Synthesis of Zeolite Y from Kaolin and Its Model Fuel Desulfurization Performance: Optimized by Box-Behnken Method

Document Type : Research Article


1 Chemical Engineering Department, Tarbiat Modares University, Tehran, I.R. IRAN

2 Chemical and Materials Engineering, Buein Zahra Technical University, Buein Zahra, Qazvin, I.R. IRAN


In this research, zeolite Na-Y was synthesized from Kaolin without an organic template under the non-hydrothermal condition to adsorb sulfur compound. Model fuel desulfurization was optimized by employing the Box-Behnken experimental design with 2 center points, the three parameters, and one response value. The objective was to find how sorption capacity is related to alkali fusion temperature, crystallization time, and aging time. Optimal DBT adsorbent was synthesized at 550 °C, minimum crystallization time, and maximum aging time. The zeolite samples were characterized by FT-IR and XRD. The crystallinity of the samples was lower than the crystallinity of commercial zeolite Y. During zeolite preparation, there was a competition between zeolite Na-Y, Na-P, Na-X and Na-A. The equilibrium results were well fitted by the Langmuir and Freundlich isotherms for the best adsorbent. The largest DBT adsorption capacity, 32.67 mg DBT/g, was calculated for the optimal adsorbent. Pseudo-first order and pseudo-second-order models were evaluated to understand the kinetics of the adsorption process. The reduction of DBT obeyed the second-order model of kinetic. Ni-Y and La-Y zeolites were prepared by the liquid-phase ion-exchange method. The maximum DBT adsorption capacity has been observed for Ni–Y (72.25 mg DBT/g) and La–Y (66.59 mg DBT/g).


Main Subjects

[2] Muzic M., Sertic‐Bionda K., Gomzi Z., Kinetic and Statistical Studies of Adsorptive Desulfurization of Diesel Fuel on Commercial Activated Carbons, Chemical Engineering & Technology, 31: 355-364 2008.
[4] Song C. E., Lee S.-G., Supported Chiral Catalysts on Inorganic Materials, Chemical Reviews, 102: 3495-3524 (2002).
[5] Selvavathi V., Chidambaram V., Meenakshisundaram A., Sairam B., Sivasankar B., Adsorptive Desulfurization of Diesel on Activated Carbon and Nickel Supported Systems, Catalysis Today, 141: 99-102 (2009).
[6] Salem A.B.S., Naphtha Desulfurization by Adsorption, Industrial & Engineering Chemistry Research, 33: 336-340 (1994).
[7] Mintova S., Olson N.H., Bein T., Electron Microscopy Reveals the Nucleation Mechanism of Zeolite Y from Precursor Colloids, Angewandte Chemie International Edition, 38: 3201-3204 (1999).
[8] Li Q., Creaser D., Sterte J., An Investigation of the Nucleation/Crystallization Kinetics of Nanosized Colloidal Faujasite Zeolites, Chemistry of Materials, 14: 1319-1324 (2002).
[9] Yang R.T., Hernández-Maldonado A.J., Yang F.H., Desulfurization of Transportation Fuels with Zeolites under Ambient Conditions, Science, vol. 301: 79-81, (2003).
[10] Velu S., Ma X., Song C., Selective Adsorption for Removing Sulfur from Jet Fuel over Zeolite-Based Adsorbents, Industrial & Engineering Chemistry Research, 42: 5293-5304 (2003).
[11] Hernández-Maldonado A.J., Yang F.H., Qi G., Yang R.T., Desulfurization of Transportation Fuels by π-Complexation Sorbents: Cu (I)-, Ni (II)-, and Zn (II)-Zeolites, Applied Catalysis B: Environmental, 56: 111-126 (2005).
[12] Hernández-Maldonado A.J., Stamatis S.D., Yang R.T., He A.Z., Cannella W., New Sorbents for Desulfurization of Diesel Fuels via π Complexation: Layered Beds and Regeneration, Industrial & Engineering Chemistry Research, 43: 769-776, (2004).
[14] Mallapur V.P., Oubagaranadin J.U.K., Lature S.S., "Synthesis of Zeolite from Inorganic Wastes." 
[15] Kovo A., Hernandez O., Holmes S., Synthesis and Characterization of Zeolite Y and ZSM-5 from Nigerian Ahoko Kaolin Using a Novel, Lower Temperature, Metakaolinization Technique, Journal of Materials Chemistry, 19: 6207-6212 (2009).
[16] Kim Y. C., Jeong J. Y., Hwang J.Y., Kim S.D., Kim W.J., Influencing Factors on Rapid Crystallization of High Silica Nano-Sized Zeolite Y without Organic Template under Atmospheric Pressure, Journal of Porous Materials, 16: 299-306 (2009).
[17] Bosch P., Ortiz L., Schifter I., Synthesis of Faujasite Type Zeolites from Calcined Kaolins, Industrial & Engineering Chemistry Product Research and Development, 2: 401-406 (1983).
[18] Basaldella E., Kikot A., Pereira E., Synthesis of Zeolites from Mechanically Activated Kaolin Clays, Reactivity of Solids, 8: 169-177 (1990).
[19] Wang J.-Q., Huang Y.-X., Pan Y., Mi J.-X., New Hydrothermal Route for the Synthesis of High Purity Nanoparticles of Zeolite Y from Kaolin and Quartz, Microporous and Mesoporous Materials, 232: 77-85 (2016).
[20] Bortolatto L. B., Santa R. A. B., Moreira J. C., Machado D. B., Martins M.A.P., Fiori M.A., et al., Synthesis and Characterization of Y Zeolites from Alternative Silicon and Aluminium Sources, Microporous and Mesoporous Materials, 248: 214-221 (2017).
[21] Covarrubias C., García R., Arriagada R., Yánez J., Garland M.T., Cr (III) Exchange on Zeolites Obtained from Kaolin and Natural Mordenite, Microporous and Mesoporous Materials, 88: 220-231 (2006).
[23] Wang J.-Q., Huang Y.-X., Pan Y., Mi J.-X., Hydrothermal Synthesis of High Purity Zeolite A from Natural Kaolin Without Calcination, Microporous and Mesoporous Materials, 199: 50-56 (2014).
[24] Abdullahi T., Harun Z., Othman M.H.D., A Review on Sustainable Synthesis of Zeolite from Kaolinite Resources via Hydrothermal Process, Advanced Powder Technology, (2017).
[25] Ma Y., Yan C., Alshameri A., Qiu X., Zhou C., Synthesis and Characterization of 13X Zeolite from Low-Grade Natural Kaolin, Advanced Powder Technology, 25: 495-499 (2014).
[27] Song C., Ma X., New Design Approaches to Ultra-Clean Diesel Fuels by Deep Desulfurization and Deep Dearomatization, Applied Catalysis B: Environmental, 41: 207-238 (2003).
[28] Oyinade A., Kovo A.S., Hill P., Synthesis, Characterization and Ion Exchange Isotherm of Zeolite Y Using Box–Behnken Design, Advanced Powder Technology, 27: 750-755 (2016).
[29] Bakhtiari G., Bazmi M., Abdouss M., Royaee S.J., Adsorption and Desorption of Sulfur Compounds by Improved Nano Adsorbent: Optimization Using Response Surface Methodology, Iranian Journal of Chemistry and Chemical Engineering (IJCCE), 36: 69-79 (2017).
[30] Jiang M., and Ng F.T., Adsorption of benzothiophene on Y Zeolites Investigated by Infrared Spectroscopy and Flow Calorimetry, Catalysis Today, 116: 530-536 (2006).
[31] Yao Z.-Y., Qi J.-H., Wang L.-H., Equilibrium, Kinetic and Thermodynamic Studies on the Biosorption of Cu (II) onto Chestnut Shell, Journal of Hazardous Materials, 174: 137-143 (2010).
[32] Kumar S., Zafar M., Prajapati J.K., Kumar S., Kannepalli S., Modeling Studies on Simultaneous Adsorption of Phenol and Resorcinol onto Granular Activated Carbon from Simulated Aqueous Solution, Journal of Hazardous Materials, 185: 287-294 (2011).
[33] Jha V.K., Nagae M., Matsuda M., Miyake M., Zeolite Formation from Coal Fly Ash and Heavy Metal Ion Removal Characteristics of Thus-Obtained Zeolite X in Multi-metal Systems, Journal of Environmental Management, 90: 2507-2514 (2009).
[34] Samiee Beyragh A., Varsei M., Meshkini M., Khodadadi Darban A., Gholami E., Kinetic and Adsorption Isotherms Study of Cyanide Removal from Gold Processing Wastewater Using Natural and Impregnated Zeolites," Iranian Journal of Chemistry and Chemical Engineering (IJCCE), 37(2):139-149 (2017).
[35] Araissi M., Elaloui E., Moussaoui Y., The removal of Cadmium, Cobalt and Nickel by Adsorption with Na-Y Zeolite, Iranian Journal of Chemistry and Chemical Engineering (IJCCE), Available Online from 15 August (2018).[in Press]
[36] Sang S., Liu Z., Tian P., Liu Z., Qu L., Zhang Y., Synthesis of Small Crystals Zeolite NaY, Materials Letters, 60: 1131-1133 (2006).
[37] Nibou D., Mekatel H., Amokrane S., Barkat M., Trari M., Adsorption of Zn2+ Ions onto NaA and NaX Zeolites: Kinetic, Equilibrium and Thermodynamic Studies, Journal of Hazardous Materials, 173: 637-646 (2010).
[39] Parr R. G., Pearson R.G., Absolute Hardness: Companion Parameter to Absolute Electronegativity, Journal of the American Chemical Society, 105: 7512-7516 (1983).
[40] Pearson R.G., Hard and Soft Acids and Bases, Journal of the American Chemical Society, 85: 3533-3539 (1963).
[41] Xiao J., Li Z., Liu B., Xia Q., Yu M., Adsorption of Benzothiophene and Dibenzothiophene on Ion-Impregnated Activated Carbons and Ion-Exchanged Y Zeolites, Energy & Fuels, 22: 3858-3863 (2008).