High Content of Sulfur in Liquid Stream Removal via new Carbonous Nano Adsorbent: Equilibrium, Kinetic study

Document Type : Original Research Paper


1 Faculty of Chemical Engineering, Urmia University of Technology, P.O.Box 5716617165, Urmia, Iran

2 Pars Oil & Gas Company (POGC), P.O.Box 14147 13111, Tehran, Iran


This research evaluates dibenzothiophene (DBT) adsorptive removal from the liquid stream on the graphitic carbon nitride (GCN) as a synthesized adsorbent at 25 0C with 3 g for 600 min. The morphological properties of GCN have been investigated by Brunauer–Emmett–Teller (BET), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), and X-ray Diffraction (XRD). The study of the characteristic properties of nano adsorbent proves the suitability of the synthesized GCN in mercaptan adsorption process with the obtained data showing a good agreement with Freundlich model. The equilibrium capacity of DBT adsorption has been calculated at about 39.1 mg/g. This has also been 25.8 mg/g for TBM (tertiary butyl mercaptan). The adsorption capacity has increased by adding to the adsorbent dosage. Thermodynamic studies expose the negative values for ΔS0 (-8.99 kJ/mol. K), ΔH0 (-21.05 kJ/mol), and ΔG0 (8.91 kJ/mol), which demonstrate that DBT adsorption has been a natural exothermic process. In addition, this experiment verifies that the substitution of N into the carbon structure improves the DBT removal efficiency in comparison with pristine CNT as an adsorbent. The removal efficiency of DBT onto GCN has been approximately 80%, i.e. 20% higher than that of pure CNT. Results show that the adsorption capacity of DBT as a cyclic source of mercaptan has been higher than Tertiary butyl mercaptan (TBM) as a liner one. The DBT adsorption mechanism is done by π–π electron interactions between the aromatic structures of DBT, lone-pair electrons of the S atoms, and the pyridinic GCN planes band.


Khan, N. A., Hasan, Z. and Jhung, S. H. (2013). Adsorptive removal of hazardous materials using metal-organic frameworks (MOFs): A review. J. Hazard. Mat., 2; 444–456. https://doi.org/10.1016/j.jhazmat.2012.11.011
Hoseini, D., Z. and Meshkat, S. S.. (2019). Experimental and modeling study of asphaltene adsorption by carbon nanotubes frommodel oil solution. J. Pet. Sci. Eng. 174; 1053-1061.
Fallah, R. N. and Azizian, S. (2012). Removal of thiophenic compounds from liquid fuel by different modi fi ed activated carbon cloths. Fuel Proc. Tech., 93(1); 45–52. https://doi.org/10.1016/j.fuproc.2011.09.012.
Advances, R. S. C. and Srivastava, V. C. (2012). Advances An evaluation of desulfurization technologies for sulfur removal from liquid fuels. RSC. adv., 2; 759–783. https://doi.org/10.1039/c1ra00309g.
Deliyanni, E., Seredych, M. and Bandosz, T. J. (2009). Interactions of 4 , 6 Dimethyldibenzothiophene with the Surface of Activated Carbons. Langmuir, 25(16); 9302–9312. https://doi.org/10.1021/la900854x.
Kumagai, S., Ishizawa, H. and Toida, Y. (2010). Influence of solvent type on dibenzothiophene adsorption onto activated carbon fiber and granular coconut-shell activated carbon. Fuel. 89(2); 365–371. https://doi.org/10.1016/j.fuel.2009.08.013.
Meshkat, S.S., Tavakoli, O. and Rashidi, A.M. (2018). Removal of mercaptan from natural gas condensate using N-doped carbon nanotube adsorbents: Kinetic and DFT study. J. Nat. Gas. Sci. Eng., 55; 288-297.
Seredych, M. and Bandosz, T. J. (2010). Adsorption of Dibenzothiophenes on Nanoporous Carbons : Identification of Specific Adsorption Sites Governing Capacity and Selectivity. Amer. Chem. Soc.,(34); 3352–3360. https://doi.org/10.1021/ef9015087.
Khaled, M. (2015). Adsorption performance of multiwall carbon nanotubes and graphene oxide for removal of thiophene and dibenzothiophene from model diesel fuel. Res. Chem. Intermed., 41; 9817–9833. https://doi.org/10.1007/s11164-015-1986-5.
Kim, J.H., Ma, X., Zhou, A. and Song, C. (2006). Ultra-deep desulfurization and denitrogenation of diesel fuel by selective adsorption over three different adsorbents: a study on adsorptive selectivity and mechanism. Catal. Today, 111; 74–83.
Peng, S. (2018). Removal of low concentration CH3SH with regenerable Cu-doped mesoporous silica. J. Colloid Int. Sci., 513; 903-911.
Saleh, T. A., Al-hammadi, S. A., Tanimu, A. and Alhooshani, K. (2018). Ultra-deep adsorptive desulfurization of fuels on cobalt and molybdenum nanoparticles loaded on activated carbon derived from waste rubber. J. Colloid And Int. Sci., 513; 779-787. https://doi.org/10.1016/j.jcis.2017.11.076.
Moosavi, E. S., Dastgheib, S. A. and Karimzadeh, R. (2012). Adsorption of Thiophenic Compounds from Model Diesel Fuel, Energies, 5(12); 4233-4250. https://doi.org/10.3390/en5104233.
Yua, G.X., Jin, M. Sun, J., Zhou, X.L., Chen, L.F. and Wang, J.A. (2013). Oxidative modification of rice hull based carbon for dibenzothiophene adsorptive removal. Catal. Today. 12; 31–37.
Muzica, M., Biondaa, K. S., Gomzia, Z., Podolskib, S. and Telenb, S. (2010). Study of diesel fuel desulfurization by adsorption. Chem. Eng. Res. Des., 88; 487–495.
Zheng, Y., Lin, L., Wang, B. and Wang, X. (2015). Graphitic carbon nitride polymers toward sustainable photoredox catalysis. Angew. Chem. Int. Ed., 54; 12868-12884.
Thomas, A., Fischer, Goettmann, A., Antonietti, F. M., Müller, J.O., Schlögl, R. and Carlsson, J.M. (2008). Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts. J. Mater. Chem., 18; 4893-4908.
Zhao, H., Tian, C., Sun, H., Xiao, K. and Wong, P. K. (2019). Enhanced adsorption and photocatalytic activities of ultrathin graphitic carbon nitride nanosheets :Kinetics and mechanism. Chem. Eng. J., 381; 122760-122778. https://doi.org/10.1016/j.cej.2019.122760.
Muzic, M., Sertic-Bionda, K. and Gomzi, Z. (2008). Kinetic and Statistical Studies of Adsorptive Desulfurization of Diesel Fuel on Commercial Activated Carbons Chem. Eng. Technol., 31; 355-367.
Cao,S., Low, J., Yu, J. and Jaroniec, M. (2015). Polymeric photocatalysts based on graphitic carbon nitride. Adv. Mater., 27; 2150-2176.
Cai, X., He, J., Chen, L., Chen, K., Li, Y., Zhang, K., Jin, Z., Liu, J., Wang, C., Wang, X., Kong, L. and Liu, J. (2017). A 2D-g-C3N4 nanosheet as an eco-friendly adsorbent for various environmental pollutants in water. Chemosphere 171; 192-201.
Hu, R., Wang, X., Dai, S., Shao, D., Hayat, T. and Alsaedi, A. (2015). Application of graphitic carbon nitride for the removal of Pb (II) and aniline from aqueous solutions. Chem. Eng. J., 260; 469–477.
Gao, G., Jiao, Y., Waclawik, E. R. and Du, A. (2016). Single Atom ( Pd / Pt ) Supported on Graphitic Carbon Nitride as an E ffi cient Photocatalyst for Visible-Light Reduction of Carbon Dioxide. J. Am. Chem. Soc., 138(19); 6292–6297  https://doi.org/10.1021/jacs.6b02692.
Jha, D., Mubarak, N. M., Belal, M., Kumar, R. and Balathanigaimani, M. S. (2019). Adsorptive removal of dibenzothiophene from diesel fuel using microwave synthesized carbon nanomaterials. Fuel, 244; 132–139.
Mguni, L. L., Yao, Y., Nkomzwayo, T., Liu, X. and Glasser, D. (2018). Desulphurization of diesel fuels using intermediate Lewis acids loaded on activated charcoal and alumina activated charcoal and alumina. Chem. Eng. Communi., 0 (0); 1–9. https://doi.org/10.1080/00986445.2018.1511983.
Xu, X., Zhang, S., Li, P. and Shen, Y. (2013). Equilibrium and kinetics of Jet-A fuel desulfurization by selective adsorption at room temperatures. Fuel, 111; 172–179. https://doi.org/10.1016/j.fuel.2013.04.068.
Tang, N., Niu, C., Li, X., Liang, C., Guo, H., Lin, L. and Zeng, G. (2018). Science of the Total Environment Ef fi cient removal of Cd 2 + and Pb 2 + from aqueous solution with amino- and thiol-functionalized activated carbon: Isotherm and kinetics modeling. Sci. Total Envir., 635; 1331–1344.
Earvin, A., Choi, S., Roces, S., Dugos, N. and Wan, M. (2017). Adsorption of benzothiophene sulfone over clay mineral adsorbents in the frame of oxidative desulfurization. Fuel. 205; 153–160.
Habimana, F., Huo, Y., Jiang, S. and Ji, S. (2016). Synthesis of europium metal – organic framework (Eu-MOF) and its performance in adsorptive desulfurization. Adsorption, 1244; 1147–1155. https://doi.org/10.1007/s10450-016-9838-1.
Batten, S.R., Champness, N.R. and Chen, X.M. (2013). Terminology of metal–organic frameworks and coordination polymers (IUPAC Recommendations. Pure Appl. Chem. 85; 1715–1724.
Lin, Z.J., Yang, Z., Liu, T.F., Huang, Y.B. and Cao, R. (2012). Microwave-assisted synthesis of a series of lanthanide metal–organic frameworks and gas sorption properties. Inorg. Chem., 51; 1813–1820.
Sano, Y., Sugahara, K., Choi, K.H., Korai, Y. and Mochida, I. (2005). Two-step adsorption process for deep desulfurization of diesel oil. Fuel, 84; 903–910.
JabariSeresht, R., Jahanshahi, M., Rashidi, A. M. and Ghoreyshi, A. A. (2013). Synthesize and characterization of graphene nanosheets with high surface area and nanoporous structure. Appl. Surf. Sci., 276; 672–681.
Díaz-Díez, M. A., Gómez-Serrano, V., Fernández-González, C., Cuerda-Correa, E. M. and Macías-García, A. (2005). Porous texture of activated carbons prepared by phosphoric acid activation of woods. Appl. Surf. Sci., 238; 309–313.
Szabo, T., Berkesi, O. and Dekany, I. (2005). Drift study of deuterium-exchanged graphite oxide. Carbon, 43; 3186–3189.
Zhao, D., Sun, Z., Li, F., Liu, R. and Shan, H. (2008). Oxidative desulfurization of thiophene catalyzed by (C4H9)4NBr·2C6H11NO coordinated ionic liquid. Energy Fuels, 22; 3065–3069.
Kwon, T., Nishihara, H., Itoi, H., Yang, Q-H. and Kyotani, T. (2009). Enhancement mechanism of electrochemical capacitance in nitrogen-/boron-doped carbons with uniform straight nanochannels. Langmuir, 25(19); 11961-11968.