Modeling and optimization of removal of toluene from aqueous solutions using iron oxide nanoparticles by RSM method

Authors
1 Sahand University of Technology
2 Member of Environmental Engineering Research Center
Abstract
Toluene is a dangerous pollutant in aqueous solutions that should be removed completely. In this paper iron oxide nanoparticles were employed for removing of toluene from aqueous solutions with initial concentration of 100 ppm by Fenton-Like process. Iron oxide nanoparticles synthesised from spent catalysts of Tabriz Petrochemical Styrene Unit using a ball mill. these nanoparticles were characterized by BET, XRD, XRF and FE-SEM analysis. The milling of spent catalysts was performed in dry ball mill. Dry ball milling of spent catalysts was carried out in presence of argon as an inert gas. Iron oxide nanoparticles with diameter about 18 nm were obtained after 4 hours by dry ball milling of spent catalysts using 15 balls with a diameter of 20 mm. The milling was performed at a rotation speed of 400 rpm.The results of BET analysis showed that specific surface of catalysts has increased more than 9 times with the milling of spent catalysts. XRD patterns showed that during dry milling, some of Fe3O4 has converted to Fe2O3. Due to the higher rate of reaction of Fe2O3 compared to the Fe3O4 in Fenton process, this conversion causes higher rate of toluene elimination from aqueous solutions. The crystal size of spent catalysts and synthesized iron oxide nanoparticles was calculated by Scherrer equation. The crystal size of spent catalysts and synthesized iron oxide nanoparticles were obtained 56.6 nm and 33.9 nm respectively which confirmed the results of BET analysis. The concentration of toluene in aqueous solutions was measured by Gas Chromatography (GC-Agilent 7890A) equipped with FID detector and HP-Plot Q column (30m × 0.530 mm× 40.0 μm) using liquid-liquid extraction by hexane. Hexane and samples were mixed with volume ratio of 1/10. Samples were injected to GC in volume of 1 micro liter by a syringe (Agilent). Experiments were performed at pH=3 and room temperature (25◦C) in a batch reactor in volume of 500 ml with a mechanical stirrer. Due to study of interaction between the parameters and determining the optimal conditions, experimental design was performed by RSM method. [H2O2]/[Catalyst], [H2O2]/[concentration of pollution] and time (min) were considered as efficient parameters on removing of toluene. Quadratic equation with high correlation coefficient fitted using RSM method. R2 and R2(adj) values of predicted model for removing of toluene in Fenton-Like process were obtained 99.14% and 98.37% respectively. The results showed that [H2O2]/[Catalyst] and [H2O2]/[concentration of pollution] have optimum ranges. The optimum ranges for [H2O2]/[Catalyst] and [H2O2]/[concentration of pollution] were obtained 0.36-0.5 and 4-5.5 respectively . Optimal values for [H2O2]/[Catalyst], [H2O2]/[concentration of pollution] and time (min) for removing of toluene in Fenton-Like process were obtained 0.460, 4.928 and 105.7 respectively. In optimum conditions for efficient parameters, complete removal of toluene by Minitab software was predicted. Experiments in the optimum conditions also confirmed the results of Minitab software. The results showed that spent catalysts of Tabriz Petrochemical which are considered as waste, have a good ability for activation of H2O2 and removing of toluene from aqueous solutions. Keywords: Toluene, Aqueous solution, Fenton-Like, Iron oxide nanoparticles, Optimization.

Keywords


[1] J. Xu, J. Tang, S. A. Baig, X. Lv, and X. Xu, "Enhanced dechlorination of 2, 4-dichlorophenol by Pd/Fe3 O 4 nanocomposites," Journal of hazardous materials, vol. 244, pp. 628-636, 2013.
[2]           D. LI and J. QU, "The progress of catalytic technologies in water purification: A review," Journal of Environmental Sciences, vol. 21, pp. 713-719, 2009.
[3]           A. Pintar, "Catalytic processes for the purification of drinking water and industrial effluents," Catalysis today, vol. 77, pp. 451-465, 2003.
[4]           "An Introduction To Indoor Air Quality (IAQ) Volatile Organic Compounds (VOCS), 2012 Aug " United State Environmental Protection Agency available from http://www.epa.gov/iaq/voc.html
[5]           K. Rusevova, F.-D. Kopinke, and A. Georgi, "Nano-sized magnetic iron oxides as catalysts for heterogeneous Fenton-like reactions—Influence of Fe (II)/Fe (III) ratio on catalytic performance," Journal of hazardous materials, vol. 241, pp. 433-440, 2012.
[6]           E. Saputra, S. Muhammad, H. Sun, H.-M. Ang, M. O. Tadé, and S. Wang, "A comparative study of spinel structured Mn3O4, Co3O4 and Fe3O4 nanoparticles in catalytic oxidation of phenolic contaminants in aqueous solutions," Journal of colloid and interface science, vol. 407, pp. 467-473, 2013.
[7]           S.-P. Sun, X. Zeng, and A. T. Lemley, "Nano-magnetite catalyzed heterogeneous Fenton-like degradation of emerging contaminants carbamazepine and ibuprofen in aqueous suspensions and montmorillonite clay slurries at neutral pH," Journal of Molecular Catalysis A: Chemical, vol. 371, pp. 94-103, 2013.
[8]           L. Xu and J. Wang, "Fenton-like degradation of 2, 4-dichlorophenol using Fe3O4 magnetic nanoparticles," Applied Catalysis B:Environmental, vol. 123, pp. 117-126, 2012.
[9]           A. O. Ifelebuegu and C. P. Ezenwa, "Removal of endocrine disrupting chemicals in wastewater treatment by Fenton-like oxidation," Water, Air, & Soil Pollution, vol. 217, pp. 213-220, 2011.
[10]         V. Kavitha and K. Palanivelu, "The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol," Chemosphere, vol. 55, pp. 1235-1243, 2004.
[11]         S. Mortazavi, A. Sabzali, and A. Rezaee, "Sequence-Fenton reaction for decreasing phenol formation during benzene chemical conversion in aqueous solutions," 2005.
[12]         S. Zhang, X. Zhao, H. Niu, Y. Shi, Y. Cai, and G. Jiang, "Superparamagnetic Fe3O4 nanoparticles as catalysts for the catalytic oxidation of phenolic and aniline compounds," Journal of hazardous materials, vol. 167, pp. 560-566, 2009.
[13]         S. G. Huling, S. Hwang, D. Fine, and S. Ko, "Fenton-like initiation of a toluene transformation mechanism," Water research, vol. 45, pp. 5334-5342, 2011.
 
[14]         L. Hou, Q. Zhang, F. Jérôme, D. Duprez, H. Zhang, and S. Royer, "Shape-controlled nanostructured magnetite-type materials as highly efficient Fenton catalysts," Applied Catalysis B: Environmental, vol. 144, pp. 739-749, 2014.
[15]         D. C. Montgomery, "Design and Analysis of Experiments: Response Surface Method and Designs," John Wiley and Sons, Inc, New York, 2005.
[16] M. Ahmadi, F. Vahabzadeh, B. Bonakdarpour, E. Mofarrah, and M. Mehranian, "Application of the central composite design and response surface methodology to the advanced treatment of olive oil processing wastewater using Fenton's peroxidation," Journal of Hazardous Materials, vol. 123, pp. 187-195, 2005.
[17]         A. Saldaña-Robles, R. Guerra-Sánchez, M. I. Maldonado-Rubio, and J. M. Peralta-Hernández, "Optimization of the operating parameters using RSM for the Fenton oxidation process and adsorption on vegetal carbon of MO solutions," Journal of Industrial and Engineering Chemistry, vol. 20, pp. 848-857, 2014.
[18]         A. Khataee, M. Kasiri, and L. Alidokht, "Application of response surface methodology in the optimization of photocatalytic removal of environmental pollutants using nanocatalysts," Environmental technology, vol. 32, pp. 1669-1684, 2011.
[19] P. V. Nidheesh, R. Gandhimathi, and S. T. Ramesh, "Degradation of dyes from aqueous solution by Fenton processes: a review," Environmental Science and Pollution Research, vol. 20, pp. 2099-2132, 2013