Optimizing oxidative desulfurization of diesel of Tehran Refinery using acid catalysts in the presence of hydrogen peroxide
Subject Areas :mahsa khorshidnia 1 , Amir Farshi 2 , Manocher Bahmaei 3
1 - MSc Student of Analytical Chemistry, Department of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran.
2 - Assistant Prof. of Department of Chemical Engineering, Research Group Refining, Oil Industry Research, Tehran, Iran.
3 - Associate Prof. of Chemistry, Department of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran.
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.
[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]
_||_[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]