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Acta hydrochim. hydrobiol.

31 (2003) 3, 249–252 249

Kurt Pilchowskia,
Eva Chmielewskáb
Adsorptive Separation of 1,2-Dichloroethane from
a
Model Wastewater by Natural Clinoptilolite
Martin Luther University
Halle-Wittenberg,
Department of Chemistry, The adsorptive separation of 1,2-dichloroethane from model wastewater by different Slovak
Institute of Analytical and
natural and octadecylammonium-modified clinoptilolites has been studied. It was found that
Environmental Chemistry,
the 1,2-dichloroethane will be adsorbed by natural as well as by surfactant-modified clin-
Kurt-Mothes-Str. 2,
06120 Halle, Germany optilolites; all clinoptilolites have a similar adsorption loading. There was also no remarkable
b
Comenius University difference between the natural and surfactant-modified clinoptilolites in respect to the ad-
Bratislava, Faculty of Natural sorption kinetics.
Science, Chair of
Environmental Protection,
Mlynska dolina B 2,
84215 Bratislava, Slovakia

Adsorptive Abtrennung von 1,2-Dichlorethan aus Modellabwasser mit


natürlichem Klinoptilolith

In der vorliegenden Arbeit wurde ein slowakischer natürlicher Klinoptilolith und dessen mit
Octadecylammoniumionen modifizierte Formen bei der adsorptiven Abtrennung von 1,2-Di-
chlorethan aus Modellabwasser untersucht. Dabei wurde festgestellt, dass das 1,2-Dichlor-
ethan sowohl durch den Naturklinoptilolith als auch durch die Oberflächen-modifizierten
Formen adsorbiert wird; alle Klinoptilolithe weisen ähnliche Adsorptionsbeladungen auf.
Auch in der Adsorptionskinetik unterscheiden sich der Naturklinoptilolith und die modifizier-
ten Formen kaum voneinander.

Keywords: Wastewater Treatment, Adsorption, Volatile Chlorinated Hydrocarbons

Schlagwörter: Abwasserreinigung, Adsorption, Leichtflüchtige chlorierte Kohlenwasser-


stoffe

Correspondence: K. Pilchowski, E-mail: pilchowski@chemie.uni-halle.de

DOI 10.1002/aheh.200300489 © 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
250 K. Pilchowski et al. Acta hydrochim. hydrobiol. 31 (2003) 3, 249–252

1 Introduction X-ray tube. The Kα-radiation was selected with a diffracted


beam monochromator. Mineral compounds were identified by
Volatile chlorinated hydrocarbons (VCHC) are used in various comparison with the JCPDF data bank in the conventional
fields of industry, mostly as solvents, extractives, or degreas- way. According to the mineralogical analysis the tuff contains
ants. These organic chemicals exhibit a high ecotoxic poten- about 70 % (wt.) of clinoptilolite and minor quantities of vol-
tial [1], therefore the applied VCHC passed into the exhaust- canic glass, feldspar, cristobalite, and quartz.
ed air or wastewaters must be eliminated afterwards. Current-
ly, the most common process for such removal is adsorption Clinoptilolite-rich tuff used in the experiments has the follow-
on activated carbon or polymeric adsorbent. ing chemical composition determined by X-ray fluorescence
analysis (mass fraction): 67.16 % SiO2; 12.30 % Al2O3; 2.30 %
Due to its high cation-exchange capacity and selectivity to- Fe2O3 ; 0.66 % Na2O; 2.91 % CaO; 1.10 % MgO; 2.28 % K2O;
wards ammonium and some metal ions, clinoptilolite, which is 0.11 % P2O5; 0.14 % MnO; 0,17 % TiO2; less than 0.01 % Sr,
a natural occurring zeolite, has often been used as an inex- Ba, Pb, Zn, and 10.90 % H2O. The SiO2/Al2O3 ratio of natural
pensive cation exchanger to control NH+4 or other cations like clinoptilolite is about 5 (4.8...5.4).
Pb2+, Ag+, Cs+, Sr2+ release in waters [2, 3].
ODA-modified zeolite was prepared as follows: A mixture of
The phenol adsorption from waters on NH+4-exchanged natu- 20 g of raw clinoptilolite-rich tuff and 100 mL of an aqueous
ral zeolite phillipsite was first studied by Garcia et al. [4]. Re- solution of octadecylammonium acetate (0.001 mol/L for C 1;
cently, it has been found that surfactant-modified zeolite, a 0.01 mol/L for C 2; 0.10 mol/L for C 3) was stirred in a glass
type of inexpensive organo-zeolite composite, can fulfil the vessel for 24 h at 60 °C. This time was considered to be suffi-
requirements for adsorption of organic pollutants from con- cient to achieve sorption equilibrium. The pH of the equilibri-
taminated waters. The adsorption of nonpolar hydrophobic um solution was kept at 3.0 on average by addition of 98 %
organic compounds used to be described by partitioning acetic acid. The mixture was then paper-filtered using a heat-
mechanism, whereas the sorption (distribution) coefficients ed Buchner funnel to yield a clear supernatant solution and
may depend proportionally on the surfactant fractional organ- ODA-treated clinoptilolite. The zeolite was washed with dis-
ic carbon content. In literature, both surfactant molecule con- tilled water, dried in a laboratory drier at 60 °C, and ground in
figuration bound on the zeolite surface and the fractional or- a mortar. After grinding the medium particle size was 0.6 mm.
ganic carbon content of the surfactant, are reported as re- According to the elementary analysis (C, H, N) the content of
sponsible factors for specific pollutants adsorption on organo ODA in samples C 0, C 1, C 2, and C 3, corresponding to the
(hexadecyltrimethylammonium(HDTMA))-modified zeolite. Li used initial ODA-concentrations, was 0 %, 5.5 %, 6.7 %, and
and Bowman [5] studied perchloroethylene sorption from 8.6 % (mass fraction) respectively.
aqueous model solutions on surfactant-loaded HDTMA-
clinoptilolite originating from the St. Cloud mine (New Mexi- A set of batch experiments was realized to evaluate the equi-
co). The uptake of cations, anions, and nonpolar organic mol- librium and kinetics of adsorption of the natural and surfactant
ecules by surfactant-modified clinoptilolite-rich tuff is de- (ODA)-modified clinoptilolites towards 1,2-dichloroethane
scribed by Bowman et al. [6]. from aqueous model solutions (deionized water, 1,2-dichlo-
roethane, pH 6.6).
The objective of our study was to examine the suitability of
natural and cationic surfactant-loaded octadecylammoni- The adsorption of 1,2-dichloroethane from model wastewater
um(ODA)-clinoptilolite-rich tuff of Slovakian origin for adsorp- was investigated in Erlenmeyer flasks at room temperature
tive separation of 1,2-dichloroethane from model wastewater. using magnetic stirring. For the determination of adsorption
In contrast to long-chain quaternary ammonium salts (e.g., as isotherms 250 mL model wastewater (initial concentration of
HDTMA) ODA is cheap and commercially available, suppos- 1,2-dichloroethane 10...85 mmol/L) combined with variable
ing the long-term tradition of ODA-bentonite production in the amounts of clinoptilolite (0.1...2 g), and for determination of
country may be enhanced by new, promising water treatment adsorption kinetics 250 mL model wastewater (initial concen-
agents [7]. tration of 1,2-dichloroethane 60 mmol/L) combined with 1 g
clinoptilolite were used. The concentration of 1,2-dichlo-
roethane was determined gaschromatographically with a
2 Experimental static headspace-technique.

The zeolitic tuff used in this study was local clinoptilolite (Slo-
vakian quarry Ni`źný Hrabovec) supplied in grain-sized frac- 3 Results
tion 0.3...1.0 mm by the company Zeocem Bystré. Mineral
composition of zeolitic rock and powder diffractograms were To characterize the adsorption capability of all clinoptilolite
obtained with a diffractometer, coupled to a copper anode samples, the adsorption isotherms of 1,2-dichloroethane

© 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


Acta hydrochim. hydrobiol. 31 (2003) 3, 249–252 Wastewater Treatment by Natural Clinoptilolite 251

were determined. As demonstrated in Figure 1, the curve fit of


the adsorption isotherms for all clinoptilolites (natural clin-
optilolite and its modifications) is assumed to be approxi-
mately linear. A good correlation was found between the ex-
perimentally obtained adsorption isotherms and the calculat-
ed ones using the equations of Henry and Redlich-Peterson
(correlation coefficient 0.998). In comparison to activated car-
bons and polymeric adsorbents [8] the adsorption capacity of
natural clinoptilolite and its modifications is relatively small.
The modification of clinoptilolite by ODA has only a slight in-
fluence on the increase of adsorption capacity.

To characterize the kinetics of the studied adsorption process


half-life periods were determined from experimental loading-
time data (see Fig. 2). On the basis of determined half-life pe-
riods the effective diffusion coefficients were evaluated using Fig. 2: Loading-time curves of 1,2-dichloroethane adsorption
the model of Boyd, Paterson, Suzuki/Kawazoe, and the LDF- from model wastewater on clinoptilolites at 25 °C.
model (see [8] for more details). The obtained diffusion coeffi- C 0: Natural clinoptilolite (no ODA)
cients for the natural clinoptilolite and its modifications were C 1: ODA-modified clinoptilolite (mass fraction of ODA: 5.5 %)
found to be of equivalent value, i.e., (1...5) · 10–8 cm2/s. In re- C 2: ODA-modified clinoptilolite (mass fraction of ODA: 6.7 %)
gards to the adsorption kinetics the modification of natural C 3: ODA-modified clinoptilolite (mass fraction of ODA: 8.6 %)
clinoptilolite by ODA did not exhibit a significant influence.
Beladungs-Zeit-Kurven der 1,2-Dichlorethan-Adsorption aus
Modellabwasser an Klinoptilolithen bei 25 °C.
C 0: Natürlicher Klinoptilolith (ohne ODA)
C 1: ODA-modifizierter Klinoptilolith (Massenanteil von ODA:
5.5 %)
C 2: ODA-modifizierter Klinoptilolith (Massenanteil von ODA:
6.7 %)
C 3: ODA-modifizierter Klinoptilolith (Massenanteil von ODA:
8.6 %)

4 Conclusion

Concluding from the obtained equilibrium and kinetic data of


Fig. 1: Isotherms of adsorption of 1,2-dichloroethane from 1,2-dichloroethane adsorption the natural zeolite clinoptilolite
model wastewater on clinoptilolites at 25 °C. and its ODA modifications are suitable for the separation of
chlorinated hydrocarbons from wastewater. They all show a
C 0: Natural clinoptilolite (no ODA) similar adsorption loading and a similar adsorption kinetics.
C 1: ODA-modified clinoptilolite (mass fraction of ODA: 5.5 %) Compared with the sorption of nonpolar perchloroethylene on
C 2: ODA-modified clinoptilolite (mass fraction of ODA: 6.7 %) HDTMA-clinoptilolite [5] ODA immobilization on the surface of
C 3: ODA-modified clinoptilolite (mass fraction of ODA: 8.6 %) clinoptilolite particles shows only a slight influence on the ad-
sorption of nonpolar 1,2-dichloroethane from the model
Isothermen der Adsorption von 1,2-Dichlorethan aus Model- wastewater.
abwasser an Klinoptilolithen bei 25 °C.
C 0: Natürlicher Klinoptilolith (ohne ODA)
C 1: ODA-modifizierter Klinoptilolith (Massenanteil von ODA:
5.5 %) References
C 2: ODA-modifizierter Klinoptilolith (Massenanteil von ODA:
6.7 %) [1] Laib, R. J.: Mutagenität und Kanzerogenität leichtflüchtiger
C 3: ODA-modifizierter Klinoptilolith (Massenanteil von ODA: halogenierter Verbindungen. VDI Berichte 745, 713–730
8.6 %) (1989).

© 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


252 K. Pilchowski et al. Acta hydrochim. hydrobiol. 31 (2003) 3, 249–252

[2] Horváthová-Chmielewská, E.: Ionenaustausch an Naturzeo- [7] Chmielewská, E., Jesenák, K., Gaplovská, K.: Potential de-
lithen bei Wasserbehandlungsprozessen. Stimul, Bratislava, creasing of arsenate and chromate in waters by organo-
1996 (ISBN 80-85697-30-0). modified clinoptilolite. Zeolite Meeting, Puebla, 2001.
[3] Collella, C.: Environmental applications of natural zeolitic [8] Kowalzik, A., Urban, I., Wahl, A., Pilchowski, K.: Adsorptive
materials based on their ion exchange properties. In: Abtrennung von LCKW aus Modellabwasser mit Adsorber-
Misaelides, P. et al. (Eds.): Natural Microporous Materials in polymeren und Aktivkohlen. Teil 1: Kinetik und Isothermen
Environmental Technology. NATO Science Series, Kluwer der Adsorption von 1,2-Dichlorethan. Vom Wasser 85, 363–
Academic Publ., Dordrecht, 1999. 376 (1995).
[4] Garcia, J. E., Gonzalez, M. M., Notario, J. S.: Phenol adsorp-
tion on naturalphillipsite. React. Polym. 21, 171–176 (1993).
[5] Li, Z., Bowman, R. S.: Sorption of perchloroethylene by sur-
factant-modified zeolite as controlled by surfactant loading.
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[6] Bowman, R. S., Sullivan, E. J., Li, Z.: Uptake of cations,
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