Lead Pollution Removal from Water via Clinoptilolite Fixed Bed Column

Sukru Dursun, Asuman Pala, M. Emin Argun

Selcuk University, Engineering Faculty, Environmental Engineering Dept., Konya, Turkey

sdursun@selcuk.edu.tr, Tel: +90 332 2232057, Fax: +90 332 2410635
Abstract Colour (dry) White Total Elements Bed kth Removal R2
Clinoptilolite (a natural zeolite) was used to investigate its adsorption depth Q qexp qcal (mL min- efficiency
Colour (wet) Light olive SiO2 (%) 70.05
capacity for the lead (II) ions from artificial polluted tap water in this study. (cm) (ml/min) (mg/g) (mg/g) 1
mg-1) (%)
For the experimental studies, Clinoptilolite mineral which is 25-140 mesh Sand (%) 82.56 Al2O3 (%) 9.84
Clay (%) 3.44 Fe2O3 (%) 0.96 10 80 0.1911 0.1389 -20 77 0.75
size was used by activating with HCl, and lead ion removal efficiencies were
Silt (%) 14.00 CaO (%) 2.15 20 80 0.0718 0.0178 -195 99 0.73
examined. Experiments were studied under laboratory batch and fixed bed
conditions. The highest removal efficiency was found as about 87% at pH 5 Structure Silty sand MgO (%) 0.58
for batch conditions. Similarly, experiments were carried out at different Density 2.14 g/cm3 Na2O (%) 0.24
temperature values, and the maximum efficiency was obtained at 30 oC. Volume weight 1.10 g/cm3 K2O (%) 1.44
Column experiments were also carried out and Thomas’ kinetic parameters Porosity (%) 48.47 MnO (%) 0.05
calculated for 20 cm and 10 cm bed height. pH 7.62 Pb3O4 (%) 0.0014
Total Salt (%) 0.03< ZnO4 (%) 0.0044
Key Words: Heavy metal, lead, adsorption, fixed bed column, zeolite, CaCO3 (%) 1.25 Cu (ppm) 1.56
clinoptilolite.
Changeable Cations (meq/100g) Zn (ppm) 34.95
INTRODUCTION Ca++ 21.00 Cd (ppm) 0.09
Heavy metal pollution is an important environmental problem in the Mg++ 12.00 Ni (ppm) 4.25
aqueous system originated from industry. There are many heavy metals Na+ 11.52 Cr (ppm) 2.36
produced from the industry that lead may be found a lot of industrial K+ 27.18 Fire lost (%) 14.06
wastewater. Heavy metal pollution exists in many industrial wastewaters,
such as metal plating facilities, mining operations, fertilizer industries, RESULTS
paints and pigments, battery and tannery industries (Argun et. al., 2007). Effect of initial Pb(II) concentration by the clinoptilolite adsorption
Some metals associated with these activities are as follows; lead, cadmium, Fig. 3. Breakthrough curves for Pb(II) ions at different bed depths. Initial
Determination of effective Pb+2 concentrations on removal efficiency of
copper, chromium etc. Heavy metals are not biodegradable and tend to concentration: 35 mg L-1 and column diameter: 1.5 cm.
clinoptilolite was studied with different concentration of Pb(II). Maximum
accumulate into living organisms, causing various diseases and other removal efficiency was obtained with 1.6 mg Pb +2/L concentrations. Later
problems. Human intake of Pb causes to disruption of the biosynthesis of on, decreasing removal efficiency was detected with increasing initial heavy
hemoglobin, rise in blood pressure, kidney damage, miscarriages and metal concentrations in the solutions. It is likely that a given mass of
abortions, brain damage and diminished learning abilities of children. This adsorbent material has a finite number of adsorption sites, and that as metal
heavy metal is also known carcinogen. Therefore, the removal of excess concentrations increase, these sites become saturated. That is, there is some
heavy metal ions from water is essential to protect human and environmental metal concentration that produces the maximum adsorption for a given
health. adsorbent mass, and thereafter, adding more metal cannot increase
adsorption because no more sites are available: all are occupied (Argun et.
The most widely used methods for removing metal ions are as follows; al., 2007).
precipitation with chemical and electrochemical methods (Chen., 2004;
Marani et al, 1995). A major problem with this type of treatment is the Effect of adsorbent doses on the Pb(II) adsorption
disposal of the precipitated wastes. Ion exchange treatment which is the Effect of adsorbent doses on the Pb(II) adsorption by the clinoptilolite
second most widely used method for metal ion removal (Petrus and was investigated with changed adsorbent doses from 1.0 to 4.0 g that
Warchol, 2003). However, ion exchange treatment does not appear to be maximum removal efficiencies have been achieved to be 67% with 2.0 g
economical. Activated carbon’s high cost has also prevented its wide usage. clinoptilolite/100 ml solution.
It has been reported that some aquatic plants (Axtell et al., 2003),
agricultural by-products (Argun et al., 2006; Argun et al., 2005), sawdust Solution pH effect on adsorption capacity
(Argun et al., 2007), clay (Márquez et al., 2004), zeolite (Karatas., 2007) Effect of pH on the adsorption of Pb(II) by the clinoptilolite was also
and microorganisms (Li et al., 2004) have the capacity to adsorb and Fig. 4. Thomas model plots of Pb(II) adsorption on the clinoptilolite at
investigated with the changing pH values from 3.0 to 9.0. The results shows different bed depth
accumulate heavy metals. that maximum removal efficiencies have been achieved to be 87 % at pH
5.0. DISCUSSIONS
Natural zeolites have been used as adsorban and ion exchanger with
discovering crystal feature and some chemical structure. It is physical This paper presents the results of Pb(II) ions removal from aqueous
Effect of sample temperature and determination of adsorption solution using a common, naturally occurring clinoptilolite. Operational
structure look like a selective sieve and named as moleculer sieve. SiO 4 and izoterm/kinetics
AlO4 octahedrals are the monomers of the zeolites that Si or Al was centre of parameters such as initial Pb(II) concentrations, adsorbent dose, pH of the
Activated 2 grams of clinoptilolite was tested for adsorption of Pb(II) at solution, temperature, and contact time clearly affect the removal efficiency.
the structure and oxygen was on the corners. Crystal structure of A and Z different sample temperature between 10 to 50 oC. Results show that
zeolites are given the Figure 1 (Anonym, 2007). The optimum Pb(II) removal by the clinoptilolite was obtained at pH 5.
optimum working temperature was about 30 oC. Removal of Pb +2 from the Column studies were also applied and seemed that fixed bed achieved
The aim of this study was removal of the ionic lead pollution from the water was 88% at this temperature; it was lowered at lower and at higher
preliminary treated water using clinoptilolit as a natural and economical equilibrium rapidly and that high lead removal efficiency obtained. Lead
temperatures adsorption mechanisms by clinoptilolite may be explained as follows:
material. In order to determine the adsorption capacity of the activated 1. Vander-walls and hydrogen binding of lead with hydroxyl group of
clinoptilolite, the equilibrium data for the adsorption of lead were analyzed clinoptilolite surfaces.
in the light of adsorption isotherm models. Mostly used adsorption 2. Ion exchange between Pb(II) ions and exchangeable cations (Na, K
isotherms are Langmuir and Freundlich equations. The straight line nature of etc.) which balance negative charge of aluminium atoms.
the graph indicates that the adsorption confirms the Langmuir model. The 3. Diffusion of Pb(II) through selective sieve of clinoptilolite named as
experimental data points were fitted to the Langmuir equation, but it was not molecular sieve (Mc Bain, 1932).
fit well to the Freundlich equation. Chemical kinetics of lead removal was A process using the clinoptilolite for the removal of heavy metal
also investigated in batch reactor for 60 min. contact time that checked with seemed to be potentially more economical than current process technology
o
0, o1, o2 and o3 order reaction equations. Only our data is quite well fit to 2nd because of its abundant availability in Turkey and economical price.
order reaction kinetic. Square of correlation coefficient was R 2=0.9806
Fig. 1. Crystal Zeolite structure unit, (Anon., 2007) which confirms good relation between contact time and concentration Acknowledgment: Dr. Dursun thanks to COST Vademecum/Financial
change by experimental period. Instruments (COST 637) for providing financial support of this symposium.
Fixed bed column studies References
In Figure 3, breakthrough curves are presented for Pb(II) ions, where C t Anonym, 2007. http://www.zeoliteproducer.com/zeolit.html
represents the time-dependent outlet metal concentration of the bed and C o Argun, M. E., Dursun, Ş., Özdemir, C., Karataş, M., 2007. Heavy metal
the inlet concentration. It can be seen that at lower bed depth, a steeper adsorption by modified oak sawdust: thermodynamics and kinetics.
breakthrough curve is obtained and the breakthrough point is moved towards Journal of Hazardous Materials. 141, 77-85.
left on the Ct/Co vs. effluent volume (Veff) at a given flow rate. Thomas Argun, M.E., Dursun, Ş., 2006. Removal of heavy metal ions using
model (Thomas, 1944) was used to calculate of column parameter (Eq. 1); chemically modified adsorbents. J. Int. Environ. Appl. Sci. 1, 27-40.
�C
o
� k Th q o M k
Th
C
o Argun, M.E., Dursun, S., Gür, K., Özdemir, C., Karatas, M., Dogan, S.,
ln
� - 1
�= - V
eff
(1)
2005. Adsorption of copper on the modified wood (pine) materials.
Fig. 2. Sketchy drawing of bi-layer on the clinoptilolite surface. Nonpolar
�C
t � Q Q
Cell. Chem. Technol. 39, 581-593.
molecules partition into the bi-layer, exchange with cations (Pb2+) bind to where kTh is the Thomas rate constant (ml min −1mg−1), qo the equilibrium
the zeolite surface. heavy metal uptake per gram of the adsorbent (mg g −1), Q is the volumetric Axtell, N.R., Sternberg, S.P.K., Claussen, K., 2003. Lead and nickel removal
flow rate (ml min -1) and M is the amount of adsorbent in the column (g). The using Microspora and Lemna minor. Bioresour. Technol. 89(1), 41-48.
MATERIALS AND METHOD kinetic coefficient kTh and the adsorption capacity of the column qo can be Chen, G (2004) Electrochemical technologies in wastewater treatment
In this study, Beyköy region clinoptilolite was used provided from determined from a plot of ln((Co/Ct)−1) against effluent volume (Veff) at a Separation and Purification Technology, 38, 11-41
Balıkesir city in Turkey. Chemical composition of the clinoptilolite is given given flow rate (Figure 4). Increasing the bed depth caused more metal ions Karatas, M., 2007. Removal of Cadmium from Water Using Clinoptilolite,
in Table 2. Materials used in this study were between 25-140 mesh sizes. contacted with clinoptilolite at the same time according to lower bed depth, Asian J. Chem. 19, 3963-3970.
Gallenkap (U.K.) thermostatic shaker incubator was used for batch so the adsorption capacity reached the equilibrium value faster (Table 2). Li, Q., Wu, S., Liu, G., Liao, X., Deng, X., Sun, D., Hu, Y., Huang, Y., 2004.
experiments. Lead concentrations were measured by Dr. Lange Cadas-200 Also metal ions had more time to contact with clinoptilolite for higher bed Simultaneous biosorption of cadmium (II) and lead (II) ions by
Spectrophotometer (Germany). The pH was adjusted to required values depth and therefore removal efficiency was higher. However for low bed pretreated biomass of Phanerochaete chrysosporium. Sep. Purif.
using Jenway 3010 pH meter. depth adsorption capacity was high because of the lower amount of Technol. 34(1-3), 135-142.
Clinoptilolite was treated with acid or base solution in different clinoptilolite. Marani, D., Macci, G., Pagano, M. 1995. Lead Precipitation in The Presence
concentration to improve its adsorption capacity. For this process, 2.0 grams of Sulphate and Carbonate Testing of Thermodynamic Predictions,
of clinoptilolite in 100 ml distilled water containing different amounts of
acid or base was shaken at different shaking seeped and temperature. With Parameters predicted from
Table 2:
Water Research, Vol. 29, No:4, pp. 1085-1092.
Márquez, G.E., Ribeiro, M.J.P., Ventura, J.M., Labrincha, J.A., 2004.
this procedure, the best activation media was determined 2.0 ml 1 M HCl Removal of nickel from aqueous solutions by clay-based beds.
additions. For this reason, activated Clinoptilolite samples with 2.0 ml 1 M
HCl were used in following experiments. After designing the activation
the Thomas model of Pb(II) Ceramics International 30(1), 111–119.
Petrus, R., Warchol, J., 2003. Ion exchange equilibria between clinoptilolite
media, to optimum adsorbent amount, Pb(II) concentration, solution pH and
sample temperature were studied before fixed bed experiment design. adsorption at different bed and aqueous solutions of Na+/Cu2+, Na+/Cd2+ and Na+/Pb2+, Microporous
and Mesoporous Materials, 61 137–146.
Thomas, H.C., 1944. Heterogeneous ion exchange in a flowing system. J.
depth (adsorbent mass: 46 g for
Column experiments were carried out using ion exchange aperture with two
different column length (1.5 cm diam.). Am. Chem. Soc. 66, 1664–1666.

. Special composition of the

Table 1
20 cm bed depth and 20 g for
clinoptilolite used in this study 10 cm bed depth)