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Removal of lead from battery manufacturing wastewater by egg shell

Article in Songklanakarin Journal of Science and Technology · May 2007

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 ORIGINAL ARTICLE

Removal of lead from battery manufacturing

wastewater by egg shell
Chumlong Arunlertaree1, Wanvisa Kaewsomboon2,
Acharaporn Kumsopa3, Prayad Pokethitiyook4
and Patra Panyawathanakit5

Abstract
Arunlertaree, C., Kaewsomboon, W., Kumsopa, A., Pokethitiyook, P. and Panyawathanakit, P.
Removal of lead from battery manufacturing wastewater by egg shell
Songklanakarin J. Sci. Technol., 2007, 29(3) : 857-868

This research was carried out to investigate the removal of lead from battery manufacturing waste-
water by egg shells. The effect of operating parameters i.e., initial pH, contact time, types of egg shell and
dose of egg shell were investigated. The characteristics and chemical compositions of egg shells were also
investigated and experimental samples were analyzed using AAS, then the data was statistically processed
using least significant difference at a 95% confidence level (p<0.05).
The results indicated that the optimum pH for lead removal using 4 types of egg shell was at pH 6, but
at this pH final concentration of lead was too low for study of adsorption isotherm. Therefore, unadjusted
pH wastewater was used with an initial lead concentration of about 2.365 mg/L, initial pH of 1.35-1.45.
Unadjusted pH wastewater decreased the use of expensive chemical reagent for adjusting pH and reduced
chemical residues in the environment due to basic properties of egg shell which immediately increased the
pH of solution. The optimum dose of egg shell was 1.0 g/100 ml of wastewater with a contact time of 90

1
Ph.D. (Fisheries), Asst.Prof., 2M.Sc. (Appropriate Technology for Resources and Environmental Develop-
ment), 3Ph.D. (Biology), Asst.Prof., Program of Appropriate Technology for Resources and Environmental
Development, Faculty of Environment and Resource Studies, Mahidol University, Salaya, Phutthamonthon,
Nakhon Pathom, 73170 Thailand. 4Ph.D. (Engineering), Assoc. Prof., Department of Biology, Faculty of
Science, Mahidol University, Paya Thai, Bangkok, 10400 Thailand. 5M.Sc. (Technology of Environmental
Management), Department of Science Service, Phaya Thai, Bangkok, 10400 Thailand.
Corresponding e-mail : [email protected]
Received, 17 April 2006 Accepted, 19 January 2007
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 858 Arunlertaree, C., et al.

minutes. The best adsorbent was natural duck egg shell, which had a significant difference from the other
types of egg shell. The final concentration of lead was 0.059 mg/L which was lower than the wastewater
quality standard.
Equilibrium modeling of the adsorption isotherm showed that removal of lead by 4 types of egg shells
were able to be described by the Freundlich model. From this study, precipitation might take part in the
adsorption process, especially at the high doses of egg shell which increased the high final pH of solution.
Finally, the result of the adsorption isotherm demonstrated that the descending lead removal efficiency was
natural duck egg shell, natural hen egg shell, boiled duck egg shell and boiled hen egg shell, respectively.

Key words : lead, egg shell, battery manufacturing, wastewater

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An important source of water pollutants is systems without proper management process. In

industrial discharge water. Most industrial waste- Thailand, lead is one of major pollutants in waste-
waters are discharged directly into natural water water. It is used as a major raw material in battery
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 859 Arunlertaree, C., et al.

manufacturing and wastewater from this industry (TDS) and total solids (TS) were analyzed accord-
can contain high concentration of lead about 0.50- ing to the standard methods. Lead was digested
25.00 mg/L ( Phomun, 2002). using nitric acid - hydrochloric acid digestion
Adsorption is a physico-chemical technique methods and its concentration determined by
which involves mass transfer between liquid and Atomic Absorption Spectrophotometer (AAS;
solid phase (Eckenfelder, 1980). This process can GBC 932 Plus) using the standard method (APHA
reduce chemical residues. However, the frequently et al., 1995).
used sorbent solid is a synthetic resin which is
quite expensive and a non-bio-degradable Egg shell preparation
substance, so it is more suitable to use agricultural Natural and boiled hen and duck egg shells
waste as the adsorbent. For example, egg shell were washed with tap water several times then
o
that has a good adsorptive properties i.e., pore air-dried and incubated in hot air oven at 40 C for
structure, CaCO3 and protein acid mucopolysac- 30 minutes (because protein component in egg
o
charide that can be developed into the adsorbent. shell can denature at high temperature; > 40 C).
Important functional groups of protein acid Consequently, egg shells were ground to a powder
mucopolysaccharide are carboxyl, amine and in a grinder, and sieved to obtain between 60-100
sulfate that can bind heavy metal ion to form mesh (0.25-0.104 mm) size particles.
ionic bond (Surasen, 2002). Moreover, egg shell
is neutralizing agent, any aqueous solution equili- The removal of lead from battery manufactur-
brated with egg shell becomes more basic (Brown ing wastewater using egg shells
and Lemay, 1985) so heavy metal can precipitate 1. The optimum pH value analysis
and deposit on egg shell particles. 1.1 The pH values of wastewater were
Other researchers removed lead from controlled at 5, 6 and 7 by using 1 M. NaOH.
synthetic wastewater but this study removed lead 1.2 100 ml of sample was added into
from battery manufacturing wastewater and there- Erlenmeyer flask and lead concentration was
fore has the advantage of direct application to real analyzed. Then 0.05 g of egg shell was added in
treatment. The main objectives of this study were; each sample and the rotary shaker was adjusted at
1) to study the optimum condition for the removal 200 rpm, 90 minutes.
of lead using natural and boiled hen and duck egg 1.3 Treated wastewater was filtered
shell 2) to study lead adsorption isotherm by the through filter paper No.4, then the lead concen-
egg shells 3) to compare the removal efficiency tration was determined.
using four types of egg shell. The results will be 2. The optimum contact time analysis
the guideline for the removing heavy metal, reduc- 2.1 0.05 g of egg shell was added into
ing chemical residues, decreasing operation cost, optimum pH wastewater (from step 1) and the
and recycling waste or by-product. rotary shaker was adjusted at 200 rpm with 30, 60,
90, 120 and 150 minutes.
Materials and Methods 2.2 Treated wastewater was filtered
through filter paper No.4, then the lead concen-
Wastewater preparation and wastewater char- tration was determined.
acteristic analysis 3. The optimum dose of egg shell analysis
Wastewater from the Battery Organization 3.1 100 ml of optimum pH wastewater
(Bang Na, Bangkok) was kept in polyethylene was added into Erlenmeyer flask, then lead con-
o
bottle and stored at 4 C in acid condition (pH < 2) centration was analyzed.
(Pollution Control Department, 1997) for pre- 3.2 0.05, 0.2, 0.5, 1.0 and 1.5 g of egg
cipitation at least 1 day. The wastewater character- shell was added into each sample and the rotary
istic included pH value, total dissolved solids shaker was adjusted at 200 rpm with optimum
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 860 Arunlertaree, C., et al.

contact time (from step 2). and initial lead concentration was higher than
3.3 Treated wastewater was filtered wastewater quality standard control of Thailand
through filter paper No.4, then the lead concen- Industrial Work Department in 1992.
tration was determined.
Chemical and physical properties of egg shells
Study of adsorption isotherm The chemical composition of all egg shells
Data from step 3 were used to study adsorp- were examined by x-ray fluorescence spectrometer
tion isotherm for determining the best adsorbent. (XRF; S4-Explorer) and the results were shown in
Langmuir's and Freundlich's adsorption isotherms Table 2. It was demonstrated that all egg shells
are the most commonly used for the description of had similar chemical contents which mainly
the adsorption data (Samuel and Osman, 1987). composed of CaCO3 and a few of other elements;
i.e. S, Mg, P, Al, K and Sr.
Statistical analysis The surface structure of 4 types of egg shells
The removal efficiency (%) were observed by scanning electron microscope
(SEM) as shown in Figure 1. It showed that egg
( A − B)
= ×100 (Kosayothin, 2002) shell surfaces were irregular shape. Pore sizes of
A
Then, A = Initial concentration (mg/L), B =
Final concentration (mg/L)
The results were investigated by using the
least significant difference at a 95% confidence
level by SPSS.

Results and Discussion

Characteristics of wastewater
The wastewater sample was collected from
(b)
battery manufacturing Bang Na, Bangkok. The
characteristics of wastewater were presented in
Table 1. The pH of wastewater was strongly acid

Table 1. Characteristics of wastewater from

battery manufacturing

Parameter Value of each Industrial effluent

parameter* standard**
Lead (mg/L) 2.365 < 0.2
Cadmium (mg/L) N.D. < 0.03
Copper (mg/L) N.D. < 1.0 (d)
SS (mg/L) 18.13 < 30
TS (mg/L) 2,245.60 - Figure 1. Morphology of 4 types of egg shell
TDS (mg/L) 2,227.47 < 2000 or < 5000 with magnification of x 5,000
pH 1.35-1.45 5.0-9.0 (a) Natural hen egg shell
* The Battery Manufacturing from Bangna, Bangkok (b) Boiled hen egg shell
** Wastewater quality standard control of Thailand (c) Natural duck egg shell
Industrial Work Department, 1992 (d) Boiled duck egg shell
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 861 Arunlertaree, C., et al.

Table 2. Chemical compositions of egg shells

Weight (%)
Element
Natural hen Boiled hen Natural duck Boiled duck
egg shell egg shell egg shell egg shell
CaCO3 96.48 96.48 96.48 95.99
S 2.31 3.59 1.24 1.92
Mg 0.404 0.440 0.996 0.927
P 0.501 0.469 0.508 0.481
Al - - - 0.309
K - - 0.0839 0.00957
Sr 0.0737 0.0734 0.118 0.093

natural and boiled hen egg shells were between of solution. Chemical precipitation was the main
0.3-0.6 µm while those of natural and boiled duck process in adjusted pH wastewater (pH 5, 6 and
egg shells were between 0.2-0.4 µm. 7), when pH level reached the optimum point,
Numerous studies have reported that the lead will precipitate as confirmed in Figure 2.
pore structure particulary affects by adsorption Solubility of lead continuously decreased from
capacity (Surasen, 2002; Polamesanaporn, 2001); pH 4 until it was in stable form at pH 7.
pictures from scanning electron microscope (SEM; 2. Effect of contact time (Unadjusted pH
HITACHI S-2500) showed that natural and boiled wastewater, 0.05 g egg shell /100 ml of waste-
duck egg shells had more pores per square-centi- water)
meter than natural and boiled hen egg shells. This The results were shown in Table 4 and
result was inconsistent with Kasetsuwan (1979). Figure 4. Removal efficiency for all types of egg
Moreover, amount and distribution of protein fiber shell at the contact time of 90, 120 and 150 mins
in natural hen and duck egg shells were higher was not significantly different, whereas the results
than in boiled hen and duck egg shells, as shown obtained at contact time 30, 60 and 90 mins were
in Figure 1.

Optimum conditions for lead removal by egg

shells
1. Effect of pH (0.05 g egg shell/100 ml
of wastewater, 90 mins of contact time)
The results were shown in Table 3 and
Figure 3. Lead removal efficiency changed signi-
ficantly at different pH. Optimum removal
efficiency of all types of egg shells was at pH 6
but unadjusted pH wastewater was conducted in
the next step of the experiment because the final
concentration of lead at pH 6 was too low for study
of adsorption isotherm. Unadjusted pH waste-
water decreased the use of expensive chemical
reagent for adjusting pH and reduced chemical
residues in the environment due to basic properties Figure 2. Mineral solubility in Pb-O-H-S-C system
of egg shell which immediately increased the pH at 25oC, 1 atm (Rose et al., 1979)
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 862 Arunlertaree, C., et al.

Table 3. Effect of pH on lead removal

Natural Hen Boiled hen Natural duck Boiled duck

Initial egg shell egg shell egg shell egg shell
pH conc. Final Removal Final Removal Final Removal Final Removal
(mg/L) conc. Efficiency conc. Efficiency conc. Efficiency conc. Efficiency
(mg/L) (%) (mg/L) (%) (mg/L) (%) (mg/L) (%)

5 1.063 0.587±0.015 a 44.78 0.650±0.014 a 38.82 0.546±0.013 a 48.67 0.630±0.014 a 40.70

6 0.349 0.077±0.005 b 78.03 0.094±0.006 b 72.97 0.073±0.004 b 79.18 0.086±0.005 b 75.36
7 N.D. N.D. c 100 N.D. c 100 N.D. c 100 N.D. c 100

Remark: Differences of superscripts in each column indicate statistically significant differences with the confidence of
95% by LSD

Table 4. Effect of contact time on lead removal

Natural Hen Boiled hen Natural duck Boiled duck

Contact Initial egg shell egg shell egg shell egg shell
time conc. Final Removal Final Removal Final Removal Final Removal
(mins) (mg/L) conc. Efficiency conc. Efficiency conc. Efficiency conc. Efficiency
(mg/L) (%) (mg/L) (%) (mg/L) (%) (mg/L) (%)

30 2.365 2.017±0.005 a 14.70 2.179±0.007 a 7.86 1.456±0.009 a 17.28 2.117±0.008 a 10.48

60 2.365 1.831±0.015 b 22.58 2.003±0.014 b 15.29 1.661±0.014 b 29.76 1.936±0.011 b 18.15
90 2.365 1.637±0.006 c 30.79 1.819±0.008 c 23.10 1.544±0.006 c 34.73 1.747±0.004 c 26.13
120 2.365 1.634±0.012 c 30.92 1.821±0.016 c 22.99 1.536±0.007 c 35.07 1.734±0.015 c 26.70
150 2.365 1.631±0.011 c 31.03 1.821±0.013 c 22.99 1.535±0.013 c 35.09 1.733±0.013 c 26.74

Remark: Differences of superscripts in each column indicate statistically significant differences with the confidence of
95% by LSD

Table 5. Effect of dose of egg shell on lead removal

Natural Hen Boiled hen Natural duck Boiled duck

Dose of Initial
egg shell egg shell egg shell egg shell
egg conc.
shell (mg/L) Final Removal Final Removal Final Removal Final Removal
(g) conc. Efficiency conc. Efficiency conc. Efficiency conc. Efficiency
(mg/L) (%) (mg/L) (%) (mg/L) (%) (mg/L) (%)

0.05 2.365 1.637±0.006a 30.80 1.819±0.009a 23.04 1.544±0.004a 34.74 1.747±0.005a 26.15
0.20 2.365 0.698±0.009b 70.50 0.950±0.008b 59.83 0.513±0.006b 78.31 0.884±0.005b 62.62
0.50 2.365 0.359±0.011c 84.83 0.548±0.018c 76.83 0.271±0.006c 88.53 0.441±0.012c 81.37
1.00 2.365 0.082±0.004d 96.53 0.122±0.005d 94.84 0.059±0.005d 97.51 0.099±0.008d 95.81
1.50 2.365 0.088±0.009d 96.42 0.120±0.006d 94.94 0.051±0.003d 97.56 0.097±0.013d 95.76

Remark: Differences of superscripts in each column indicate statistically significant differences with the confidence of
95% by LSD

significantly different. Therefore, the optimum equilibrium time to remove lead in synthetic waste-
contact time for all types of egg shell should be at water by egg shell could be reached at about 80
90 mins. This result was consistent with Pawebang min. Similary the study of Lee et al. (1998) on the
and Sukcharoen (1999), who reported that the removal of lead by crab shell particle showed that
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 863 Arunlertaree, C., et al.

types of egg shell should be 1.0 g. Dose of egg

shell affected the removal of lead, because the
removal efficiency of solutes increased with
increasing dose of adsorbent (Eamsiri et al., 2005).
The removal efficiency increased according to the
increasing dose of egg shell at an appropriate
level.
According to the chemical composition
analysis in Table 2, egg shell mainly composed of
Figure 3. Effect of pH on lead removal by 4 types CaCO3. Major alkaline contributors in egg shell
of egg shell
was CaCO3 so it was expected that any aqueous
solution equilibrated with egg shell became more
basic that confirmed by following mechanism
(Brown and Lemay, 1985).
2+ 2-
CaCO3 Ca + CO3
2- - -
CO3 + H2O HCO3 + OH

Hydrolysis reaction of CaCO3 gave basic

2+ -
Figure 4. Effect of contact time on lead removal solution because Ca and OH increased the pH of
by 4 types of egg shell the solution as well as in this experiment, adding
various doses of egg shell into wastewater
increased the pH of solution as shown in Table 6.
This basic property of egg shells, which
increased the pH of solution, was of advantage to
decrease the use of expensive chemical reagent for
adjusting pH of wastewater (decreasing operation
cost) and reduced chemical residues in the envi-
ronment. At optimum condition (1.0 g of egg shell/
100 ml of wastewater), the final pH and final
concentration of lead were lower than wastewater
Figure 5. Effect of dose of egg shell on lead quality standard control of Thailand Industrial
removal by 4 types of egg shell Work Department, 1992

the necessary contact time to reach equilibrium Adsorption isotherm

was about 90-120 mins. Experiments were conducted to determine
3. Effect of dose of egg shell (Unadjusted the adsorption isotherm of lead using egg shells
pH wastewater, 90 mins of contact time) at 0.05, 0.2, 0.5, 1.0 and 1.5 g in 100 ml of un-
The results were shown in Table 5 and adjusted pH wastewater (pH 1.35-1.45). Initial
Figure 5. Removal efficiency for the doses of all lead concentration was approximately 2.365 mg/
types of egg shell of 0.05, 0.2, 0.5, and 1.0 g were L. The experimental datas were calculated to
significantly different whereas the results obtained determine the adsorption isotherm by using the
from using 1.0 and 1.5 g. were not significantly Langmuir and Freundlich models.
different. Therefore, an appropriate dose for all The Langmuir equation was expressed as :
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 864 Arunlertaree, C., et al.

Table 6. Final pH at various doses of egg shell

Dose of Final pH at various doses of egg shell

Egg shell Natural hen Boiled hen Natural duck Boiled duck
(g) egg shell egg shell egg shell egg shell
0.05 1.45±0.01 1.43±0.02 1.45±0.02 1.44±0.04
0.20 1.75±0.02 1.74±0.01 1.76±0.02 1.73±0.02
0.50 4.48±0.03 4.44±0.03 4.52±0.01 4.44±0.02
1.00 5.85±0.01 5.80±0.02 5.89±0.03 5.82±0.02
1.50 5.88±0.02 5.85±0.02 5.92±0.02 5.84±0.01

Xm bCe 1 x
Qe = (Samuel and Osman,1987) Log Qe = log K + logCe ; (Qe = )
1 + bCe n m
where; Plotting Log Qe against log Ce, a straight line, slope
X = the amount of solute adsorbed per unit was 1/n and intercept was log K. The calculated n
weight value was qualitative related to the distribution of
Xm = amount of solute adsorbed per unit site bonding energies. K values could be used to
weight of adsorbent required for compare the removal efficiency of each adsorbent.
monolayer coverage of the surface The final concentrations (Ce) of lead, as
B = a constant related to the heat of shown in Table 7, were plotted as Ce/Qe versus Ce
adsorption for the Langmuir model as shown in Figure 6, and
Ce = equilibrium concentration of the log Qe versus log Ce for the Freundlich model
solute (Figure 7), and values of the constants for each
For linearization of the data, Equation could be type of egg shells were determined after lineariz-
written in the form : ing the equations through linear regression analy-
Ce 1 C sis.
= + e The K values and all constant values in
Qe bXm Xm
Langmuir (Xm,b) and Freundlich (K,1/n) equations
Plotting Ce/Qe against Ce, a straight line, slope was were also presented in Table 8. In our experimental
1/Xm and an intercept is 1/bXm. The b value was ranges, the results of all egg shells tended to be
the ratio between adsorption rate and desorption described by the Freundlich model, because the
rate. Xm could be used to compare the removal regression line obtained from the Freundlich curve
efficiency of each adsorbent. fit better than the Langmuir curve. K values in
The Freundlich equation was expressed as : Freundlich equation could be used to compare the
x removal efficiency of each adsorbent. It was
= KCe1/n (Samuel and Osman,1987) shown that the descending lead removal efficiency
m
on K value of each egg shell was natural duck egg
where; shell (K = 1.2362), natural hen egg shell (K =
x = the amount of solute adsorbed 0.9889), boiled duck egg shell (K = 0.7901) and
m = the weight of adsorbent boiled hen egg shell (K = 0.6834), respectively.
Ce = the solute equilibrium concentration The n values obtained from this study were higher
K and 1/n = constants characteristic of the than 1, which may indicate that the energies of
system adsorption were decreased with increasing surface
For linearization of the data, the Freundlich equa- area of egg shell that bind with the heavy metal
tion was written in logarithmic form : ion. The results were consistent with Polamesana-
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 865 Arunlertaree, C., et al.

Table 7. Final concentration of lead at various doses of egg shell and adsorption
capacity

Types of Dose of Final Solute Adsorption

egg shell egg shell Conc. Adsorbed capacity Ce/Qe Log Ce Log Qe
(g) (mg/L) (mg) (mg/g)
m Ce x Qe, x/m

Natural hen 0.05 1.637 0.073 1.457 1.124 0.214 0.163

egg shell 0.20 0.698 0.167 0.834 0.837 -0.156 -0.079
0.50 0.359 0.201 0.401 0.895 -0.445 -0.397
1.00 0.082 0.228 0.228 0.359 -1.086 -0.641
1.50 0.088 0.228 0.152 0.580 -1.056 -0.819
Boiled hen 0.05 1.819 0.055 1.092 1.665 0.260 0.038
egg shell 0.20 0.950 0.950 0.708 1.343 -0.022 -0.150
0.50 0.548 0.201 0.363 1.508 -0.261 -0.440
1.00 0.122 0.224 0.224 0.544 -0.914 -0.649
1.50 0.120 0.225 0.150 0.802 -0.921 -0.825
Natural duck 0.05 1.544 0.082 1.643 0.940 0.189 0.216
egg shell 0.20 0.513 0.185 0.926 0.554 -0.290 -0.033
0.50 0.271 0.201 0.419 0.647 -0.567 -0.378
1.00 0.059 0.231 0.231 0.256 -1.229 -0.637
1.50 0.051 0.231 0.154 0.331 -1.292 -0.812
Boiled duck 0.05 1.747 0.062 1.236 1.414 0.242 0.092
egg shell 0.20 0.884 0.148 0.741 1.194 -0.054 -0.130
0.50 0.441 0.192 0.385 1.146 -0.356 -0.415
1.00 0.099 0.227 0.227 0.437 -1.004 -0.645
1.50 0.097 0.227 0.151 0.642 -1.013 -0.820

Table 8. Constants and correlation coefficients for lead removal with

4 types of egg shell

Type of Langmuir model Freundlich model

egg shell Xm b R 2
K 1/n R2
Naturalhen 2.5602 0.7297 0.7283 0.9889 0.6923 0.9553
egg shell
Boiled hen 1.7908 0.7207 0.6829 0.6834 0.6453 0.9423
egg shell
Natural duck 2.5094 1.1347 0.8250 1.2362 0.6600 0.9680
egg shell
Boiled duck 1.9547 0.8095 0.7467 0.7901 0.6441 0.9570
egg shell

porn (2001), who found that the Cd removal egg shells have more protein fiber than boiled hen
efficiency of natural hen egg shell was higher and duck egg shells when observed by SEM. Thus
than protein - removed hen egg shell. protein fiber which comprising of carboxyl and
From this experiment, natural hen and duck amine groups may promote the natural duck and
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 866 Arunlertaree, C., et al.

Figure 6. Langmuir adsorption isotherm on lead removal by 4 types of egg shells

Figure 7. Freundlich adsorption isotherm on lead removal by 4 types of egg shell

hen egg shell to bind lead ions better than boiled shell so that the amount of adsorbent increased.
duck and hen egg shell. Moreover, acid condition In addition, removal efficiency of duck egg shell
of wastewater may cause protein fiber in natural was higher than that of hen egg shell because duck
hen and duck egg shell to be contracted and egg shells had more pores per square-centimeter
+
tightly captured, blocking the reaction between H than hen egg shells, that was consistent with
and CaCO3. This phenomenon resulted in de- Kasetsuwan (1979). Chemical composition analy-
creasing solubility of natural hen and duck egg sis from XRF in Table 2 indicated that CaCO3 in
Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 867 Arunlertaree, C., et al.

4 types of egg shells may slightly affect the environment due to basic properties of egg shell
removal efficiency. which immediately increased pH of solution. The
From this study, removal of lead might optimum contact time and optimum dose of egg
occur through more than one type of mechanism shell were 90 mins and 1.0 g/100 ml of waste-
i.e., adsorption and precipitation, especially at the water, respectively. Final concentration of lead at
high doses of egg shell (0.5-1.5 g/100 ml of optimum condition was lower than the wastewater
wastewater) which increased final pH more than quality standard.
4 so precipitation might take part in the adsorp- The adsorption isotherm data tended to fit
tion process. As confirmed with Figure 2, the with the Freundlich model. From this research,
solubility of lead continuously decreased from pH precipitation might take part in the adsorption
4 until it was in stable form at pH 7; as a result process, especially at the high doses of egg shell.
-
lead might form complexes with OH as Pb(OH)2, The result of the adsorption isotherm demonstrated
so lead hydroxyl species might participate in the that the descending lead removal efficiency was
adsorption and precipitate onto the egg shell natural duck egg shell, natural hen egg shell, boiled
structure. However, at low dose of egg shell (0.05- duck egg shell and boiled hen egg shell, respect-
0.2 g/100 ml of wastwater), the final pH of solu- ively. (as discussed earlier). In the study of adsorp-
tion was lower than 4 so adsorption was the main tion isotherm, final pH should be stable but in this
mechanism. experiment, final pH varied according to various
These results were consistent with other doses of egg shell. This was the limitation of using
studies performed with basic adsorbent material real wastewater for uncontrolled final pH and it
i.e., fly ash and bentonite. The mechanism that was different from synthetic wastewater. When
influenced zinc removal characteristics of bentonite fixed dose of egg shell was added into various
was adsorption, ion exchange and precipitation (at initial concentration of synthetic wastewater, final
the high pH level i.e., pH 8), zinc might form pH was stable.
-
complex with OH so zinc hydroxyl species might In summary, the egg shell could remove
participate in the adsorption and precipitate onto lead due to its physical and chemical properties
the bentonite structure (Kaya and Oren, 2005). such as CaCO3 contents (95-96 %), pore structure
Moreover, the results were consistent with Boon- and functional group i.e., carboxyl, amine and
paniad (1998) who studied the removal of lead and sulfate group. Moreover, egg shell was a neutraliz-
zinc by fly ash. Hydroxide ion might participate ing agent, any aqueous solution equilibrated with
in the adsorption process and increase the pH egg shell became more basic so heavy metals
of solution so adsorption capacity was increased. could precipitate and deposit on egg shell particles.
Formation of Pb(OH)2 on the surface of ash was
presumably the mechanism followed by adsorp- Acknowledgements
tion. Precipitation of some Pb(OH)2 could be
deposited on fly ash particles. The authors would like to thank Faculty
of Graduate Studies, Mahidol University for
Conclusion Supported in Part by the Thesis Grant. Apprecia-
tion was also expressed to Mr. Somnuk Parnthong
The results from this work showed that the at Battery Organization, Bang Na, Bangkok, for
optimum pH was at pH 6 but final concentration supporting with wastewater used in this study
of lead was too low for study of adsorption iso- and all staffs at the Central Instrument Facility
therm, so unadjusted pH wastewater was used in (CIF), Center of Nanoimaging and Department of
this study. Unadjusted pH wastewater decreased Chemistry at Faculty of Science, Mahidol Uni-
the use of expensive chemical reagent for adjust- versity for supporting with AAS, SEM and XRF.
ing pH and reduced chemical residues in the
 Songklanakarin J. Sci. Technol. Removal of lead from battery manufacturing wastewater
Vol. 29 No. 3 May - Jun. 2007 868 Arunlertaree, C., et al.

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