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Technical note
Abstract
Natural Bulgarian zeolite was tested for its ability to remove Cu2+ from model wastewater. Inuence of process variables was
investigated. It was found that the optimum wastewater to zeolite ratio is 100:1 and the optimum pH value of water to be treated is
5.5 to 7.5. Zeolite with ner particles shows a higher uptake capacity. The simultaneous presence of Ca2+ and Mg2+ in con-
centrations similar to their concentrations in Bulgarian natural water does not signicantly inuence the uptake of Cu2+. Zeolite
modication by treating it with NaCl, CH3COONa and NaOH increases its uptake ability. Copper ions are strongly immobilized
by modied zeolite and secondary pollution of water caused by its contact with preloaded zeolite is very low (1.52.5% of Cu2+
preliminary immobilized have been released back into acidied water). Contacting with 2 mol dm 3 NaCl can easily regenerate
loaded zeolite; best results were obtained for zeolite modied with NaCl. Requirements of Bulgarian standards for industrial was-
tewater can be met by a one-stage process for an initial Cu2+ concentration of 10 mg dm 3, and by a two stage process for an initial
Cu2+ concentration of 50 mg dm 3. Uptake of Cu2+ by zeolite from neutral wastewater has proved to be as eective as Cu2+
removal by precipitation of copper hydroxide. The process of Cu2+ uptake by natural zeolite is best described by the kinetic
equation for adsorption. This fact, together with the correlation found between the Cu2+ uptake and the amount of Na+, Ca2+
and K+ released into solution by zeolite shows that the ion exchange sorption plays the basic role in Cu2+ uptake by natural
zeolite. The value obtained for the apparent activation energy (26.112 kJ mol 1) implies that the process can be easily carried out
with a satisfactory rate. The uptake equilibrium is best described by the Langmuir adsorption isotherm, with Langmuir constants
KL=6.410 2 dm3 mg 1 and M= 6.74 mg g 1. The apparent equilibrium constant found shows moderate anity of zeolite for
Cu2+. Values of G and H found show the spontaneous and endothermic nature of the process of Cu2+ uptake by natural
zeolite. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Natural and modied zeolite; Wastewater treatment; Copper ions removal
energy, important for the practical application of zeo- changing that parameter and keeping other parameters
lites in wastewater treatment; and (d) determine the constant. Uptake eciency was calculated using the
adsorption equation which best describes the equili- equation:
brium uptake and to calculate thermodynamic para-
meters (G , H , and S ) for the practical Uptake; % Co Ceq =Co 100 1
implementation of zeolites technology.
where Co and Ceq are the initial and the equilibrium
concentration of pollutant, mg dm 3.
2. Methods and materials Desorption experiments were made in order to check
how strongly Cu2+ ions were immobilised by zeolite.
Bulgarian natural zeolite was used. It had the following One gram of preloaded natural and modied (by con-
chemical compositions, in mass %: SiO2 68:70, tacting with NaCl, CH3COONa and with NaOH) zeolite
Fe2 O3 2:28, TiO 0:15, Al2 O3 11:83, CaO 2:66, which showed the highest uptake was placed in contact
MgO 0:76, MnO 0:04, Na2 O 1:60, K2 O 4:01, with (a) distilled water acidied to pH=2.5 by HNO3
P2 O3 0:14, SO3 0:225, ignition loss=7.62, totalling addition, and (b) 2 mol dm 3 NaCl solution for 6 h.
100.02. Clinoptilolite was found to be the predominate Each experimental result was obtained by averaging
material. Its cation exchange capacity determined as the data from two parallel experiments. Kinetic equa-
described in Kallo and Sherry [1] was 134.3 meq/100 g. tions for the rst order reversible [9] and rst and sec-
Zeolite was modied by heating and by placing it in con- ond order irreversible reactions [10] are the equations
tact (at solution to mass of zeolite ratio equal to 1 dm3:100 most often used to describe the removal of heavy metal
g) with chemicals as shown in Table 1. Solutions contain- ions from polluted water by use of natural material. It
ing Cu2+ in concentrations of 50 and 10 mg dm 3 were has been stated [3] that the uptake of heavy metal ions
prepared by dissolving corresponding quantities of by zeolite is controlled by ion exchange adsorption.
Cu(NO3)2 in distilled water. Solutions of Ca(NO3)2 and That is why the kinetic equation describing adsorption
Mg(NO3)2, prepared with distilled water, were added to [11] was also considered. Data tting to the equations
Cu(NO3)2 solutions in the amounts necessary to obtain mentioned above were tested in the usual way [12]. The
the corresponding ratios of concentrations of Ca2+ and data were processed in a suitable manner and checked
Mg2+ to concentrations of Cu2+. A Merck SQ 118 spec- whether they t to one of the following straight lines
trophotometer and Merck reagents were used to deter- found after mathematical transformations of the corre-
mine the Cu2+ concentration in each solution. sponding kinetic equations.
Determination of Na+, K+, Ca2+ and Mg2+ concentra- For the rst order reversible reactions:
tions in treated solution were made with an inductively
coupled plasmaatomic emission spectroscopy (ICP ln 1 Co Ct =Co Ceq k0 t 2
AES) analysis. The composition of zeolite was determined
by means of classical silicate analysis. pH values were where Ct is the concentration of Cu2+ at any time t, k0
measured with a Metrohm E 588 pH-mV-meter. Experi- is the overall rate constant, Co and Ceq are as described
ments were conducted batchwise; 1 g zeolite was stirred above.
with a LR 40 Medingen/Dresden paddle stirrer (at 400 For the rst order irreversible reactions:
rpm) in each solution. Temperature was kept constant
with a universal UTU-2/77 ultra-thermostat (Poland). ln Co =C k 3
The inuence of a specic process parameter was
determined by calculating Cu2+ uptake by zeolite and For the second order irreversible reactions:
Table 1
Conditions for zeolite modication Co C =Co C k 4
temperature. The apparent activation energy of the where Ceq,s and Ceq,l were the equilibrium concentra-
process was determined in the usual way, using Arrhe- tions of Cu2+ in solution and on the sorbent corre-
nius equation and the fact that the concentration of spondingly.
reagents does not depend on the temperature, [12].
Activation energy was found from the plot of ln v vs. 1/
T, where 3. Results and discussion
G R:T: ln K 10
were removed in the rst 20 min, as can be seen in Fig. 1. Having in mind results shown in Fig. 2, it can be sta-
Then up to the third hour the uptake increased only ted that higher Cu2+ removal due to uptake by zeolite
about 10%. That is why, a contact time of 10 min was (most probably by ions exchange adsorption) is
chosen in experiments aimed at revealing possible dif- observed in neutral water. An increase in Cu2+ removal
ferences in Cu2+ removal, due to the inuence of parti- was observed at pHini. of 10.8. It could be assigned to
cle sizes, pH value of solution and modication of precipitation of Cu(OH)2. Taking into consideration a
zeolite. solutions pH value, concentration of Cu2+ and the
To investigate the inuence of zeolite particle size on solubility product of copper hydroxide [16], that is
Cu2+ removal, tests were made under the following 5.610 20, it was estimated that Cu(OH)2 could be
conditions: solution concentrations of 10 and 50 mg precipitated. Removal eciency due to precipitation
dm 3 Cu2+; a pH of 5; a contact time of 10 min; and was 88.4 and 93.7% for initial Cu2+ concentrations of
v:m ratio of 100:1. Results obtained are presented in 10 and 50 mg dm 3 correspondingly. These values are in
Table 2. the range of values for Cu2+ uptake by natural zeolite
Use of zeolite with ner particles leads to an increase from neutral solution.
in Cu2+ uptake both for higher and lower copper con- Natural water, consequently the main part of indus-
centrations. Application of zeolite with more coarse trial wastewater, contains Ca2+ and Mg2+. The average
particles considerably decreases Cu2+ removal for solu- concentrations of Mg2+ and Ca2+ in Bulgarian water
tions with higher Cu2+ concentration. This probably is are 26 and 70 mg dm 3, respectively, and generally the
due to the smaller number of sites available for ion ratio CCa2+/CMg2+ is about 2 to 2.8 [15]. That is why,
exchange and adsorption. the inuence of Ca2+ and Mg2+ presence on the uptake
The inuence of solution pH value on Cu2+ uptake of Cu2+ was investigated during the simultaneous
was investigated under the following conditions: solu- addition of Ca2+ and Mg2+ (to Cu2+ solution) in con-
tion concentrations of 10 and 50 mg dm 3 Cu2+; a centrations giving ratios of CCa2+/CCu2+=2 and
contact time of 10 min; v:m ratio of 100:1; zeolite par- CMg2+/CCu2+=1. All other parameters were kept con-
ticle sizes between 0.09 and 0.325 mm; and pH values stant. Signicant changes in Cu2+ uptake by natural
(referred to as pHini.) of 3.0, 5.0, 7.0, 9.3, and 10.8. zeolite were not observed.
Results obtained are presented in Fig. 2. The inuence of zeolite modication on Cu2+ uptake
was investigated under the following experimental con-
ditions: solutions containing 50 mg dm 3 Cu2+; v:m
Table 2 ratio of 100:1; pHini.of 5.0; contact time of 10 min; and
Inuence of zeolite particle size on Cu2+ removal
zeolite particle sizes between 0.09 and 0.325 mm.
Zeolite particles Removal at an initial Removal at an initial Results obtained are presented in Table 3.
size (mm) concentration of concentration of Treatment of zeolite with HCl decreases the eciency
10 mg dm 3 Cu2+ (%) 50 mg dm 3 Cu2+ (%) of Cu2+ uptake, as can be seen from Table 3. As shown
<0.09 89.34 73.89 previously [1], the cation exchange capacity of zeolites is
0.090.325 82.64 56.90 reduced by the presence of K+, and the smaller the Si/
0.3250.400 78.33 41.04 Al ratio the greater is the ion exchange capacity. Con-
sequently, the lower uptake ability of treated zeolite is
expected, bearing in mind changes in zeolite composi-
tion caused by zeolite treatment with HCl. Increased
Cu2+ uptake by zeolite modied with NaCl and
CH3COONa is probably due to the raised relative con-
centration of more easily exchangeable Na+, as a result
of the modication. This statement is supported by
results from the ICP analysis showing that Na+ were
predominately exchanged in that case. Increased Cu2+
Table 3
Inuence of zeolite modication on Cu2+ removal
Type of None A B C D E F G H I
modicationa
Cu2+uptake 56.9 54.2 51.8 94.5 92.9 91.2 94.6 91.8 29.0 30.6
(%)
2+
Fig. 2. Inuence of solution pH value on Cu uptake: (a) 10 mg
a
dm 3 Cu2+, (b) 50 mg dm 3 Cu2+. As described in Table 1.
M.I. Panayotova / Waste Management 21 (2001) 671676 675
It has been found that the Cu2+ uptake process obeys Fig. 3. Adsorption isotherm of Cu2+.
the kinetic equation describing adsorption with correla-
tion coecients of r=0.994 and r=0.939 correspond-
ingly for solutions containing initially 50 and 10 mg Ka=0.4308. Figures obtained for KL, M and Ka are in
dm 3 of Cu2+. Hence, it could be stated that ion the range of values found for adsorption of heavy metals
exchange adsorption plays the main role in Cu2+ on natural materials, such as soil [13] and natural and
immobilization by natural zeolite, on the basis of: (a) activated bentonite [17] and show a medium anity of
kinetic equations describing the process, (b) a correlation zeolite for Cu2+. By placing the values found for M and
observed between Cu2+ uptake and the amount of metal KL in the Langmuir equation, a predictive expression
ions (mainly Na+, Ca2+ and K+) released into the describing Cu2+ sorption by zeolite could be obtained:
solution by zeolite, and (c) ndings on the inuence of
the solutions pH value. Probably, more easily accessible
zeolite cations are being exchanged in the rst hour. It is x=m6:39510 26:737C=16:39510 2C 14
likely that exchange ions situated deeper in zeolite chan-
nels are being exchanged in the next few hours. Thermodynamic parameters for the process of Cu2+
It was found that Cu2+ uptake increased with tem- uptake by natural zeolite are presented in Table 4.
perature for natural unmodied zeolite. An apparent Values found for Go, Ho and So are indicative of the
activation energy of 26.112 kJ mol 1 was found for spontaneous nature of the uptake process. The increase
Cu2+ uptake from solutions containing initially 50 mg of the equilibrium constant with increasing temperature
dm 3 of Cu2+. The value obtained shows that the pro- and positive values obtained for Ho show the endother-
cess can be easily carried out with a satisfactory rate. A mic nature of Cu2+ uptake. Results obtained in our
small decrease in the uptake rate with increasing tem- experiments generally agree with the results previously
perature was observed for zeolite modied with NaCl, found for the uptake of heavy metal ions by natural
perhaps due to the increased desorption of Cu2+ with materials [9,18].
increasing temperature.
The isotherm for Cu2+ uptake by zeolite (at pHini.=
5, contact time of 240 min, v:m=100:1 and particles size 4. Conclusions
0.090.325 mm) is presented in Fig. 3. Processing the
data obtained at room temperature and tting them to Natural Bulgarian zeolite can be used to remove
adsorption isotherms has shown that the equilibrium is Cu2+ from nearly neutral wastewater at a water to
best described by the traditional linear Langmuir iso-
therm, with a correlation coecient of r=0.998. Values
Table 4
obtained for Langmuir constants are correspondingly: Thermodynamic parameters for the Cu2+ adsorption on natural zeo-
KL=6.39510 2 dm3 mg 1and M=6.737 mg g 1. The lite
constant M is generally accepted as the adsorption
Temperature Uptake K G , H , S , J mol 1
maximum of the adsorbent with respect to the specic 1 1
(K) (%) J mol J mol K 1
solute, and KL is related to the energy of adsorption [13]
The apparent equilibrium constant Ka can be assumed 295 67.54 2.385 2131.6 +23988.7 +88.5
as a relative indicator for zeolite anity for Cu2+ [17]. 305 76.05 3.285 3017.7 +27355.4 +99.6
315 78.47 4.625 4006.7 +18745.6 +72.2
It may be calculated as the product of the Langmuir 323 83.11 5.521 4590.8
equation parameters KL and M, [17], in our case
676 M.I. Panayotova / Waste Management 21 (2001) 671676
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