Effects of Water Content on SO2/N2 Binary Adsorption Capacities of 13X and 5A Molecular Sieve, Experiment, Simulation, and Modeling

Document Type : Research Paper


1 Research Institute of Petroleum Industry

2 Research Institute of Petroleum Industry Faculty of Natural resources, Malayer University


In this work, SO2 adsorption on 13X and 5A was explored at different concentrations, and the results were compared to molecular simulation and models. The adsorbent saturation tests were performed at four different concentrations of 250, 500, 750, and 1000 ppm, and it was observed that saturation would take more time for higher SO2 concentrations. Grand Canonical Monte Carlo method was used for simulation. In addition, extra framework cations of Na were used 13X structure and Na and Ca Cations were used in 5A structure. The results of the simulation were compared to experiments. The effect of water molecule content on adsorption was determined by inserting a different number of water molecules. Also, the outcome of experiments and simulations were in good agreement. The results showed that 13X is a better adsorbent for SO2 than 5A. 13X zeolite with 96 water molecules and 5A with 99 were provided the best prediction of experimental results. Yoon-Nelson and BDST models were also used to find the rate of adsorption capacity reduction related to breakthrough curve and loading amount. The results of the two model suggested that 13X has a higher loading capacity while 5A provided longer saturation time.


Lee C., Richter A., Lee H., Kim Y. J., and et al., “Impact of Transport of Sulfur Dioxide from the Asian Continent on the Air Quality over Korea during May 2005,” Atmos. Environ., 2008, 42 (7), 1461–1475.
Vet R. and Ro C. U., “Contribution of Canada-United States Transboundary Transport to Wet Deposition of Sulphur and Nitrogen oxides-A Mass Balance Approach,” Atmos. Environ., 2008, 42(10), 2518–2529.
Benko T., Teichmann C., Mizsey P., and Jacob D., “Regional Effects and Efficiency of Flue Gas Desulphurization in the Carpathian Basin,” Atmos. Environ., 2007, 41(38), 8500–8510.
Gurjar B. R., Butler T. M., Lawrence M. G., and Lelieveld J., “Evaluation of Emissions and Air Quality in Megacities,” Atmos. Environ., 2008, 42(7), 1593–1606.
Iran Energy Balance Sheet of 1394 (2015-2016), Tehran, 2017.
Pulido R. and Fernández G., “Mexican Bottom of Barrel Life Cycle Environmental Improvement Proposal,” Enery, 2007, 32(4), 619–626.
Gupta A., Gaur V., and Verma N., “Breakthrough Analysis for Adsorption of Sulfur-Dioxide over Zeolites,” Chem. Eng. Process., 2004, 43(1), 9–22.
Allen S. J., Ivanova E., and Koumanova B., “Adsorption of Sulfur Dioxide on Chemically Modified Natural Clinoptilolite,” Acid Modification. Chem. Eng. J., 2009, 152, 389–395.
Ivanova E. and Koumanova B., “Adsorption of Sulfur Dioxide on Natural Clinoptilolite Chemically Modified with Salt Solutions,” J. Hazard. Mater. Ma., 2009, 167, 306–312.
Tsibranska I. and Assenov A., “Experimental Verification of the Model of Adsorption in Biporous Particles,” Chem. Eng. Process., 2000, 39(2), 149–159.
Golchoobi A., Khosravi A., Modarress H., and Ahmadzadeh A., “Effect of Charge, Size and Temperature on Stability of Charged Colloidal Nano Particles,” Chinese J. Chem. Phys., 2012, 25(5), 617–624.
Wang H. and Meng F., “The Permeability Enhancing Mechanism of Menthol on Skin Lipids: A Molecular Dynamics Simulation Study,” J. Mol. Model., 2017, 23(10), 279.
Li W., Zhu Y., Wang G., Wang Y., and et al., “Molecular Model and ReaxFF Molecular Dynamics Simulation of Coal Vitrinite Pyrolysis,” J. Mol. Model., 2015, 21(8), 188.
Jasik M. and Szefczyk B., “Parameterization and Optimization of the Menthol Force Field from Molecular Dynamics Simulations,” J. Mol. Model., 2016, 22, 234.
Alptekin S., “Structural Phase Transition of BeTe: An Ab Initio Molecular Dynamics Study,” J. Mol. Model., 2017, 23(9), 261.
Wang J., Yang M., Deng D., and Qiu S., “The Adsorption of NO, NH3, N2 on Carbon Surface: A Density Functional Theory Study,” J. Mol. Model., 2017, 23(9), 262.
Golzar K., Modarress H., and Amjad-Iranagh S., “Effect of Pristine and Functionalized Single- and Multi-Walled Carbon Nanotubes on CO2 Separation of Mixed Matrix Membranes Based on Polymers of Intrinsic Microporosity (PIM-1): A Molecular Dynamics Simulation Study,” J. Mol. Model., 2017, 23(9), 266.
Yu S., Bo J., and Jiahong L., “Simulations and Experimental Investigations of the Competitive Adsorption of CH4 and CO2 on Low-Rank Coal Vitrinite,” J. Mol. Model., 2017, 23(10), 280.
Khosravi A., Golchoobi A., Modarress H., and Ahmadzadeh A., “The Effects of Partial Charges and Water Models on Water Adsorption in Nanostructured Zeolites, Application of PN-TrAz Potential in Parallel GCMC,” Mol. Simul., 2013, 39(6), 495–504.
Golchoobi A. and Pahlavanzadeh H., “Molecular Simulation, Experiments and Modelling of Single Adsorption Capacity of 4A Molecular Sieve for CO2-CH4 Separation,” Sep. Sci. Technol., 2016, 51(14), 2318–2325.
Golchoobi A. and Pahlavanzadeh H., “Extra-Framework Charge and Impurities Effect, Grand Canonical Monte Carlo and Volumetric Measurements of CO2/CH4/N2 Uptake on NaX Molecular Sieve,” Sep. Sci. Technol., 2017, 52 (16), 2499–2512.
Rahmati M. and Modarress H., “Nitrogen Adsorption on Nanoporous Zeolites Studied by Grand Canonical Monte Carlo Simulation,” J. Mol. Struct. THEOCHEM., 2009, 901, 110–116.
Tasharrofi S., Taghdisian H., and Golchoobi A., “Vertically Aligned Double Wall Carbon Nanotube Arrays Adsorbent for Pure and Mixture Adsorption of H2S, Ethylbenzene and Carbon Monoxide, Grand Canonical Monte Carlo Simulation,” J. Mol. Graph. Model., 2018, 81(C), 86–96.
Carvalhoa A. J. P., Ferreirab T., and Candeiasa A. J. E., “Molecular Simulations of Nitrogen Adsorption in Pure Silica MCM-41 Materials,” J. Mol. Struct. THEOCHEM., 2005, 729, 65–69.
Herdes C., Valente A., Lin, Z., Rocha J., and et al., “Selective Adsorption of Volatile Organic Compounds in Micropore Aluminum Methylphosphonate-R: A Combined Molecular Simulation-Experimental Approach,” Langmuir, 2007, 23, 7299–7305.
Agnihotri S., Kim P., Zheng Y., Mota J. P. B., and et al., “Regioselective Competitive Adsorption of Water and Organic Vapor Mixtures on Pristine Single-Walled Carbon Nanotube Bundles,” Langmuir, 2008, 24, 5746–5754.
Ewald P. P., “Die Berechnung Optischer Und Elektrostatischer Gitterpotentiale,” Ann. Phys., 1921, 369(3), 253–287.
Yi H., Deng H., Tang X., Yu Q., and et al., “Adsorption Equilibrium and Kinetics for SO2 NO, CO2 on Zeolites FAU and LTA,” J. Hazard. Mater., 2012, 203, 111–117.
Deng H., Yi H., Tang X., Yu Q., and et al., “Adsorption Equilibrium for Sulfur Dioxide Nitric Oxide, Carbon Dioxide, Nitrogen on 13X and 5A Zeolites,” Chem. Eng. J., 2012, 188, 77–85.
Ckenfelder W. W., “Industrial Water Pollution Control,” McGraw-Hill: NewYork, 1989.
Ryzhikov A., Hulea V., Tichit D., Leroi C., and et al., “Methyl Mercapt=an and Carbonyl Sulfide Traces Removal through Adsorption and Catalysis on Zeolites and Layered Double Hydroxides,” Appl. Catal. A Gen., 2011, 397(1-2), 218–224.
Volesky B. and Prasetyo I., “Cadmium Removal in a Biosorption Column,” Biotechnol. Bioeng., 1994, 43, 1010–1015.
Yoon Y. H. and Nelson J. H., “Application of Gas Adsorption Kinetics I. A Theoretical Model for Respirator Cartridge Service Life,” Am. Ind. Hyg. Assoc. J., 1984, 45(8), 509–516.