Synthesis of Nanozeolite and its Efficiency in Reducing the Ca2+ of Shiraz Oil Refinery Wastewater

Document Type : Research Paper


1 Assist. Prof., Dept. of Environmental Engineering, College of Environment, Karaj, Iran

2 MSc of Chemical Engineering-HSE, Dept. of Environmental Engineering, College of Environment, Karaj, Iran


The production of industrial wastewater with a variety of compounds is one of the major environmental challenges of human societies, posing a great threat to the health of society. In this study, synthesis of Y-type nanozeolite and its efficiency in reducing the Ca2+ of Shiraz oil refinery effluent compared to acid treated natural zeolite was investigated. Synthensis of nanozeolites was performed by sol-gel method using sodium silicate and sodium aluminate solution. The synthesized samples were analyzed by X-ray diffraction analysis, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) test. The X-ray diffraction results confirmed the crystalline structure of Y-type nanozeolites. The scanning electron microscopy images showed the formation of mesoporous particles. The specific porosity of the synthesized nanozeolite and also the total porosity were determined as 805.4m2/g and 0.4222 m3/g, respectively by BET analysis. Based on the nitrogen gas absorption / desorption isotherm, the presence of mesopores along the micro-pore in synthesized nanozeolite was confirmed. Kinetic studies showed the adsorption kinetics of both adsorbents are fit well with pseudo-second-order model, indicating that the interaction between the absorber surface and the adsorbent is the determining factor in adsorption process and diffusion of the Ca2+ ions to the inside of mesoporous zeolite canals is fast. The removal amount of Ca2+ from wastewater of oil-refinery for natural zeolite(50 g) and nano zeolite(5 g) in 1 L wastewater  after equilibrium time was determined as 60% and 95%, respectively and pH=7 was determined as the optimum pH.


Abdullahi, T., Harun, Z. & Othman, M. H. D. 2017. A review on sustainable synthesis of zeolite from kaolinite resources via hydrothermal process. Advanced Powder Technology, 28, 1827-1840.
Ada, K., Ergene, A., Tan, S. & Yalçın, E. 2009. Adsorption of remazol brilliant blue R using ZnO fine powder: equilibrium, kinetic and thermodynamic modeling studies. Journal of Hazardous Materials, 165, 637-644.
Ahmedzeki, N. S., Yilmaz, S. & Al-Tabbakh, B. A. 2016. Synthesis and characterization of nanocrystalline zeolite Y. Al-Khwarizmi Engineering Journal, 12, 79-89.
Asatekin, A. & Mayes, A. M. 2009. Oil industry wastewater treatment with fouling resistant membranes containing amphiphilic comb copolymers. Environmental Science and Technology, 43, 4487-4492.
Ates, A. & Akgül, G. 2016. Modification of natural zeolite with NaOH for removal of manganese in drinking water. Powder Technology, 287, 285-291.
Charkhi, A., Kazemeini, M., Ahmadi, S. J. & Kazemian, H. 2012. Fabrication of granulated NaY zeolite nanoparticles using a new method and study the adsorption properties. Powder Technology, 231, 1-6.
Choudhary, A., Kumari, S. & Ray, S. 2017. Tuning of catalytic property controlled by the molecular dimension of palladium–schiff base complexes encapsulated in zeolite Y. ACS Omega, 2, 6636-6645.
Chung, H.-K., Kim, W.-H., Park, J., Cho, J., Jeong, T.-Y. & Park, P.-K. 2015. Application of langmuir and freundlich isotherms to predict adsorbate removal efficiency or required amount of adsorbent. Journal of Industrial and Engineering Chemistry, 28, 241-246.
Dehghan, R. & Anbia, M. 2018. Rapid transformation of amorphous nanoparticles into crystalline Y nanozeolites using poly (vinyl alcohol) layers covered onto the amorphous nanoparticles. Crystal Growth and Design, 18, 7296-7304.
Faisal, M., Mulana, F., Gani, A. & Daimon, H. 2015. Physical and chemical properties of wastewater discharged from tofu industries in Banda Aceh city, Indonesia. Research Journal of Pharmaceutical, Biological and Chemical Sciences, 6, 1053-1058.
Frising , T. & Leflaive, P. 2008. Extraframework cation distributions in X and Y faujasite zeolites: a review. Microporous and Mesoporous Materials, 114, 27-63.
Gupta, V. K., Ali, I., Saleh, T. A., Nayak, A. & Agarwal, S. 2012. Chemical treatment technologies for waste-water recycling- an overview. RSC Advances, 2, 6380-6388.
Higgins, J., Lapierre, R. B., Schlenker, J., Rohrman, A., Wood, J., Kerr, G., et al. 1988. The framework topology of zeolite beta. American Chemical Society, Division of Petroleum Chemistry, Preprints;(USA), 33.
Jaroniec, M. & Sayari, A. 2002. Nanoporous Materials III, Elsevier Pub. Amesterdam. The Netherlands.
Keller, A. A., Wang, H., Zhou, D., Lenihan, H. S., Cherr, G., Cardinale, B. J., et al. 2010. Stability and aggregation of metal oxide nanoparticles in natural aqueous matrices. Environmental Science and Technology, 44, 1962-1967.
Khavarpour, M. 2018. Adsorption of malachite green from aqueous solution by nanozeolite clinoptilolite: equilibrium, kinetic and thermodynamic studies. International Journal of Engineering, 31, 1-11.
Kithome, M., Paul, J., Lavkulich, L. & Bomke, A. 1998. Kinetics of ammonium adsorption and desorption by the natural zeolite clinoptilolite. Soil Science Society of America Journal, 62, 622-629.
Mansouri, N., Rikhtegar, N., Panahi, H. A., Atabi, F. & Shahraki, B. K. 2013. Porosity, characterization and structural properties of natural zeolite-clinoptilolite-as a sorbent. Environment Protection Engineering, 39.
Mccabe, W. L., Smith, J. C. & Harriott, P. 1993. Unit operations of chemical engineering, McGraw-Hill, New York.
Meyers, R. A. 2004. Handbook of Petroleum Refining Processes, McGraw-Hill, New York.
Rachman, R. A., Martia, U. T. I., Aulia, W., Iqbal, R. M., Widiastuti, N. & Kurniawan, F. 2018. Combination of microbial fuel cell and zeolite Na-Y adsorption for chromium removal.  AIP Conference Proceedings, AIP Publishing, 020073.
Rahman, M., Awang, M. & Yusof, A. 2012. Preparation, characterization and application of zeolite-Y (Na-Y) for water filtration. Australian Journal of Basic and Applied Sciences, 6, 50-54.
Ramishvili, T., Tsitsishvili, V., Chedia, R., Sanaia, E., Gabunia, V. & Kokiashvili, N. 2017. Preparation of ultradispersed crystallites of modified natural clinoptilolite with the use of ultrasound and its application as a catalyst in the synthesis of methyl salicylate. American Journal of Nano Research and Applications, 5, 26-32.
Ranade, V. V. & Bhandari, V. M. 2014. Industrial Wastewater Treatment, Recycling and Reuse, Butterworth-Heinemann.
Rios Reyes, C., Appasamy, D. & Roberts, C. 2011. An integrated remediation system using synthetic and natural zeolites for treatment of wastewater and contaminated sediments. Dyna, 78, 125-134.
Sánchez-Hernández, R., Padilla, I., López-Andrés, S. & López-Delgado, A. 2018. Al-waste-based zeolite adsorbent used for the removal of ammonium from aqueous solutions. International Journal of Chemical Engineering, 2018, doi. org/10.1155/2018/1256197.
Tan, I., Ahmad, A. & Hameed, B. 2009. Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2, 4, 6-trichlorophenol on oil palm empty fruit bunch-based activated carbon. Journal of Hazardous Materials, 164, 473-482.
Viswanadham, N., Kamble, R., Singh, M., Kumar, M. & Dhar, G. M. 2009. Catalytic properties of nano-sized ZSM-5 aggregates. Catalysis Today, 14, (1), 182-186.
Wang, R., Sang, S., Zhu, D., Liu, S. & Yu, K. 2018. Pore characteristics and controlling factors of the Lower cambrian hetang formation shale in northeast Jiangxi, China. Energy Exploration and Exploitation, 36, 43-65.
Wang, S. & Peng, Y. 2010. Natural zeolites as effective adsorbents in water and wastewater treatment. Chemical Engineering Journal, 156, 11-24.
Weber, T. W. & Chakravorti, R. K. 1974. Pore and solid diffusion models for fixed‐bed adsorbers. AIChE Journal, 20, 228-238.