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Structural Property Improvements of Bentonite with Sulfuric Acid Activation and a Test in Catalytic Wet Peroxide Oxidation of Phenol

  • Suna Balci EMAIL logo
Published/Copyright: December 15, 2018

Abstract

The acid activation of bentonite from Middle Anatolia, consisting of mostly montmorillonite, with a hot solution of H2SO4 with different concentrations was carried out. SEM images, nitrogen sorption isotherms and FTIR spectra were used to examine structural changes of the bentonite with acid activation. Acid–base titration method was applied to determine surface acidities. SEM images, nitrogen sorption isotherms indicated that the acid activation caused considerable increases both in the surface area and pore volumes by changing the morphology and aluminum content. FTIR spectra showed the enhancement both in Lewis and Brønsted acidities, significant increases in H–bonding to the structure with acid concentration. Acid treatment gave good structural properties with high surface acidity. Stable structured acid activated bentonite with 2 M was tested in catalytic wet peroxide oxidation (CWPO) of phenol together with raw bentonite. Around 96 % phenol removal was achieved in 135 minutes at reaction temperature of 50 °C while the raw bentonite did not show good results. The data were in agreement with the first order dependency with respect to phenol.

Acknowledgements

This work is partially funded by Research Fund BAP 06/2009-20 of Gazi University. The author wishes to express her greatest thanks to Ayşen Dağeri and Funda Turgut Başoğlu for their help in some part of experimental studies.

References

Adams, J. M., and R. W. McCabe. 2013. “Clay Minerals as Catalyst,” in Development in Clay Science: Handbook of Clay Science Vol. 5, edited by F. Bergaya, and G. Lagaly, 491–538. Amsterdam: Elsevier.10.1016/B978-0-08-098259-5.00019-6Search in Google Scholar

Akpomie, K. G., and F. A. Dawodu. 2016. “Acid-Modified Montmorillonite for Sorption of Heavy Metals from Automobile Effluent.” Beni-Suef University Journal of Basic and Applied Sciences 5 (1): 1–12.10.1016/j.bjbas.2016.01.003Search in Google Scholar

Alejandre, A., F. Medina, P. Salagre, A. Fabregat, and J. E. Sueiras. 1998. “Characterization and Activity of Copper and Nickel Catalysts for the Oxidation of Phenol Aqueous Solutions.” Applied Catalysis B: Environmental 18: 307–15.10.1016/S0926-3373(98)00050-2Search in Google Scholar

Al-Shahrani, S. S. 2014. “Treatment of Wastewater Contaminated with Cobalt Using Saudi Activated Bentonite.” Alexandria Engineering Journal 53 (1): 205–11.10.1016/j.aej.2013.10.006Search in Google Scholar

Antonio Ortiz, N. J., S. G. Solis, V. E. Thomassiny, and F. Ruf. 2008. “Amorphous Adsorbent, Method of Obtaining the Same and Its Use in the Bleaching of Fats And/Or Oils.” CA-2668729A1.Search in Google Scholar

Arena, F., R. Di Chio, B. Gumina, L. Spadaro, and G. Trunfio. 2015. “Recent Advances on Wet Air Oxidation Catalysts for Treatment of Industrial Wastewaters.” Inorganica Chimica Acta 431: 101–09.10.1016/j.ica.2014.12.017Search in Google Scholar

Auer, H., and H. Hofmann. 1993. “Pillared Clays Characterization of Acidity and Catalytic Properties and Comparison with Some Zeolites.” Applied Catalysis A: General 97: 23–38.10.1016/0926-860X(93)80064-WSearch in Google Scholar

Balci, S., and E. Gökçay. 2002. “Effects of Drying Methods and Calcination Temperature on the Physicochemical Properties of Iron Intercalated Clays.” Materials Chemistry and Physics 76: 46–51.10.1016/S0254-0584(01)00503-XSearch in Google Scholar

Barrault, J., C. Bouchoule, K. Echachoui, N. Frini-Srasra, M. Trabelsi, and F. Bergaya. 1998. “Catalytic Wet Peroxide Oxidation (CWPO) of Mixed (Al-Cu)-Pillared Clays.” Applied Catalysis B: Environmental 15: 269–74.10.1016/S0926-3373(97)00054-4Search in Google Scholar

Barzetti, T., E. Selli, D. Moscotti, and L. Forni. 1996. “Pyridine and Ammonia as Probes for FTIR Analysis of Solid Acid Catalysts.” Journal of the Chemical Society, Faraday Transactions 92: 1401–07.10.1039/ft9969201401Search in Google Scholar

Bendou, S., and M. Amrani. 2014. “Effect of Hydrochloric Acid on the Structural of Sodic-Bentonite Clay.” Journal of Minerals and Materials Characterization and Engineering 2: 404–13.10.4236/jmmce.2014.25045Search in Google Scholar

Bieseki, L., H. Treichel, A. S. Araujo, and S. B. Castellã Pergher. 2013. “Porous Materials Obtained by Acid Treatment Processing Followed by Pillaring of Montmorillonite Clays.” Applied Clay Science 85: 46–52.10.1016/j.clay.2013.08.044Search in Google Scholar

Brezovska, S., B. Marina, D. Burevski, B. Angusheva, V. Boseska, and L. Stojanovska. 2005. “Adsorption Properties and Porous Structure of Sulfuric Acid Treated Bentonites Determined by the Adsorption Isotherm of Benzene Vapor.” Journal of the Serbian Chemical Society 70: 33−40.10.2298/JSC0501033BSearch in Google Scholar

Chen, C., and T. Cheng. 2013. “Wet Air Oxidation and Catalytic Wet Air Oxidation for Refinery Spent Caustics Degradation.” Journal of the Chemical Society of Pakistan 35: 244–50.Search in Google Scholar

Christidis, G. E., P. W. Scott, and A. C. Dunham. 1997. “Acid Activation and Bleaching Capacity of Bentonites from the Islands of Milos and Chios, Aegean, Greece.” Applied Clay Science 12: 329–47.10.1016/S0169-1317(97)00017-3Search in Google Scholar

Cordova Villegas, L. G., N. Mashhadi, M. Chen, D. Mukherjee, K. E. Taylor, and N. A. Biswas. 2016. “Short Review of Techniques for Phenol Removal from Wastewater.” Current Pollution Reports 2: 157–67.10.1007/s40726-016-0035-3Search in Google Scholar

de Los Monteros, A. E., G. Lafaye, A. Cervantes, G. D. Angel, J. Barbier Jr, and G. Torres. 2015. “Catalytic Wet Air Oxidation of Phenol over Metal Catalyst (Ru, Pt) Supported on TiO2-CeO2 Oxides.” Catalysis Today 258 (2): 564–69.10.1016/j.cattod.2015.01.009Search in Google Scholar

Didi, M. A., B. Makhoukhi, A. Azzouz, and D. Villemin. 2009. “Colza Oil Bleaching through Optimized Acid Activation of Bentonite; A Comparative Study.” Applied Clay Science 42: 336–44.10.1016/j.clay.2008.03.014Search in Google Scholar

Divate, S. B., and R. V. Hinge. 2014. “Review on Research Removal of Phenol from Wastewater by Using Different Methods.” International Journal of Scientific and Research Publications 5: 1–3.Search in Google Scholar

Fajerwerg, K., and H. Debellefontaine. 1996. “Wet Oxidation of Phenol by Hydrogen Peroxide Using Heterogeneous Catalysis Fe-ZSM-5: A Promising Catalyst.” Applied Catalysis B: Environmental 10: L229–35.10.1016/S0926-3373(96)00041-0Search in Google Scholar

Gua, J., and M. Al-Dahhan. 2003. “Catalytic Wet Oxidation of Phenol by Hydrogen Peroxide over Pillared Clay Catalyst.” Industrial & Engineering Chemistry Research 42: 2450–60.10.1021/ie020344tSearch in Google Scholar

Iboukhoulef, H., A. Amrane, and H. Kadi. 2016. “Removal of Phenolic Compounds from Olive Mill Wastewater by a Fenton-Like System H2O2/Cu(II)—Thermodynamic and Kinetic Modeling.” Desalination and Water Treatment 57: 1–6.10.1080/19443994.2014.978385Search in Google Scholar

Inchaurrondo, N., J. Cechini, J. Font, and P. Haure. 2012. “Strategies for Enhanced CWPO of Phenol Solutions.” Applied Catalysis B: Environmental 111: 641–48.10.1016/j.apcatb.2011.11.019Search in Google Scholar

Jing, G., M. Luan, and T. Chen. 2016. “Progress of Catalytic Wet Air Oxidation Technology.” Arabian Journal of Chemistry 9: S1208–13.10.1016/j.arabjc.2012.01.001Search in Google Scholar

Kazemi, P., M. Peydayesh, A. Bandegi, T. Mohammadi, and O. Bakhtiari. 2014. “Stability and Extraction Study of Phenolic Wastewater Treatment by Supported Liquid Membrane Using Tributyl Phosphate and Sesame Oil as Liquid Membrane.” Chemical Engineering Research and Design 92: 375–83.10.1016/j.cherd.2013.07.023Search in Google Scholar

Kim, K. H., and S. K. Ihm. 2011. “Heterogeneous Catalytic Wet Air Oxidation of Refractory Organic Pollutants in Industrial Wastewaters: A Review.” Journal of Hazardous Materials 186: 16–34.10.1016/j.jhazmat.2010.11.011Search in Google Scholar PubMed

Komadel, P. 2016. “Acid Activated Clays: Materials in Continuous Demand.” Applied Clay Science 131: 84–99.10.1016/j.clay.2016.05.001Search in Google Scholar

Komadel, P., and J. Madejová. 2013. “Acid Activation of Clay Minerals,” in Development in Clay Science: Handbook of Clay Science Vol. 5, edited by F. Bergaya, and G. Lagaly, 385–409. Amsterdam: Elsevier.10.1016/B978-0-08-098258-8.00013-4Search in Google Scholar

Kulkarni, S. J., and J. P. Kaware. 2013. “Review on Research for Removal of Phenol from Wastewater.” International Journal of Scientific and Research Publications 3: 1–4.Search in Google Scholar

Lal, K., and A. Garg. 2015. “Catalytic Wet Oxidation of Phenol under Mild Operating Conditions: Development of Reaction Pathway and Sludge Characterization.” Clean Technologies and Environmental Policy 17: 199–210.10.1007/s10098-014-0777-9Search in Google Scholar

Lowell, S., J. E. Shields, M. A. Thomas, and M. M. Thommes. 2006. Characterization of Porous Solids and Powders: Surface Area and Pore Size and Density. NewYork: Kluwer Academic Publishers.Search in Google Scholar

Lucas, M. S., and J. A. Peres. 2009. “Removal of COD from Olive Mill Wastewater by Fenton’s Reagent: Kinetic Study.” Journal of Hazardous Materials 168: 1253–59.10.1016/j.jhazmat.2009.03.002Search in Google Scholar PubMed

Madejová, J., H. Pálková, and L. Jankovič. 2015. “Near-Infrared Study of the Interaction of Pyridine with Acid-Treated Montmorillonite.” Vibrational Spectroscopy 76: 22–30.10.1016/j.vibspec.2014.11.003Search in Google Scholar

Nguyen, Q. T., and D. G. Baird. 2006. “Preparation of Polymer–Clay Nanocomposites and Their Properties.” Polymers for Advanced Technologies 25 (4): 270–85.10.1002/adv.20079Search in Google Scholar

Nieto, Leopoldo Martínez, Gassan Hodaifa, Salvador Rodríguez, José A. Giménez, and Javier Ochando. 2011 (9). “Degradation of organic matter in olive-oil mill wastewater through homogeneous Fenton-like reaction.” Chemical Engineering Journal 173 (2): 503–10.10.1016/j.cej.2011.08.022Search in Google Scholar

Noyan, H., M. Önal, and Y. Sarıkaya. 2007. “The Effect of Sulphuric Acid Activation on the Crystallinity, Surface Area, Porosity, Surface Acidity, and Bleaching Power of a Bentonite.” Food Chemistry 105: 156–63.10.1016/j.foodchem.2007.03.060Search in Google Scholar

Önal, M., and Y. Sarıkaya. 2007. “Preparation and Characterization of Acid-Activated Bentonite Powders.” Powder Technology 172: 14–18.10.1016/j.powtec.2006.10.034Search in Google Scholar

Pires, C. A., A. C. C. Dos Santos, and E. Jordão. 2015. “Oxidation of Phenol in Aqueous Solution with Copper Oxide Catalyst Supported on γ-Al2O3 Pillared Clay and TiO2: Comparison of the Performance and Cost Associated with Each Catalyst.” Brazilian Journal of Chemical Engineering 32: 837–48.10.1590/0104-6632.20150324s00002232Search in Google Scholar

Pliego, G., J. A. Zazo, P. Garcia-Munoz, M. Munoz, J. A. Casas, and J. J. Rodriguez. 2015. “Trends in the Intensification of the Fenton Process for Wastewater Treatment- an Overview.” Critical Reviews in Environmental Science and Technology 45: 2611–92.10.1080/10643389.2015.1025646Search in Google Scholar

Pouran, S. R., A. A. Abdul Raman, and W. M. A. Wan Daud. 2014. “Review on the Application of Modified Iron Oxides as Heterogeneous Catalysts in Fenton Reactions.” Journal of Cleaner Production 64: 24–35.10.1016/j.jclepro.2013.09.013Search in Google Scholar

Pеtrоvić, Z., P. Dugić, V. Аlеksić, S. Bеgić, J. Sаdаdinоvić, V. Мićić, and N. Kljajić. 2014. “Composition, Structure and Textural Characteristics of Domestic Acid Activated Bentonite.” Contemporary Materials 1: 133–39.10.7251/COMEN1401133PSearch in Google Scholar

Quintanilla, A., J. A. Casas, and J. J. Rodriguez. 2010. “Hydrogen peroxide-promoted-CWAO of Phenol with Activated Carbon.” Applied Catalysis B: Environmental 93: 339–45.10.1016/j.apcatb.2009.10.007Search in Google Scholar

Ribeiro, R. S., A. M. T. Silva, J. L. Figueiredo, J. L. Faria, and H. T. Gomes. 2016. “Catalytic Wet Peroxide Oxidation: A Route Towards the Application of Hybrid Magnetic Carbon Nanocomposites for the Degradation of Organic Pollutants. A Review.” Applied Catalysis B: Environmental 187: 428–60.10.1016/j.apcatb.2016.01.033Search in Google Scholar

Rokhina, E. V., and J. Virkutyte. 2011. “Environmental Application of Catalytic Processes: Heterogeneous Liquid Phase Oxidation of Phenol with Hydrogen Peroxide.” Critical Reviews in Environmental Science and Technology 41: 125–67.10.1080/10643380802669018Search in Google Scholar

Santos, A., P. Yustos, S. Rodriguez, and F. Garcia-Ochoa. 2006. “Wet Oxidation of Phenol, Cresols and Nitrophenols Catalyzed by Activated Carbon in Acid and Basic Media.” Applied Catalysis B: Environmental 65: 269–81.10.1016/j.apcatb.2006.02.005Search in Google Scholar

Sun, X., C. Wang, Y. Li, W. Wang, and J. We. 2015. “Treatment of Phenolic Wastewater by Combined UF and NF/RO Processes.” Desalination 355: 68–74.10.1016/j.desal.2014.10.018Search in Google Scholar

Taylor, D. R., and W. Hills. 1991. “Process for Making Acid Activated Bleaching Earth Using High Susceptibility Source Clay and Novel Bleaching Earth Product.” US-5008226.Search in Google Scholar

Taylor, D. R., and D. B. Jenkins. 1998. “Acid Activated Clays.” Transactions of the Society of Mining Engineers of AIME 282: 1901–10.Search in Google Scholar

Taylor, D. R., and C. B. Ungermann. 1999. “Process for Making Acid Activated Bleaching Earth Using High Susceptibility Source Clay and Novel Bleaching Earth Product.” US- 5008226A.Search in Google Scholar

Tehrani-Bagha, A. R., and T. Balchi. 2018. “Catalytic Wet Peroxide Oxidation in Advanced Oxidation Processes for Waste Water Treatment,” in Ameta and Rakshit Ameta, Emerging Green Chemical Technology, edited by C. Suresh, 375–402. London: Academic Pres.10.1016/B978-0-12-810499-6.00012-7Search in Google Scholar

Tjong, S. C 2006. “Synthesis and Structure-Property Characteristics of Clay-Polymer Nanocomposites,” in Nanocrystalline Materials: Their Synthesis-Structure-Property Relationships and Applications, edited by S. C. Tjong, 311– 48. Amsterdam: Elsevier.10.1016/B978-008044697-4/50023-5Search in Google Scholar

Tomul, F. 2016. “The Effect of Ultrasonic Treatment on Iron–Chromium Pillared Bentonite Synthesis and Catalytic Wet Peroxide Oxidation of Phenol.” Applied Clay Science 120: 121–34.10.1016/j.clay.2015.11.007Search in Google Scholar

Velde, B 1995. Origin and Mineralogy of Clays: Clays and the Environment, 8. New York: Springer.10.1007/978-3-662-12648-6_2Search in Google Scholar

Vicente, M. A., A. Gil, and F. Bergaya. 2013. “Pillared Clays and Clay Minerals,” in Development in Clay Science: Handbook of Clay Science Vol. 5, edited by F. Bergaya, and G. Lagaly. Amsterdam: Elsevier.10.1016/B978-0-08-098258-8.00017-1Search in Google Scholar

Wang, N., T. Zheng, G. Zhang, and P. Wang. 2016. “A Review on Fenton-Like Processes for Organic Wastewater Treatment.” Journal of Environmental Chemical Engineering 4: 762–87.10.1016/j.jece.2015.12.016Search in Google Scholar

Yıldız, N., Z. Aktaş, and A. Çalımlı. 2004. “Sulphuric Acid Activation of a Calcium Bentonite.” Particulate Science and Technology 22: 21–33.10.1080/02726350490422392Search in Google Scholar

Yu, K., N. Kumar, A. Aho, J. Roine, I. Heinmaa, D. Y. Murzin, and A. Ivaska. 2016. “Determination of Acid Sites in Porous Aluminosilicate Solid Catalysts for Aqueous Phase Reactions Using Potentiometric Titration Method.” Journal of Catalysis 335: 117–24.10.1016/j.jcat.2015.12.010Search in Google Scholar

Yu, W., P. Wang, C. Zhou, H. Zhao, D. Tong, H. Zhang, H. Yang, S. Ji, and H. Wang. 2017. “Acid-Activated and WOx-loaded Montmorillonite Catalysts and Their Catalytic Behaviors in Glycerol Dehydration.” Chinese Journal of Catalysis 38: 1087–100.10.1016/S1872-2067(17)62813-4Search in Google Scholar

Zhansheng, W. U., L. I. Chun, S. Xifang, X. Xiaolin, D. Bin, L. Jine, and Z. Hongsheng. 2006. “Characterization, Acid Activation and Bleaching Performance of Bentonite from Xinjiang.” Chinese Journal of Chemical Engineering 14: 253–58.10.1016/S1004-9541(06)60067-0Search in Google Scholar

Zheng, R., H. Gao, Z. Ren, D. Cen, and Z. Chen. 2017. “Preparation of Activated Bentonite and Its Adsorption Behavior on Oil-Soluble Green Pigment.” Physicochemical Problems of Mineral Processing 53: 829−45.Search in Google Scholar

Zhou, S., C. Zhang, H. Hu, Y. Wang, R. Xu, C. Xia, H. Zhang, and H. Song. 2014. “Catalytic Wet Peroxide Oxidation of 4-Chlorophenol over Al-Fe-, Al-Cu-, and Al-Fe-Cu-pillared Clays: Sensitivity, Kinetics and Mechanism.” Applied Clay Science 95: 275–83.10.1016/j.clay.2014.04.024Search in Google Scholar

Received: 2018-06-30
Revised: 2018-10-22
Accepted: 2018-12-05
Published Online: 2018-12-15

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