp reduced accessibility of Hg(II)
ions to intra-particle diffusion was probably reduced.
For ageing, adsorption capacity for the uncoated kaolinite
was lower when compared with the coated kaolinite. This
may be ascribed to increased presence of active and
reactive sites on the surface of the Cu-Oxide coated
kaolinite. As ageing was increased, hydroxylation
increased thus leading to the formation of new active and
reactive sites.
CONCLUSIONS
Adsorption of Hg(II) ions on Cu-Oxide coated kaolinite was
investigated in batch mode systems. Adsorption properties
such as initial metal concentration, particle concentration
and ageing effect demonstrated complex behavior.
Adsorption capacity decreased with increase in metal
concentration. Here, as the metal concentration was
increased, the reactive and active sites became saturated.
Increase in particle concentration led to a decrease in
adsorption. In this case, the values for coated kaolinite
were higher when compare with uncoated kaolinite. Over
the range of residence time investigated, adsorption
capacity for the uncoated kaolinite was lower when
compared with the coated kaolinite. Increased presence of
reactive and active sites may account for this
development. Therefore, the highlight of the conclusions
are as follows:
1) Adsorption capacity increased from 300 to 400
mg/kg over the range of initial metal concentration
investigated.
2) Higher Cp reduced the specific surface area for
adsorption. Hg(II) ions
3) As ageing was increased, hydroxylation probably
increased thus leading to the formation of new
reactive sites.
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Accepted 14 July, 2017

Citation: Egirani DE, Latif MT, Poyi NR, Wessey N, Acharjee

S (2017). SYNTHESIS AND CHARACTERIZATION OF
KAOLINITE COATED WITH CU-OXIDE AND ITS EFFECT
ON THE REMOVAL OF AQUEOUS MERCURY(II) IONS:
PART II. International Research Journal of Chemistry and
Chemical Sciences, 4(1): 043-048.

Copyright: 2017 Egirani et al. This is an open-access

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SYNTHESIS AND CHARACTERIZATION OF KAOLINITE COATED WITH CU-OXIDE AND ITS EFFECT ON THE REMOVAL OF AQUEOUS MERCURY(II) IONS: PART II