Determination of Parameters Affecting Copper Removal from Solutions by Clinoptilolite: Adsorption Isotherm and Thermodynamic

Abstract

The clinoptilolite mineral which is a zeolite type is one of the natural cation exchangers. In this study, the removal of copper ions from solutions using Bigadiç clinoptilolite by ion exchange method was investigated. Experiments were carried out in batch mode as a function of the solution pH, temperature, ionic strength and conditioning with NaOH and KOH. The ion exchange reaction reached to the equilibrium within 24 hours. Copper sorption capacity of the clinoptilolite increased with high solution pH, high temperature, and low ionic strength. Conditioning of the raw clinoptilolite with NaOH and KOH provided 10.4 and 10.06 fold capacity increase respectively. The increase of capacity with temperature increase showed that the sorption process was endothermic in nature. Also, the ion exchange reaction between clinoptilolite and copper ions was found as more spontaneous at high temperatures. Maximum sorption capacity of the clinoptilolite sample was calculated as 48.45 mg g-1 after conditioning with NaOH. Sorption equilibrium data were analyzed by the Langmuir and Freundlich models. It was seen that the fitness of isotherm data to the Langmuir isotherm was very good than Freundlich model. The obtained results showed that the Bigadiç clinoptilolite would be used effectively in removal of copper ions from industrial wastewaters especially after conditioning with NaOH

Keywords

• Clinoptilolite, copper, ion exchange, isotherm, thermodynamic

Klinoptilolit Minerali ile Çözeltilerden Bakır Giderimini Etkileyen Parametrelerin Belirlenmesi: Adsorpsiyon İzotermi ve Termodinamiği

Abstract

Bir zeolit türü olan klinoptilolit minerali doğal katyon değiştiricilerden bir tanesidir. Bu çalışmada iyon değişimi metodu ile Bigadiç klinoptiloliti kullanarak çözeltilerden bakır iyonlarının giderimi araştırılmıştır. Deneyler kesikli modda çözelti pH, sıcaklık, iyon şiddeti, NaOH ve KOH ile şartlandırmanın bir fonksiyonu olarak gerçekleştirilmiştir. Iyon değişimi reaksiyonu dengeye 24 saatte gelmiştir. Klinoptilolitin adsorpsiyon kapasitesi yüksek pH, yüksek sıcaklık ve düşük iyonik şiddet ile artmıştır. Ham klinoptilolitin NaOH ve KOH ile şartlandırılması sırasıyla 10.4 ve 10.06 kat kapasite artışı sağlamıştır. Kapasitenin sıcaklık artışı ile artması prosesin endotermik doğada olduğunu göstermiştir. Ayrıca, bakırın klinoptilolit ile iyon değişimi reaksiyonunun yüksek sıcaklıklarda kendiliğinden daha kolay gerçekleşeceği bulunmuştur. Klinoptilolitin maksimum kapasitesi NaOH ile şartlandırma sonrasında 48.45 mg g-1 olarak hesaplanmıştır. Sorpsiyon denge verileri Langmuir ve Freundlich modelleri ile analiz edilmiştir. İzotherm verilerinin Langmuir izotermine uyumunun Freundlich izoterminden çok daha iyi olduğu görülmüştür. Elde edilen sonuçlar, Bigadiç klinoptilolitinin özellikle NaOH ile şartlandırma sonrasında atık sulardan bakır gideriminde etkili bir şekilde kullanılabileceğini göstermiştir

Keywords

• Klinoptilolit, bakır, iyon değişimi; izoterm, termodinamik

References

1. Akgul, M., Karabakan, A., Acar, O., Yurum, Y., 2006. Removal of silver (I) from aqueous solutions with Clinoptilolite. Microporous and Mesoporous Materials, 94: 99-104.
2. Barancikova, G., Makovnikova, J., 2003. The influence of humic acid quality on the sorption and mobility of heavy metals. Plant Soil Environment, 49: 565-571.
3. Bayramoglu, G., Altintas, B., Arica, M.Y., 2009. Adsorption kinetics and thermodynamic parameters of cationic dyes from aqueous solutions by using a new strong cation-exchange resin. Chemical Engineering Journal, 152: 339-346.
4. Cabrera, C., Gabaldon, C., Marzal, P., 2005. Sorption characteristics of heavy metal ions by a natural zeolite. Journal of Chemical Technology and Biotechnology, 80: 477-481.
5. Cojocaru, C., Trznadel, G.Z., 2007. Response surface modeling and optimization of copper removal from aqua solutions using polymer assisted ultrafiltration. Journal Membrane Science, 298: 56-70.
6. Özdemir, Y., Dogan, M., Alkan, M., 2006. Adsorption of cationic dyes from aqueous solutions by sepiolite. Microporous and Mesoporous Materials, 96: 419-427.
7. Demirbas, A., Pehlivan, E., Gode, F., Altun, T., Arslan G., 2005. Adsorption of Cu(II), Zn(II), Ni(II), Pb(II), and Cd(II) from aqueous solution on Amberlite IR-120 synthetic resin. Journal of Colloid and Interface Science, 282: 20-25.
8. Dogan, M., Alkan, M., 2003. Adsorption kinetics of methyl violet onto perlite. Chemosphere, 50: 517-528.

9. Ekmekyapar, F., Aslan, A., Bayhan, Y.K., Cakici, A., 2006. Biosorption of copper(II) by nonliving lichen biomass of Cladonia rangiformis hoffm. Journal of Hazardous Materials, 137: 293-298.
10. Erdem, E., Karapinar, N., Donat, R., The removal of heavy metal cations by natural zeolites. Journal of Colloid and Interface Science, 280: 309-314.
11. Ersoy, B., Celik, M.S., 2002. Electrokinetic properties of Clinoptilolite with mono- and multivalent electrolytes. Microporous and Mesoporous Materials, 55: 305-312.
12. Escobar, C., Soto-Salazar, C., Toral, M.I. J., 2006. Optimization of the electrocoagulation process for the removal of copper, lead and cadmium in natural waters and simulated wastewater. Environmental Management, 81: 384-391.
13. Freundlich, H. M. F., 1906. Over the adsorption in solution. The Journal of Physical Chemistry, 57: 385-470.
14. Hansen, H.K., Rojo, A., Ottosen, L.M., 2005. Electrodialytic remediation of copper mine tailings. Journal of Hazardous Materials, 117: 179-183.
15. Hsieh, C.H., Loa, S.L., Kuan, W.H., Chena, C.L., 2006. Adsorption of copper ions onto microwave stabilized heavy metal sludge. Journal of Hazardous Materials, 136: 338-344.
16. Hui, K.S., Chao, C.Y.H., Kot, S.C., 2005. Removal of mixed heavy metal ions in wastewater by zeolite 4A and residual products from recycled coal fly ash. Journal of Hazardous Materials,127: 89-101.
17. Inglezakis, V.J., Loizidou, M.D., Grigoropoulou, H.P., 2002. Equilibrium and kinetic ion exchange studies of Pb2+, Cr3+, Fe3+ and Cu2+ on natural Clinoptilolite. Water Research, 36: 2784-2792.
18. Kocaoba, S., Orhan, Y., Akyüz, T., 2007. Kinetics and equilibrium studies of heavy metal ions removal by use of natural zeolite. Desalination, 214: 1-10.
19. Langmuir, I., 1916. The adsorption of gases on plane surface of glass, mica and platinum. Journal of The American Chemical Society, 40: 1361-1368.
20. Özdemir, Y., Dogan, M., Alkan, M., 2006. Adsorption of cationic dyes from aqueous solutions by Sepiolite. Microporous and Mesoporous Materials, 96; 419-427.
21. Özmetin, C., Aydın, Ö., Kocakerim, M.M., Korkmaz, M., Özmetin, E., 2009. An empirical kinetic model for calcium removal from calcium impurity-containing saturated boric acid solution by ion exchange technology using Amberlite IR–120 resin. Chemical Engineering Journal, 148: 420-424.
22. Petrus, R. Warchol, J.K. 2005. Heavy metal removal by clinoptilolite.An equilibrium study in multi-component systems. Water Research, 39: 819-830.
23. Sprynskyy, M., Buszewski, B., Terzyk, A.P., Namiesnik, J., 2006. Study of the selection mechanism of heavy metal (Pb2+, Cu2+, Ni2+, and Cd2+) adsorption on clinoptilolite. Journal of Colloid and Interface Science, 304: 21-28.
24. Wıngenfelder, U., Hansen, C., Furrer, G., Schulin, R., 2005. Removal of Heavy Metals from Mine Waters by Natural Zeolites. Environmental Science and Technology, 39: 4606-4613.
25. Woinarski, A.Z., Snape, I., Stevens ,G.W., Stark, S.C., 2003. The effects of cold temperature on copper ion exchange by natural zeolite for use in a permeable reactive barrier in Antarctica.Cold Regions Science and Technology, 37: 159-168.