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Environment International 31 (2005) 845 854

www.elsevier.com/locate/envint

Sorption of metal ions from aqueous solution using bone char


Keith K.H. Choy, Gordon McKay*
Department of Chemical Engineering, Hong Kong University of Science and Technology, Clear Water Bay Road, Kowloon, Hong Kong SAR, China

Available online 14 July 2005

Abstract

The sorption of cadmium, copper and zinc from aqueous solutions onto bone char has been studied in both single and binary multi-
component systems. Equilibrium experimental studies have been performed to determine the sorption capacity of bone char for each metal
ion. The isotherm results have been analysed using single and multi-component equilibrium models. The rate of sorption of the metal ions
onto bone char has been studied using an agitated batch adsorber. The concentration versus time decay curves have been measured and a
number of mass transfer models have been developed and tested based on diffusion controlled sorption. The results of the equilibrium and
rate studies are presented and discussed in the paper. The possible mechanisms of metal sorption are also discussed. Finally a series of fixed
bed column studies have been performed and analysed using a diffusion mass transport model. The experimental results show a displacement
effect for the binary metal ion breakthrough curves.
D 2005 Elsevier Ltd. All rights reserved.

Keywords: Adsorption; External mass transfer; Surface diffusion; Metal ions; Bone char; Multi-component

1. Introduction al., 1993), goethite (Grossl et al., 1994), kaolin (Arias et al.,
2002) and peat (Chen et al., 1990; Allen et al., 1994). A
When water is polluted with heavy metal ions, it can be number of studies have been carried out on the removal of
detrimental and sometimes deadly to living things. More- zinc ions from wastewaters including activated carbon
over, their discharge in aqueous solutions over land enables (Gabaldon et al., 1996), sludge (Gao et al., 1997) and peat
them to be sorbed by various components in soil and then (McKay and Porter, 1997a). Some of the adsorption
re-adsorbed via crops into the animal and human food capacities are shown in Table 1.
chains. One of the major methods for the removal of In order to predict the behaviour of metal ions in the
pollutants from wastewaters and aqueous solutions is by presence of adsorbents it is necessary to carry out modelling
adsorption onto porous solid adsorbents. studies, based on equilibrium capacity studies, diffusion mass
In recent years several new economically priced sorbents transport, kinetics, complexation modelling or ion exchange.
have been tested to assess their ability to remove metal ions. Within the porous adsorbent particles, the fundamental mass
The sorption of cadmium ions has been tested using transport mechanisms can be generally limited by external
agricultural waste (Periasamy and Namasivayam, 1994), film, pore, and surface diffusion. Some models based on one
carbon (Gabaldon et al., 1996), goethite (Wang and Xing, or two diffusion-resistances are available in the literature
2002), kaolin (Arias et al., 2002), lignite (Allen et al., 1997), (Brauch and Schlunder, 1975; Crittenden and Weber,
peat (McKay and Porter, 1997a,b) and biomass, plants and 1978a,b; Weber and Wang, 1987; Smith and Weber, 1989;
algae (Trujillo et al., 1999; Yang and Volesky, 1999; Terry Ko et al., 2001). The experimental data obtained from the
and Stone, 2002). Several sorbents have been used to pilot-plant columns has been substituted into a film pore
remove copper ions from wastewaters including carbon diffusion model; the results demonstrate that there is a
(Namasivayam and Kadirvelu, 1997), chitosan (Findon et variation in the determined values of effective pore diffusivity
with C 0 and d p, suggesting that surface diffusion was likely to
* Corresponding author. Tel.: +852 2358 8412; fax: +852 2358 0054. be involved in the mass transfer process to describe the
E-mail address: kemckayg@ust.hk (G. McKay). sorption of metal ion onto bone char (Ko et al., 2001).
0160-4120/$ - see front matter D 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envint.2005.05.036
846 K.K.H. Choy, G. McKay / Environment International 31 (2005) 845 854

Table 1 in order to obtain an equation which accurately represents


Materials used as adsorbents for metal ions the results and therefore can be used for design purposes.
Metal ion Adsorbent Capacity Reference Several sorption equilibrium equations are available for the
(mg/g)
data analysis. In this study, two isotherm equations,
Cadmium Activated carbon 73.0 Ozer and Tumen, 2003 namely, the Langmuir equation and Sips equation (or
Coirpith-activated 93.4 Kadirvelu and
sometimes known as Langmuir Freundlich equation),
carbon Namasivayam, 2003
Ca-bentonite 7.28 Alvarez-Ayuso and were employed to study the adsorption process.
Garcia-Sanchez, 2003 Langmuir isotherm:
Na-bentonite 26.2 Alvarez-Ayuso and
Garcia-Sanchez, 2003
KL Ce KL
qe and qm 1
Mucor rouxii 8.46 Yan and 1 aL C e aL
biomass Viraraghavan, 2003
Amberlite 2.56 Bermejo-Barrera Sips isotherm:
XAD-2 resin et al., 2003 KLF Cen
Zinc Ca-bentonite 5.75 Alvarez-Ayuso and qe : 2
Garcia-Sanchez, 2003 1 aLF Cen
Na-bentonite 23.1 Alvarez-Ayuso and
Garcia-Sanchez, 2003
The Langmuir isotherm, which is derived based on a
Mucor rouxii 20.5 Yan and monolayer homogeneous surface adsorption process, is one
biomass Viraraghavan, 2003 of the most commonly used isotherms for equilibrium
Tree fern 7.58 Ho et al., 2002 studies. The bone char, however, mainly contains carbon
Coal 1.20 Karabulut et al., 2000 and hydroxyapatite randomly distributed on the surface
Copper Ca-bentonite 7.72 Alvarez-Ayuso and
Garcia-Sanchez, 2003
which may introduce heterogeneity onto the surface, thus
Na-bentonite 30.0 Alvarez-Ayuso and violating the assumption of the Langmuir isotherm equation.
Garcia-Sanchez, 2003 Therefore, in the present study, the Langmuir equation is
Mucor rouxii 20.3 Yan and regarded as an empirical expression. The Sips isotherm
biomass Viraraghavan, 2003 equation is characterized by the heterogeneity factor, n, and
Amberlite 6.86 Bermejo-Barrera
XAD-2 resin et al., 2003
it can be employed to describe the heterogeneous system.
Tree fern 10.6 Ho et al., 2002 The Ideal Adsorbed Solution Theory (IAST) was
Coal 1.62 Karabulut et al., 2000 developed to predict equilibria in dilute multi-component
Chitosan bead 80.7 Ngah et al., 2002 liquid adsorption systems by Radke and Prausnitz (1972).
The IAST has a sound thermodynamic basis and requires
only single component isotherm parameters to predict the
The surface diffusion model pictures the sorption sorption equilibrium for the multi-component system. The
process as occurring at the outer surface of a sorbent, IAST is based on the assumption that the adsorbed phase
followed by the diffusion of the sorbate along the sorbent can be treated as an ideal solution of the adsorbed
surface. Recently, surface diffusion modelling has also components.
been shown to be applicable for metal ion sorption From the mass balance for each non-volatile component
systems (Theis et al., 1992; Smith and Amini, 2000; i, the sum of the material in the solid phase and the liquid
Gupta, 1998; Trivedi and Axe, 2000). This paper presents phase at equilibrium must be equal to its initial solution
the sorption of cadmium, copper and zinc ions onto bone phase concentration,
char in single and multi-component systems. Equilibrium
M
studies have been performed and the experimental data C0;i Ce;i qe;i 3
analysed using Sips and Langmuir isotherm equations. V
Agitated batch kinetic studies were performed for the The IAST dictates that the spreading pressure should be
single and multi-component systems and the data ana- constant for each component in a given system:
lysed using a surface diffusion model. Fixed column
p 1 p 2 p 3 N pn 4
studies were carried out to determine if the effect of
displacement can be predicted by the model in binary From the overall mass balance, the sum of the mole in each
metal ion systems. phase must be exactly equal to unity, i.e. for the solid phase:
n
~ si 1 5
i1
2. Theory
The best-fit isotherms for the single component systems are
2.1. Equilibrium isotherm used to calculate the spreading pressure, for instance, the
Langmuir and Sips isotherms may be used. The spreading
The experimental data from the equilibrium studies pressure, p, and reduced spreading pressure, P, can be
were substituted into different sorption equilibrium models evaluated from Eq. (7) or Eq. (9):
K.K.H. Choy, G. McKay / Environment International 31 (2005) 845 854 847

For Langmuir isotherm: 2) Pore diffusion makes a negligible contribution to mass


0
KL;i Ce;i transport.
q0e;i 0
6 3) The adsorbent particles are assumed to be identical
1 aL;i Ce;i spheres of radius R.
 
Z 4) A linear driving force describes the liquid film transport
q0e;i Ce;i KL;i  
Ce0 0
p i SA 0 0
Pi 0
dCe;i ln 1 aL;i Ce;i resistance at the outer surface of the particle.
Rg T 0 Ce;i aL;i
7 In addition, a material balance equation for the batch reactor
system is necessary to describe the adsorption process.
For Sips isotherm: The concentration of solute inside the typical particle at
 ni
0 distance r from the centre and at time t is defined by q i (r,t)
KLF;i Ce;i
0
qe;i  ni 8 and the variation of q i with distance and time is governed by
0
1 aLF;i Ce;i the diffusion equation:
 
  Bq Ds B 2 Bq
Z 0 0
qe;i Ce;i 2 r 12
pi SA Ce;i
0 Bt r Br Br
Pi 0
dCe;i
Rg T 0 Ce;i Assuming a constant diffusivity, D s, during each experi-
  h  ni i ment, the differential equation for the two resistances,
KLF;i 0
ln 1 aLF;i Ce;i 9 external film mass transport and surface diffusion, are:
aLF;i ni

Hence, transforming the reduced spreading pressure into Bq  m
Ds kf CV  Cs kf qV  qjr : 13
those based on single-component data produces the follow- Br r V
ing for one component of a multi-component system:
" !#
0 M n Sj 2.2.2. Fixed bed model
V Ce;i
C0;i ~ si 10
V j1 q0e;i The fixed bed film surface diffusion model is based on
the assumption that the adsorbate penetration rate is
For the Langmuir isotherm, rearranging Eqs. (6) and (7) determined by the external film diffusion and the surface
allows each to be substituted into Eq. (10) to obtain the diffusion. In accordance with these assumptions and mass
equivalent pure component fluid and adsorbed-phase con- transport mechanisms, the following set of mathematical
centrations at the specified spreading pressure: equations can be derived and solved.
(1) The overall mass balance for the process dynamics is
0 exp aL;i P=KL;i  1
Ce;i 11 the following: (rate of solute in by flow  rate of solute out
aL;i by flow) rate of accumulation of solute in the fluid phase,
The Newton Raphson method was used to identify values and in the solid phase:
of P and s i that minimize the error between the       
BC BC 1e Bq
experimental initial liquid-phase solute concentrations, v q 0 14
BZ t Bt Z e Bt Z
which are predicted by the IAST. Similarly, in the case of
Sip isotherm, Eqs. (8) and (9) will be combined into Eq. (2) Mass transfer through the stagnant liquid film for a
(10) to find out the solution. spherical particle corresponds to the following: the rate of
accumulation of solute in the solid phase is equal to the rate
2.2. Diffusion mass transport model of transfer of solute across the liquid film.
 
Bq 3kf
2.2.1. Batch kinetic model q C  C s 15
The basis of the homogeneous surface diffusion model Bt R
(HSDM) was proposed by Mathews and Weber (1976) and (3) When the dominant effect is surface diffusion, the
included the effect of external mass transfer, unsteady-state adsorption rate has the following form:
surface diffusion in the particle and a non-linear adsorption  
isotherm. Once reaching the surface, adsorption occurs Bq 1 B 2 Bq
2 Ds r 16
instantaneously and equilibrium is assumed to be estab- Bt r Br Br
lished. The underlying assumptions of HSDM are as
follows: The initial conditions include the following: (1) q = 0 for all
r at t = 0; (2) C)Z=0 = C 0 at t = 0.
1) The adsorbent particle (GAC) is assumed to be a To predict the breakthrough curve, the numerical
homogeneous solid in which the adsorbate is transported solutions for the fluid and solid phase PDEs are solved by
by surface diffusion. using a finite difference method and are coupled at the
848 K.K.H. Choy, G. McKay / Environment International 31 (2005) 845 854

particle surface a using suitable adsorption equilibrium Table 3


isotherm. The effect of the concentration and mass
Concentration (mM) Mass (g)
2 6.5
3. Experimental section 2.5 7.5
3 8.5
4 9.5
3.1. Physical and chemical properties of bone charcoal 5 10.5
Temperature = 20 -C, pH = 4.9, particle size = 500 710 Am.
The bone char used in this study was Brimac 216, 20/60
mesh supplied by Tate & Lyle Process Technology. The
physical and chemical properties of bone char were can be measured. Equilibrium was reached with the bone
provided by the manufacturer. Table 2 shows that the main char after 72 h. To ensure equilibrium was attained, 5 days
composition of bone char is calcium hydroxyapatite of agitation time were used for all equilibrium experiments
(CaHAP). for the three metal ions.

3.2. Pretreatment of sorbent 3.6. Adsorption equilibrium isotherm

The bone char was sieved, rinsed with DI water and dried A fixed mass of bone charcoal was weighed into 120 ml
at 103 105 -C for 24 h and then allowed to cool in the test bottles. Metal ion solutions were prepared and then
desiccator. pipetted into the test bottles. The initial pH of the solutions
was adjusted to 5.0 by the addition of dilute sulfuric acid.
3.3. Sorbates The test bottles were put in the shaker bath for 5 days and
were shaken at the maximum shaking rate (200 rpm).
The wastewater usually contains sulfate ions in solution.
In this research, analytical grade Cadmium(II) sulfate 3.7. Batch kinetic experiments
(3CdSO4I8H2O) and copper(II) sulfate (CuSO4I5H2O) used
in the experiments were supplied by Riedel-de Haen An adsorber vessel in a batch stirred tank configuration
Chemicals. The analytical grade zinc (II) sulfate was used in all of the experiments. The design of the
(ZnSO4I7H2O) was supplied by BDH chemicals. All standard agitated batch adsorber has been described in
solutions were adjusted to pH = 5.0 using dilute sulfuric previous papers (Furusawa and Smith, 1973; Choy et al.,
acid. 2001). The adsorber vessel was a 2 dm3 plastic beaker with
0.13 m internal diameter. It can hold a volume of 1.7 dm3
3.4. Analytical techniques metal ion solution. A six bladed, flat plastic impeller was
used to achieve complete mixing and the diameter of the
The concentrations of metal ion solutions were measured impeller and the blade height were 0.065 m and 0.013 m,
by Inductively Coupled Plasma-Atomic Emission Spec- respectively. A motor was used.
trometer (ICP-AES). Five calibration standards (15, 30, 45, The standard condition of the batch kinetic experi-
60 and 90 mg/dm3) were prepared and the samples were ments was fixed at the mass of bone char (8.5 g), at a
automatically measured three times in one aspiration. fixed particle size (500710 Am), a fixed temperature
(20 T 2 -C), a fixed pH (4.9 T 0.1), and a fixed initial
3.5. Agitation time for sorption isotherm concentration of metal ion solution 3 mM (see Table 3).
The effect of initial metal ion concentration was studied
Initially the required agitation time to reach equilibrium by varying the initial concentrations of metal ion solution
was determined before the equilibrium sorption isotherms (i.e. 2, 2.5, 3, 4 and 5 mM) and the other conditions were
fixed.
Table 2
Physical and chemical properties of bone char (source: Tate & Lyle Table 4
Company Limited) Experimental conditions for the copper zinc ions fixed bed sorption
Chemical composites Physical properties system on bone char
Items Limits Items Limits Experimental conditions
3
Acid insoluble ash 3 wt.% max. Bulk density (dry) 640 kg/m Flowrate 75 ml/min
Calcium carbonate 7 9 wt.% Carbon surface area 50 m2/g Bone char mean particle size 605 Am
Calcium sulfate 0.1 0.2 wt.% Total surface area 100 m2/g Initial concentration of copper ion 1.5 mmol/l
Carbon content 9 11 wt.% Pore volume 0.225 cm3/g Initial concentration of zinc ion 1.5 mmol/l
CaHAP 70 76 wt.% Moisture 5 wt.% max. Column diameter 4.5 cm
Iron-as Fe2O3 <0.3 wt.% Column height 25 cm
K.K.H. Choy, G. McKay / Environment International 31 (2005) 845 854 849

Table 5 0.7
The Langmuir and Sips single component isotherm constants and the SSE 0.6 a
values for three metal ions
0.5
Cd Cu Zn

qe, mmole/g
Langmuir isotherm 0.4
aL 158 69.2 62.2 0.3
KL 75.4 49.1 31.4
qm 0.477 0.709 0.505 0.2
SSE 8.03  10 3 2.02  10 2 2.19  10 2 0.1

Sips isotherm 0.0


a LF 88.9 67.0 41.2 0.0 1.0 2.0 3.0 4.0 5.0 6.0
K LF 15.7 47.5 20.8
0.9
n 1.30 0.843 1.33
SSE 7.90  10 3 1.14  10 2 2.18  10 2 0.8
b
0.7

qe, mmole/g
0.6
3.8. Fixed bed experiments
0.5
0.4
The experimental setup and procedures to carry out the
0.3
fixed bed experiments have been described in detail in the
0.2
previous paper (Ko et al., 2000). The metal ion solution is
0.1
0.0
0.7 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0
a Ce, mmole/dm3
0.6
Cu (exp) Cu (Langmuir) Cu (Sips)
0.5 Cd (exp) Cd (Langmuir) Cd (Sips)
qe, mmole/g

0.4
Cu (exp) Cu (Langmuir) Cu (Sips) Fig. 2. Experimental data and predictive curves for the sorption of Cd Cu
Zn (exp) Zn (Langmuir) Zn (Sips) ions at (a) 4:6 and (b) 3:7 mole ratio.
0.3

0.2
pumped vertically upwards inside the column. Rotameters
0.1 were calibrated to give the correct flow rate. Sample points
0.0 were located at 5, 10, 15, 20 and 25 cm height in the column
0.7 enabling a series of 10 cm3 sample syringes to be used to
b withdraw samples from the centre point of the bed for
0.6
analysis. The metal ion concentrations were determined
0.5 using ICP-AES. This procedure enabled the breakthrough
qe, mmole/g

0.4 Cu (exp) Cu (Langmuir) Cu (Sips) curves to be obtained. Table 4 shows the conditions for the
Zn (exp) Zn (Langmuir) Zn (Sips)
copper zinc ions system.
0.3

0.2

0.1
4. Results and discussion

0.0 4.1. Equilibrium isotherm


0.4
4.1.1. Single component equilibrium studies
c The experimental data were substituted into different sorption
0.3
equilibrium models in order to obtain the best fit isotherm. In this
qe, mmole/g

study, two isotherm equations, i.e. the Langmuir equation (Eq. (1))
0.2 and the Sips equation (Eq. (2)), were used to study the adsorption

Cu (exp) Cu (Langmuir) Cu (Sips)


0.1 Zn (exp) Zn (Langmuir) Zn (Sips)
Table 6
Selected properties of the metal ions (Lide, 1998; Nightingale, 1959)
0.0 Metal ions Ionic Hydrated Paulings
0.0 1.0 2.0 3.0 4.0 5.0 6.0 )
radius (A )
ionic radius (A electronegativity
Ce, mmole/dm3
Cu2+ 0.73 4.19 1.90
Cd2+ 0.95 4.26 1.69
Fig. 1. Experimental data and predictive curves for the sorption of (a) Cd
Zn2+ 0.74 4.30 1.65
Cu ions, (b) Cu Zn ions and (c) Cd Zn ions at equal mole ratio.
850 K.K.H. Choy, G. McKay / Environment International 31 (2005) 845 854

3.1 m=10.5g Table 8


Fixed bed model prediction results for the copper zinc ions fixed bed
a) Cu2+ Ion m=9.5g

2.6
m=8.5g sorption system on bone char
m=7.5g
Ct (mmol/dm3)

m=6.5g kf Ds SEE
2.1 HSDM
Cu2+ 6.06  10 4 1.61 10 9 0.488
Zn2+ 5.99  10 4 2.43  10 9 0.280
1.6

1.1 of theoretical and experimental data were made to evaluate the


deviation of the values using both isotherm models.
0.6 Figs. 1 and 2 show the sorption of binary metal ions onto bone
0 50 100 150 200
char. The sorption capacities for the copper ions in the three binary
5.8
HSDM sorption systems are always higher than the cadmium and zinc ions
b) Zn2+ Ion C(0)=5.351 mmol/dm3
C(0)=4.372 mmol/dm3 and the sorption capacity for the cadmium ions is also higher than the
4.7 C(0)=3.363 mmol/dm3 zinc ions. The possible reason may be due to the selectivity of ion
C(0)=2.782 mmol/dm3
C(0)=2.263 mmol/dm3 exchange in multi-component systems and the selectivity of metal
Ct (mmol/dm3)

3.7 ions onto bone char follows the order Cu2+ > Cd2+ > Zn2+. This result
trend is matched with the reversed order of hydrated ionic radii (Cu2+
2.6 (4.19 A ) > Cd2+ (4.26 A ) > Zn2+ (4.30 A ), see Table 6) and the
Paulings electronegativity (Cu2+ (1.90) > Cd2+ (1.69) > Zn2+ (1.65))
1.6 but does not coincide with the ionic radii values.
Lee and Moon (2001) studied the sorption of metal ions onto
0.5 natural zeolites. As zeolite removes the metal ions from solution by
0 50 100 150 200 both ion adsorption and ion exchange effects, the selectivity
Time (min)
properties should be similar to CaHAP (bone char). The selectivity
Fig. 3. Effect of sorbent mass and metal ion concentration on the adsorption of the NaCl-treated natural zeolite and the chabazite for heavy metals
of (a) Cu2+ and (b) Zn2+ ions onto bone char using HSDM. encountered follows the order Cs+ >> Pb2+ > Cd2+  Cu2+. The result
trend is also matched with the reversed order of hydrated ionic radii
process. The isotherm constants, Langmuir monolayer capacities [Cs+ (3.30A ) > Pb2+ (4.01 A ) > Cu2+ (4.19 A ) > Cd2+ (4.26 A
)].
and the corresponding sum of squares errors (SSE) values of three The predictions for the sorption of Cd Cu and Cu Zn ions are
metal ion systems are given in Table 5. The Langmuir and Sips quite reasonable, using the Langmuir and the Sips isotherms in the
equations produce comparable equilibrium correlation results.

4.1.2. Multi-component equilibrium studies


The IAST can be used to predict multi-component adsorption
isotherms using single component equilibrium data. Comparisons

Table 7
The surface diffusivities for Cu2+ and Zn2+ ion onto bone char at different
conditions
System C0 M kf Ds Total SSE
Cu2+ 5.19 8.5 6.06  10 4 5.40  10 9 0.149
4.28 8.5 6.06  10 4 5.12  10 9
3.21 8.5 6.06  10 4 3.72  10 9
2.63 8.5 6.06  10 4 2.76  10 9
2.11 8.5 6.06  10 4 2.11 10 9
3.21 10.5 6.06  10 4 3.65  10 9 0.170
3.21 9.5 6.06  10 4 3.43  10 9
3.21 8.5 6.06  10 4 3.72  10 9
3.21 7.5 6.06  10 4 3.60  10 9
3.21 6.5 6.06  10 4 3.56  10 9
Zn2+ 5.35 8.5 5.99  10 4 8.49  10 9 0.034
4.37 8.5 5.99  10 4 7.56  10 9
3.36 8.5 5.99  10 4 4.94  10 9
2.78 8.5 5.99  10 4 3.87  10 9
2.26 8.5 5.99  10 4 3.10  10 9
3.36 10.5 5.99  10 4 5.01 10 9 0.042
3.36 9.5 5.99  10 4 4.75  10 9
3.36 8.5 5.99  10 4 4.94  10 9
3.36 7.5 5.99  10 4 5.10  10 9 Fig. 4. Experimental data points and prediction curves for a Cu Zn binary
3.36 6.5 5.99  10 4 4.80  10 9 system based on homogeneous surface diffusion model.
K.K.H. Choy, G. McKay / Environment International 31 (2005) 845 854 851

1.00
D s and SSE values are presented in Table 7. The correlation
between the theoretical decay curves and the experimental data
points in most cases is good.
0.80
The effect of initial metal ion concentration is presented in Fig.
3b for a wide range of initial metal ion concentrations for the zinc
ion systems. The correlation between experimental and theoretical
Ct/Co

0.60
results is excellent, and the fitted parameters, k f and D s are also
listed in Table 7. It was found that the parameter D s was increasing
0.40 with increasing initial metal ion concentration and the surface
diffusion appears to depend on the initial metal ion concentration
of each system. It may be due to the surface coverage having an
0.20 effect on the diffusion for different initial metal ion concentration
0.0 2.0 4.0 6.0 8.0 10.0 systems.
t, hours
pH = 4.8 pH = 4.0 pH = 3.0 4.2.2. Fixed bed model
Fig. 5. The sorption of zinc ions on bone char at different pHs.
The experimental conditions and results of the fixed bed model
prediction based on the IAST and Sips isotherms for the Cu Zn
binary system is shown in Table 8. Fig. 4 illustrates the theoretical
IAST model. The IAST does not accurately predict the exper- and experimental breakthrough curves for a Cu Zn binary system
imental data in Cd Cu in 4:6 or 3:7 ratio systems. The sorption onto bone char in a fixed bed adsorption column. The values of k f
capacities for these binary systems may be enhanced. The were obtained from the correlation of the best-fit computer model
interaction between metal ions and sorbent may be the main factor for k f. This expression is:
affecting the quality of prediction. The prediction for the Cd Cu in
Sh 0:325=eRe0:36 Sc1=3 : 17
the 4:6 ratio systems appears better than the Cd Cu in the 3:7 ratio
system. It is lower than the Wilson and Geankoplis correlations (1966)
The overall performance of the IAST using the Langmuir and which gives values of 2.59  10 3 and 2.66  10 3 cm/s for
the Sips equations can provide a reasonable curve fitting to the copper and zinc compared to our model values of 6.06  10 4 and
experimental data. However, the prediction deviates from the 5.99  10 4 cm/s. The D s values in our system are in the range of
experimental data in the non-equimolar ratio systems except for 10 9 10 10 cm2 s. Only a few other values are available in the
Cu Cd in 3:7 ratio systems. literature. Trivedi and Axe (2000, 2001) reported D s values in the
range of 10 10 10 13 cm2/s for a range of metal ions sorbing on
4.2. Diffusion mass transport model hydrous oxide surfaces. Robinson et al. (1994) obtained values of
3.5 6.0  10 9 for metal ions on zeolites ion exchange resin and
4.2.1. Batch model values of 10 7 10 8 cm2/s were obtained for metal ion sorption
The experimental data and theoretical curves by the HSDM for onto hydroxyapatite (Suzuki and Takeuchi, 1994). The values
the effect of varying the mass of bone char added to a solution obtained in the present work are typical of the values obtained for
(same C 0) for copper ion system are shown in Fig. 3a and the k f, ion exchange/hydroxyapatite surface.

Zn (2.2mM)
After Zn-220ppm
Intensity [a.u.]

Cu-204ppm
Cu (2.0mM)

Cd Cd-356ppm
(3.6mM)

Blank

10.00 20.00 30.00 40.00 50.00 60.00


Degrees 2- Theta

Fig. 6. The XRD patterns of bone char after the sorption of metal ions at pH 3.0.
852 K.K.H. Choy, G. McKay / Environment International 31 (2005) 845 854

3.50
manufacturing process, the lone pair of electrons associated with
3.00 the oxygen atoms chemisorbed on to the surface and would be
coordinated to the inner transition metal vacant d-orbitals of the
[Ca] and {[Cu]o-[Cu]t} mM

2.50 europium ion to form a type coordination bond. A part of copper


and zinc ions may be adsorbed in a similar way. But no conclusive
2.00
evidence for this effect has been shown in this research. However,
1.50
we can conclude from the calcium ion exchange mechanism that a
part of metal ions uptake is due to the ion exchange process. The
1.00 sorption mechanisms can be attributed to at least three pathways:

0.50
1. Ion exchange of divalent metal ions from hydroxyapatite.
0.00 2. Sorption of metal ions from the hydroxyapatite surface lattice.
0.0 2.0 4.0 6.0 8.0 10.0 3. Sorption of metal ions from the carbon surface.
t, hour
Cu-2.1mM Cu-2.7mM Cu-3.1mM Cu-4.1mM Cu-5.0mM

Fig. 7. The removal rate of copper ions at pH 4 with different initial 5. Conclusions
concentrations of copper ions. The lower curves are the ion exchange rate
of calcium ions.
The Langmuir and the Sips equations were used in IAS
theory and modelling to correlate the experimental sorption
equilibrium capacity data in multi-component systems. The
4.2.3. Discussion of sorption mechanism results show that the sorption of metal ions for multi-
In this study of the sorption kinetic, the solutions were adjusted component systems can be predicted reasonably well from
at different pH values. Fig. 5 shows the sorption of zinc ions onto the IAS theory with the Langmuir equation or the Sips
bone char at different pHs. The concentrations of solution are equation for metal ions. Although the equal molar and
controlled at around 3 mM. The higher the pH of the solution, the unequal molar equilibrium data can be predicted in some
higher is the sorption rate which can be obtained. The decreasing cases by the IAS theory, the results for the mole ratios of 3:7
sorption rate may be caused by the particle attrition at low pH or
for the Cd Cu systems are not predicted very well. A
the sorption of hydrogen ions competing with zinc ions. Both
effects may happen at low pH during the sorption.
possible reason may be interaction between the metal ions
Fig. 6 shows the XRD patterns of bone char after the sorption of affecting the accuracy of calculation without incorporating
metal ions. The bone char was agitated with the copper and zinc activity coefficients into the model.
ions at pH 3. The three main peaks in XRD pattern became blurred The sorption kinetic of three metal ions, namely,
when the bone char was agitated with the metal solutions at pH 4. cadmium (II) ion, zinc (II) ion and copper (II) ion in the
When the solution adjusted to pH 3, the main three peaks in the three binary and one ternary systems is well correlated by
XRD pattern merged to one peak. Hence, the hydroxyapatite the Langmuir-type equation. The adsorption rate data of
adsorbing the metal ions at low pH decreases the crystallinity of metal ions onto bone char have been successfully correlated
structure. If the lower pH solution was used in the experiment, the using the HSDM and the diffusivities of Cu2+ ion and Zn2+
XRD pattern became a poorly crystalline compound. It is ion onto bone char at different conditions were determined.
interesting that the crystalline form of the CaHAP does not have
Finally, the well predicted system, namely copper plus zinc,
a great change in a blank solution with low pH but only in the
metal ion solution with low pH. The possible reason is that the
by the IAST has been incorporated into a fixed bed HSDM
metal ions in solution are adsorbed on the CaHAP surface and and used reasonably successfully to predict the break-
undergo the ion exchange process to form new apatite compound through curves in this multi-component system based on the
[i.e. Ca10x Mx (PO4)6(OH)2]. However, the solubility of the new individual single component isotherm data.
crystal may be unstable at that pH and then form a non-crystalline
phase compound. From the results, the crystalline form of CaHAP
in bone char decreases when the pH of metal solutions decreases 6. Notation
during the sorption.
The sorption of metal ions competing with the hydrogen ions
may be the other reason to cause the decrease in metal removal
rate. At pH 4.0, the sorption rates of copper ions onto bone char are q g/cm3 Particle density
shown in Fig. 7. The upper curves represent the removal rate of p Spreading pressure
copper ions from the solution. At the same time, the calcium ions P Reduced spreading pressure
( Void fraction of the bed
exchange from the hydroxyapatite lattice with the copper ions to
AL dm3/mmol Langmuir isotherm constant
the solution. The exchange capacities are around 40% of the total
a L,i dm3/mmol Binary Langmuir isotherm constant
sorption capacity at 10 h. a LF dm3/mmol Sips isotherm constant
In addition, the carbon content was reported to adsorb the C0 mmol/dm3 Initial liquid-phase concentration
radioactive ion, europium (152Eu3+). The authors (Abdel Raouf and Ce mmol/dm3 Equilibrium liquid-phase concentration
Daifullah, 1997) suggested that the carbons were activated at high Ds cm2/s Surface diffusion coefficient
temperatures to develop basic oxides on their surfaces during the dp Am Surface diffusion coefficient
K.K.H. Choy, G. McKay / Environment International 31 (2005) 845 854 853

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Engineering, Hong Kong University Science and Techno- sorption of metal ions on bone char. Chem Eng Sci 2000;55:5819 29.
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