بهینه سازی گوگردزدایی اکسایشی گازوییل پالایشگاه تهران با کاتالیست های اسیدی در حضور هیدروژن پراکسید
محورهای موضوعی : مهندسی شیمیمهسا خورشید نیا 1 , امیر فرشی 2 , منوچهر بهمئی 3
1 - دانشجوی کارشناسی ارشد شیمی تجزیه، دانشکده شیمی، واحد تهران شمال، دانشگاه آزاد اسلامی، تهران، ایران.
2 - استادیار مهندسی شیمی، تصفیه فناوریهای پالایش، پژوهشگاه صنعت نفت، تهران، ایران.
3 - دانشیار شیمی تجزیه، دانشکده شیمی، واحد تهران شمال، دانشگاه آزاد اسلامی، تهران، ایران.
کلید واژه: کاتالیست, گازوییل, هیدروژن پراکسید, استیک اسید, گوگردزدایی اکسایشی, فرمیک اسید,
چکیده مقاله :
در این پژوهش، گوگرد زدایی از گازوییل پالایشگاه تهران با روش اکسایشی بررسی شده است. برای بررسی این فرایند عملکرد سامانه های متفاوت اکسایش پیشرفته (استیک اسید/هیدروژن پراکسید، فرمیک اسید/هیدروژن پراکسید) همراه با استخراج استونیتریل، برای گوگردزدایی از گازوییل پالایشگاه تهران با گوگرد اولیه ppm13370 در یک واکنشگاه ناپیوسته بررسی شد. اثر عامل های عملیاتی متفاوت مانند نسبت مولی اسید به گوگرد (nacid/ns) (15، 20 و 25)، نسبت مولی هیدروژن پراکسید (اکسنده) به گوگرد (no/ns) (5، 10 و 15)، دما و همچنین، زمان واکنش بررسی شد. آزمایش های بسیار نشان داد در شرایط بهینه حذف گوگرد از گازوییل با سامانه استیک اسید/هیدروژن پراکسید، مقدار گوگرد به ppm 9130 با بازده 31 درصد و با سامانه فرمیک اسید/هیدروژن پراکسید، مقدار گوگرد بهppm 2500 با بازده 81 درصد رسید. همچنین، بررسی آزمایش ها این نکته را تایید کرد که حذف کامل گوگرد برش های سنگین نفتی مانند گازوییل با روش های معمولی گوگرد زدایی اکسایشی امکان پذیر نیست.
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]