Document Type : Research Paper

Authors

1 ffiliation: Department of Chemical Engineering, University of Technology, Baghdad, Iraq.

2 Chemical Engineering Department, University of Technology, Baghdad, Iraq.

Abstract

The strict new regulations to reduce the sulfur content of fuel require new economical and efficient ways to remove the sulfur from the organic sulfur components. In the current work, sulfur was removed from the actual crude oil containing 2.5 wt.% from southern Iraq, specifically the Halfaya Oil Field was studied using adsorption desulfurization with activated carbon (AC). The effects of different operating conditions, including the dose of AC (0.2-1.0 gm), time (15–120 min) and temperature (30–50°C) were investigated. The best operating conditions were obtained as 0.8 gm AC, 90 minutes and 50℃, respectively. Langmuir, Freundlich and Temkin isotherm models were implemented. The steady data were best denoted via Temkin models with correlation coefficient (R2= 0.974). The kinetics sulfur components on activated carbon were examined by using pseudo-first order, pseudo-second order kinetics models and Intra-Particle diffusion. The adsorption process can be well described by pseudo-first order adsorption kinetic model with correlation coefficient (R2 = 0.9552). Thermodynamic parameters, which include Gibbs Free Energy (ΔGo), Enthalpy (ΔHo) and Entropy (ΔSo), were determined in the present research and showed that the adsorption of sulfur components on activated carbon is spontaneous, endothermic and increases the randomness of the sulfur compounds on the surface of the adsorbent. The content of sulfur in the treated crude oil was reduced from 2.5% to 1.8% corresponding to a desulfurization efficiency of 28%.

Keywords

[1] J. I. A. Chengzao, “Breakthrough and significance of unconventional oil and gas to classical petroleum geology theory”. Petroleum Exploration and Development, 44(1), 1-10, 2017.
[2] R. Javadli, & A. De Klerk, “Desulfurization of heavy oil". Applied Petrochemical Research, 1(1-4), 3-19, 2012.
[3] D. Monticello, & W. Finnerty, “Microbial desulfurization of fossil fuels”. Annual Reviews in Microbiology, 39(1), 371-389, 1985.
[4] M. R. Gray, A. R. Ayasse, E. W. Chan, & M. Veljkovic, “Kinetics of hydrodesulfurization of thiophenic and sulfide sulfur in Athabasca bitumen”. Energy & fuels, 9(3), 500-506, 1995.
[5] W. Abdul-Kadhim, M. A. Deraman, S. B. Abdullah, S. N. Tajuddin, M. M. Yusoff, Y. H. Taufiq-Yap, & M. H. A. Rahim, “Efficient and reusable iron-zinc oxide catalyst for oxidative desulfurization of model fuel”. Journal of environmental chemical engineering, 5(2), 1645-1656, 2017.
[6] O. W. Agbroko, K. Piler, & T. J. Benson, “A Comprehensive Review of H2S Scavenger Technologies from Oil and Gas Streams”. ChemBioEng Reviews, 4(6), 339-359, 2017.
[7] I. Ahmed, & S. H. Jhung, “Composites of metal–organic frameworks: preparation and application in adsorption”. Materials Today, 17(3), 136-146, 2014.
[8] J. M. Palomino, D. T. Tran, A. R. Kareh, C. A. Miller, J. M. Gardner, H. Dong, & S. R. Oliver, “Zirconia-silica based mesoporous desulfurization adsorbents”. Journal of Power Sources, 278, 141-148, 2015.
[9] T. A. Saleh, “Simultaneous adsorptive desulfurization of diesel fuel over bimetallic nanoparticles loaded on activated carbon”. Journal of Cleaner Production, 172, 2123-2132, 2018.
[10] M. Tymchyshyn, M. “Deep desulphurization of diesel fuels”. Lakehead University, 2008.
[11] A. Takahashi, F. H. Yang, & R. T. Yang, “New sorbents for desulfurization by π-complexation: thiophene/benzene adsorption”. Industrial & Engineering Chemistry Research, 41(10), 2487-2496, 2002.
[12] A. D. Hammad, Z. Yusuf, & N. Al-Rasheedi, “In-situ electrochemical desulfurization of crude oil and its fraction”. Saudi Aramco Journal of Technology, 1-5, 2012.
[13] H. Kalavathy, B. Karthik, & L. R. Miranda, “Removal and recovery of Ni and Zn from aqueous solution using activated carbon from Hevea brasiliensis: batch and column studies”. Colloids and Surfaces B: Biointerfaces, 78(2), 291-302, 2010.
[14] G. Yu, S. Lu, H. Chen, & Z. Zhu, “Diesel fuel desulfurization with hydrogen peroxide promoted by formic acid and catalyzed by activated carbon”. Carbon, 43(11), 2285-2294, 2005.
[15] S. M. Jabbar,“Desulfurization of Al-Ahdab Crude Oil using Adsorption-Assisted Oxidative Process”. PhD Thesis, University of Technology, 2013.
[16] I. Al Zubaidi, N. N. Darwish, Y. El Sayed, Z. Shareefdeen, & Z. Sara, “Adsorptive desulfurization of commercial diesel oil using granular activated charcoal”. Int. J. Adv. Chem. Eng. Biol. Sci, 2, 15-18, 2015.
[17] N. K. Ibrahim, “Desulfurization and kinetic study of diesel fuel by batch adsorption on activated carbon”. Engineering and Technology Journal, 33(8 Part (A) Engineering), 1901-1916, 2015.
[18] Y. A. Abd Al-Khodor, & T. M. Albayati, “Employing sodium hydroxide in desulfurization of the actual heavy crude oil: Theoretical optimization and experimental evaluation”. Process Safety and Environmental Protection, 136, 334-342, 2020.
[19] J. Shu, S. Cheng, H. Xia, L. Zhang, J. Peng, C. Li, & S. Zhang, S. “Copper loaded on activated carbon as an efficient adsorbent for removal of methylene blue”. RSC Advances, 7(24), 14395-14405, 2017.
[20] A. Adeyi, & F. Abekanmi, “Comparative analysis of adsorptive desulphurization of crude oil by manganese dioxide and zinc oxide”. Research Journal of Chemical Sciences. 2, 14-20, 2012.
[21] A. A. Olajire, J. J. Abidemi, A. Lateef, & N. U. Benson, “Adsorptive desulphurization of model oil by Ag nanoparticles-modified activated carbon prepared from brewer’s spent grains”. Journal of Environmental Chemical Engineering, 5(1), 147-159, 2017.
[22] S. Houda, C. Lancelot, P. Blanchard, L. Poinel, & C. Lamonier, “Oxidative Desulfurization of Heavy Oils with High Sulfur Content: A Review”. Catalysts, 8(9), 344, 2018.
[23] A. D. Mohammed, A. G. Isah, M. Umaru, S. Ahmed, & Y. N. Abdullahi, “Comparative study on sulphur reduction from heavy Petroleum-Solvent extraction and microwave irradiation approach”. IJEE, 3, 949-960, 2012.
[24] V. Toteva, A. Georgiev, & L. Topalova, “Oxidative desulphurization of light cycle oil: Monitoring by FTIR spectroscopy”. Fuel Processing Technology, 90(7-8), 965-970, 2009.
[25] A. Farshi, & P. Shiralizadeh, “Sulfur reduction of heavy fuel oil by oxidative desulfurization (ODS) method”. Petroleum & Coal, 57(3), 2015.
[26] R. Tetrisyanda, A. Wiguno, R. R. Ginting, M. C. Dzikrillah, & G. Wibawa, “Residue Oil Desulfurization Using Oxidation and Extraction Method”. Indonesian Journal of Chemistry, 18(2), 242-249, 2017.
[27] I. Langmuir, “The constitution and fundamental properties of solids and liquids”. Part I. Solids. Journal of the American Chemical Society, 38(11), 2221-2295, 2016.
[28] H. Freundlich, “Uber die adsorption in losungen, Zeitschrift fur Physikalische Chemie-Leipzig”, 57, 385-470, 1906.
[29] K. Vijayaraghavan, T. V. N. Padmesh, K. Palanivelu, & M. Velan, “Biosorption of nickel (II) ions onto Sargassum wightii: application of two-parameter and three-parameter isotherm models”. Journal of Hazardous Materials, 133(1-3), pp.304-308, 2006.
[30] G. I. Danmaliki, & T. A. Saleh, “Effects of bimetallic Ce/Fe nanoparticles on the desulfurization of thiophenes using activated carbon”. Chemical Engineering Journal, 307, 914-927, 2017.
[31] M. Temkin, & V. Pyzhev, “Kinetics of the synthesis of ammonia on promoted iron catalysts”. Jour Phys Chem (USSR), 13, 851-867, 1940.
[32] M. Hosseini, S. F. Mertens, M. Ghorbani, & M. R. Arshadi, “Asymmetrical Schiff bases as inhibitors of mild steel corrosion in sulphuric acid media”. Materials Chemistry and Physics, 78(3), pp.800-808, 2003.
[33] T. A. Saleh, K. O. Sulaiman, S. A. AL-Hammadi, H. Dafalla, & G. I. Danmaliki, “Adsorptive desulfurization of thiophene, benzothiophene and dibenzothiophene over activated carbon manganese oxide nanocomposite: with column system evaluation”. Journal of Cleaner Production, 154, 401-412, 2017.
[34] S. Lagergren, “Zur theorie der sogenannten adsorption geloster stoffe”. Kungliga Svenska Vetenskapsakademiens. Handlingar, 24, 1-39, 1898.
[35] M. Nkosi, "Desulphurization of petroleum sistillates using adsorption method” (Doctoral dissertation), 2014.
[36] Y. S. Ho, & G. McKay, “Pseudo-second order model for sorption processes”. Process Biochemistry, 34(5), 451-465, 1999.
[37] T. W. Weber, & R. K. Chakravorti, “Pore and solid diffusion models for fixed‐bed adsorbers”. AIChE Journal, 20(2), 228-238, 1974.
[38] I. A. W. Tan, A. L. Ahmad, & B. H. Hameed, “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(2-3), 473-482, 2009.