Removal of Phenol and 4-Chlorophenol from Aqueous Environment with Modified Nanobentonite

Öz

In recent years, chemicals and drugs used in industry and agriculture have started to be harmful to all living things in the environments in which they are discharged. With the regulations prepared by environmental protection agencies and municipalities, hazardous chemicals are classified and minimum concentrations in wastewater are determined. Purification and purification processes have become mandatory for wastewater outside these limit values. In our study, the removal of phenol (P) and 4-chlorophenol (4-CP) with modified alkyl ammonium nanobentonite (MANB) from the aqueous solution was investigated. Balance time, concentration, pH effect, adsorban dosage effect and desorption were investigated in P and 4-CP adsorption. Adsorbed amount; 4.69 mg/g for P and 6.18 mg/g for 4-CP. Balance time 45 min. and the adsorbent desorption was performed in 30% (v/v) ethyl alcohol medium. Adsorption experiments were carried out at different temperature ranges of 25, 35 and 45C. Chemical structure, thermal and morphological characterization of samples were performed at the beginning and after adsorption. The suitability of the initial concentrations of the studied substances to the MANB microspheres was investigated for Langmuir and Freundlich adsorption isotherm models. 

Anahtar Kelimeler

• Nanobentonite
• Modification
• Adsorbent
• Phenols
• Wastewater

Modifiye Nanobentonitle Sulu Ortamdan Fenol ve 4-Klorofenolün Giderilmesi

Öz

Son yıllarda endüstri ve tarımda kullanılan kimyasal ve ilaçlar deşarj edildikleri ortamlarda tüm canlılar için zararlı olmaya başlamıştır. Çevre koruma ajansları ve belediye gibi kurumların bu konudaki hazırladıkları yönetmeliklerle zararlı kimyasallar sınıflandırılmış ve atık sulardaki bulunabilecekleri minimum derişimler belirlenmiştir. Bu sınır değerler dışında kalan atık sular için saflaştırma ve arıtma prosesleri zorunlu hale gelmiştir. Çalışmamızda fenol (P) ve 4-klorofenolün (4-CP) modifiye alkil amonyum nanobentonit (MANB) ile kesikli sistemde, sulu çözeltiden giderimi araştırılmıştır. P ve 4-CP adsorplanmasında denge zamanı, konsantrasyon, pH etkisi, adsorbent dozaj etkisi ve desorpsiyonu incelenmiştir. Adsorplanan miktarı; P için 4,69 mg/g, 4-CP için 6,18 mg/g olarak elde edilmiştir. Denge zamanı 45 dak. olup adsorbentin desorpsiyonu % 30 (v/v)’ luk etil alkol ortamında yapılmıştır. Adsorpsiyon deneyleriı 25, 35 ve 45C değişik sıcaklık aralıklarında yapılmıştır. Örneklerin kimyasal yapı, termal ve morfolojik karakterizasyonu başlangıçta ve adsorpsiyondan sonra yapılmıştır. Çalışılan maddelerin başlangıç derişiminin MANB mikrokürelerin Langmuir ve Freundlich adsorpsiyon izoterm modellerine uygunluğu incelenmiştir. Deneysel bulguların Freundlich izoterm adsorpsiyon modeline uygun olduğu saptanmıştır.

Anahtar Kelimeler

• nanobentonit
• modifikasyon
• adsorbent
• fenol
• atık sular

Kaynakça

1. Ahmaruzzaman Md. (2008). Adsorption of phenolic compounds on low-cost adsorbents: Areview. Advances in Colloid and Interface Science, 143: 48-67
2. Akçay M. (2006) Characterization and adsorption properties of tetrabutyl ammonium montmorillonite (TBAM) clay: Thermodynamic and kinetic calculations, Journal of Colloid and Interface Science, 296:16–21.
3. Aksu, Z. Yener, J. (2001). Comparative adsoption/biosorption study of monochlorinated phenols onto various sorbents. Waste Management, 21:695-702.
4. Atia, A.A. (2008). Adsorption of chromate and molybdate by cetylpyridinium bentonite. Applied Clay Science, 41:73–84.
5. Banat, F. A., Al-Bashir, B., Al-Asheh, S., Hayajneh, O. (2000). Adsorption of phenol by bentonite. Environmental Pollution, 107:391-398.
6. Bors, J., Patzko, A., Dekany, I. (2001). Adsorption behavior of radioiodides in hexadecylpyridiniumhumate complexes, Applied Clay Science, 19: 27-37.
7. Dabrowski, A., Podkoscielny, P., Hubicki, Z., Barczak, M. (2005). Adsorption of phenolic compounds by actived carbon-a critical review. Chemosphere 58:1049-1070
8. Dann, S.E. (2002) Reactions and Characterization of Solids (Basic Concepts In Chemistry), Royal Society of Chemistry, Chambridge, 201.

9. Denizli, A., Özkan G. and Uçar M., (2002), Dye-affinity microbeads for removal of phenol and nitrophenols from aquatic systems. Journal of Applied Polymer Science., 83 (11), 2411-2418.
10. Denizli, A., Özkan G and Uçar M, (2001). Removal of Chlorophenols from Aquatic Systems with Dye-affinity Microbeads. Separation and Purification Technology, 24: 255-262
11. Dultz, S., Riebe, B., Bunnenberg, C. (2005). Temperature effects on iodine adsorption on organo-clay minerals II. Structural effects, Applied Clay Science, 28:17– 30.
12. Evcin Atilla, Uçar Mustafa, Kayıran Dilek, Selimoglu Münevver, 4 Klorofenolün Hidroksiapatit ile Sulu Ortamdan Uzaklaştırılması. AKÜ FEMÜBİD 14 (2014) OZ5737 (233-237)
13. Garmia D., Zaghouane-Boudiaf H., Viseras Ibbora C., Preparation and characterization of new low cost adsorbent beads based on activated bentonite encapsulated with calcium alginate for removal of 2,4-dichlorophenol from aqueous medium, International Journal of Biological Macromolecules, Volume 115, 2018, Pages 257-265, https://doi.org/10.1016/j.ijbiomac.2018.04.064.
14. Hernández-Hernández, Karina & Illescas, Javier & Díaz-Nava, C. & Martínez-Gallegos, Sonia & Muro, Claudia & Ortega-Aguilar, Rosa & Rodríguez-Alba, Efraín & Rivera, Ernesto. (2018). Preparation of nanocomposites for the removal of phenolic compounds from aqueous solutions. Applied Clay Science. 157. 10.1016/j.clay.2018.01.020.
15. İpekoğlu, B., Kurşun, İ., Bilge, Y., Barut, A. (1997). Türkiye Bentonit Potansiyeline Genel Bir Bakış. 2. Endüstriyel Hammaddeler Sempozyumu, 16-17 Ekim İzmir, 51-57.
16. Kara, M. (1999). Toksik Ağır Metal İyonlarının Sepiyolit Üzerine Adsorpsiyon Mekanizması. Dr. Tezi, İTÜ, İstanbul, 247 sayfa.
17. Kozak, M., Domka, L. (2004) Adsorption of the quaternary ammonium salts on montmorillonite, Journal of Physics and Chemistry of Solids, 65:441–445.
18. Kuleyin A. (2007). Removal of Phenol and 4-Chlorophenol by Surfactant- Modified Natural Zeolite. Journal of Hazardous Materials, 144:307 – 315.
19. Kuśmierek, K. The removal of chlorophenols from aqueous solutions using activated carbon adsorption integrated with H2O2 oxidation. Reac Kinet Mech Cat 119, 19–34 (2016). https://doi.org/10.1007/s11144-016-1039-0
20. Majdan, M., Maryuk, O., Gladysz-Plaska, A., Pikus, S., Kwiatkowski, R. (2008). Spektral characteristics of the bentonite loaded with benzyldimethyloctadecyl ammonium chloride, hexadecyltrimethyl ammonium bromide and dimethyldioctadecyl ammonium bromide, Journal of Molecular Structure, 874: 101–107.
21. Nourmoradi H., Avazpour M, Ghasemian N, Heidari M, Moradnejadi K., KhodarahmiF., Javaheri M., Mohammadi Moghadam F., Surfactant modified montmorillonite as a low cost adsorbent for 4-chlorophenol: Equilibrium, kinetic and thermodynamic study, Journal of the Taiwan Institute of Chemical Engineers,Volume 59, 2016, Pages 244-251, https://doi.org/10.1016/j.jtice.2015.07.030.
22. Olaniran AO, Igbinosa EO (2011) Chlorophenols and other related derivatives of environmental concern: properties, distribution and microbial degradation processes. Chemosphere 83:1297–1306
23. Pera-Titus M, Garcia-Molina V, Ban˜os MA, Gimenez J, Esplugas S (2004) Degradation of chlorophenols by means of advanced oxidation processes: a general review. Appl Catal B Environ 47:219–256
24. Oruçoğlu, E. ve Hacıyakupoğlu, S. (2010). Organo-bentonitler ve karakterizasyonlarında kullanılan yöntemler. İstanbul Teknik Üniversitesi, Maden Fakültesi, Enerji Enstitüsü, Ayazağa Kampüsü, İstanbul
25. Sarıgök, Ü. (1987). Anorganik Endüstriyel Kimya, Güryay Matbaacılık, İstanbul.
26. Sanjay P, K., Priti A, M., Amit K, B., Sadhana S, R. (2008). Adsorption of phenol and o- chlorophenol on surface altered fly ash based moleculer sieves. Chemical Engineering Journal, 138:73-83.
27. Soto ML, Moure A, Dominguez H, Parajo JC (2011) Recovery, concentration and purification of phenolic compounds by adsorption: a review. J Food Eng 105:1–27
28. Şenel S, Kara A, Alsancak G, Denizli A, J. Hazardous Materials, (2006). B138:317-324.
29. Şentürk H.B., Özdeş D., Gündoğdu A., Duran C., Soylak M. (2009). Removal of Phenol from Aqueous Solutions by Adsorption Onto Organomodified Tirebolu Bentonite: Equilibrium, Kinetic and Thermodynamic Study, Journal of Hazardous Materials, 172: 353–362.
30. Uçar S. (2009). Sulu Ortamda Bulunan Fenol ve Klorofenollerin Aktive Edilmiş Klinoptilolit Kullanılarak Uzaklaştırılması. Yüksek Lisans Tezi, Afyon Kocatepe Üniversitesi, Fen Bilimleri Enstitüsü, Afyonkarahisar.
31. Uçar Mustafa, Evcin Atilla, Kayıran Dilek, Ünverdi Haydar, Klorofenolün Al2O3 Katkılı Hidroksiapatit Ile Sulu Ortamdan Uzaklaştırılması. AKÜ FEMÜBİD 14 (2014) OZ5737 (225-232)
32. Uçar Songül, Evcin Atilla, Uçar Mustafa, Alibeyli Rafig, Majdan Marek (2015). Aktive Edilmis Klinoptilolit Kullanılarak Sulu Ortamdan Fenol ve Klorofenollerin Uzaklastırılması. Hacettepe Journal of Biology and Chemistry, 43(3), 235-249., Doi: 10.15671/HJBC.20154314246
33. Uçar Mustafa, Adsorption Science & Technology, 2019, Volume 37, pp 664-679; doi:10.1177/0263617419870671
34. Xie, W., Gao, Z., Liu, K., Pan, W.P., Vaia, R., Hunter, D., Singh, A. (2001a) Thermal characterization of organically modified montmorillonite, Thermochimica Acta, 367-368: 339-350.
35. Xie, W., Gao, Z., Pan, W.P., Hunter, D., Singh, A., Vaia, R. (2001b) Thermal degradation chemistry of alkyl quaternary ammonium montmorillonite, Chemistry of Materials, 13: 2979-2990.
36. Yariv, S. (2004) The role of charcoal on DTA curves of organo-clay complexes: an overview, Applied Clay Science, 24, 225– 236.
37. Yıldız, N., Gönülşen, R., Çalımlı, A. (2006) Tek ve çift katyonlu organobentonitlerin hazırlanması ve karakterizasyonu, Kibited, 1, 2, 93-105.
38. Zhu, L. And Chen, B. (2000). Sorption Behavior of p-nitrophenol on the Interface between Anion-Cation Organobentonite and Water. Env.Sci. and Tech. 32: 3374- 3378.
39. Zhu, L., Zhu, R. (2007). Simultaneous sorption of organic compounds and phosphate to inorganic–organic bentonites from water, Separation and Purification Technology, 54: 71–76.