Optimizing oxidative desulfurization of diesel of Tehran Refinery using acid catalysts in the presence of hydrogen peroxide

Subject Areas :

mahsa  khorshidnia ¹ (MSc Student of Analytical Chemistry, Department of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran.)
Amir  Farshi ² (Assistant Prof. of Department of Chemical Engineering, Research Group Refining, Oil Industry Research, Tehran, Iran.)
Manocher  Bahmaei ³ (Associate Prof. of Chemistry, Department of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran.)

Received: 2023-03-19 Accepted : 2023-07-20 Published : 2023-11-22

Keywords: catalyst, acetic acid, hydrogen peroxide, gasoil, formic acid, Oxidative desulfurization,

Abstract :

In this research, desulfurization of diesel from Tehran Refinery was investigated by oxidation method. To investigate this process, the performance of different advanced oxidation systems (acetic acid/hydrogen peroxide, formic acid/hydrogen peroxide) along with acetonitrile extraction were investigated for desulfurization of diesel fuel with 13370 ppm primary sulfur in a discontinuous reactor. The effect of different operating factors such as molar ratio of acid to sulfur (nacid/ns) (15, 20, and 25), molar ratio of hydrogen peroxide (oxidant) to sulfur (no/ns) (5, 10, and 15), temperature and also reaction time were investigated. Many tests showed that in the optimal conditions for removing sulfur from gas oil with the acetic acid/hydrogen peroxide system, the amount of sulfur reached to 9130 ppm with an efficiency of 31%, and with the formic acid/hydrogen peroxide system, the amount of sulfur reached to 2500 ppm with an efficiency of 81%. Also, the examination of the experiments confirmed this point that it is not possible to completely remove the sulfur from heavy oil fractions such as diesel with normal oxidative desulfurization methods.

References:

[1] Mcketta JJ. Petroleum Processing Handbook. New York: Marcel Dekker Inc.; 1992.

[2] Ghorbani Y. Sulfur compounds removal methods from crude oil. Farayad Noo Mag. 2013;43:19-39.
dor: 20.1001.1.17356466.1392.8.43.2.3 [In Persian]

[3] Houda S, Lancelot C, Blanchard P, Poinel L, Lamonier C. Oxidative Desulfurization of Heavy Oils with High Sulfur Content: A Review. Applied Catalysis A: General. 2008;8:344. doi: org/10.3390/catal8090344

[4] Li CX, Nie Y, Wang ZH. Extractive desulfurization of fuel oil using alkylimidazole and its mixture with dialkylphosphate ionic liquids. Industrial & Engineering Chemistry Research 2007;46(15):5108-5112. doi: org/10.1021/ie070385v

[5] Ma X, Song C. New design approaches to ultra-clean diesels fuels by deep desulfurization and deep dearomatization. Applied Catalysis B: Environmental. 2003:41(1-2):207-238. doi: org/10.1016/S0926-3373(02)00212-6

[6] El-Ali B, Ali MF, Al-Malk A, Martinie G, Siddiqu MN. Deep desulphurization of gasoline and diesel fuels using non-hydrogen consuming techniques. Fuel. 2005:85:1354-1363. doi: org/10.1016/j.fuel.2005.12.006

[7] Guth ED, Diaz AF, inventors; KVB Engineering, Inc., assignee. Method for Removing Sulfur and Nitrogen in Petroleum Oils. US patent 3847800. Nov 12, 1974.

[8] Chen B, Haung C, Li Y, Liu Z, Zhang J. Desulfurization of gasoline by extraction with new ionic liquids. Energy Fuels. 2004;46:111–150. doi: org/10.1016/S1872-5813(09)60015-3

[9] Farshi A, Shiralizadeh P. Sulfur reduction of heavy fuel oil by oxidative desulfurization (Ods) Method. Petroleum & Coal. 2015;57(3):295-302.  

[10] Paspek SC, inventor; The Standard Oil Company, assignee. Upgrading Heavy Hydrocarbons with Supercritical Water and light Olefins. US patent 4483761. Nov 20, 1984.

[11] Khorshidnia M. Comparison effect of catalyst of MoO₂, formic and acetic acid on desulfurization of gasoil with using oxidative desulfurization (Ods) Method [dissertation]. [Tehran]: Islamic Azad University-Tehran North Branch; 2015. 147p.   

[12] Behrouzifar A. A review on main challenges of hydrodesulfurization process for sulfur removal from fossil fuels. Farayad Noo Mag. 2019;64:73-91. dor: 20.1001.1.17356466.1397.13.64.5.3 [In Persian]

[13] Bibak F, Moradi G. Oxidative Desulfurisation of Model Oil and Real Sample Using MoO₃/g-C₃N₄ Catalyst and Optimization of Operating Conditions by Box-Benken Method. Petroleum Research. 2019;29(98-1):18-20. doi: doi.org/10.22078/pr.2018.3351.2538 [In Persian]

[14]  Khatamian M, Chenari Z, Yavari  A, Divband  B. Karimi  Z, Mohammadzadeh  S, Mardangahi B, Fazli-Shokouhi S. Performance Investigation of MoO₃/Clin and Mn₂O₃-MoO₃/Clin nanocomposites in adsorption/catalytic oxidation process of thiophen. Journal of Applied Research in Chemistry. 2023;17(2):38-49. doi: org/10.30495/jacr.2023.1976957.2083 [In Persian]