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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
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
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
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
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
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.
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
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
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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