Abstract
Due to the rising demands of cleaner fuels (free from sulfur), most of the oil industries are implementing the process of the desulfurization. In present work, the extractive desulfurization (EDS) efficiency of binary solvents composed as mixtures of bronsted acidic ILs ([Hnmp][HSO4] and [Hnmp][H2PO4]) and nonvolatile organic solvent known as dimethylformamide (DMF), is investigated for the model fuel oil (containing thiophene as S-compounds). The main advantages of using binary solvents are; low viscosity of extractant and reduced cost of the process. Effect of key operating parameters such as temperature, time, multiple steps, initial S-content in oil and oil:binary solvent (w/w) ratio on the S-removal efficiency is examined. Based on the obtained results, optimal 40 °C and 45 min are chosen as operating temperature and extraction time, respectively. Almost 95% of S-removal (decrease from 500 to 22 ppm and 28 ppm) is obtained through five steps extraction for both binary solvents, also these exhibited remarkable extraction performances for different initial S-content of fuel oil. The recyclability and reusability of solvents are investigated, where it is observed that binary solvent has reasonable effectiveness when reused for four times. The solvents can also be regenerated without undergoing any change in the actual structure of ILs. This study shows that EDS based on the binary solvents can be a suitable option to produce the cleaner fuel oils.
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Abro R, Abdeltawab AA, Al-Deyab SS, Yu G, Qazi AB, Gao S, Xs Chen (2014) A review of extractive desulfurization of fuel oils using ionic liquids. RSC Adv 4(67):35302–35317. https://doi.org/10.1039/c4ra03478c
Abro R, Gao SR, Chen XC, Yu GR, Abdeltawab AA, Al-Deyab SS (2016) Oxidative desulfurization of gasoline by ionic liquids coupled with extraction by organic solvents. J Braz Chem Soc 27(6):998–1006. https://doi.org/10.5935/0103-5053.20150355
Ahmed I, Jhung SH (2016) Adsorptive desulfurization and denitrogenation using metal-organic frameworks. J Hazard Mater 301:259–276. https://doi.org/10.1016/j.jhazmat.2015.08.045
Alonso L, Arce A, Ma Francisco, Rodrı´guez O, Soto AS (2007) Gasoline desulfurization using extraction with [C8mim][BF4] ionic liquid. AIChE J 53(12):3108–3115. https://doi.org/10.1002/aic.11337
Anantharaj R, Banerjee TS (2011) COSMO-RS based predictions for the desulphurization of diesel oil using ionic liquids: effect of cation and anion combination. Fuel Process Technol 92(1):39–52. https://doi.org/10.1016/j.fuproc.2010.08.018
Asumana C, Yu G, Li X, Zhao J, Liu G, Chen XS (2010) Extractive desulfurization of fuel oils with low-viscosity dicyanamide-based ionic liquids. Green Chem 12(11):2030. https://doi.org/10.1039/c0gc00118j
Asumana C, Haque MR, Yu L, Wu X, Chen X, Gs Yu (2013) Desulfurization of real fuel oils by extraction with ionic liquids. Sep Sci Technol 48(17):2582–2588. https://doi.org/10.1080/01496395.2013.804559
Bhutto AW, Abro R, Abbas T, Yu G, Chen X (2016a) Desulphurization of fuel oils using ionic liquids. In: Al-Megren H, Xiao T (eds) Petrochemical catalyst materials, processes, and emerging technologies, IGI Global, pp 254–284
Bhutto AW, Abro R, Gao S, Abbas T, Chen X, Gs Yu (2016b) Oxidative desulfurization of fuel oils using ionic liquids: a review. J. Taiwan Inst Chem Eng 62:84–97. https://doi.org/10.1016/j.jtice.2016.01.014
Boon JA, Levisky JA, Pflug JL, Wilkes JS (1986) Friedel-Crafts reactions in ambient-temperature molten salts. J Org Chem 51(4):480–483. https://doi.org/10.1021/jo00354a013
Chen X, Liu G, Yuan S, Asumana C, Wang W, Yu GS (2012a) Extractive desulfurization of fuel oils with thiazolium-based ionic liquids. Sep Sci Technol 47(6):819–826. https://doi.org/10.1080/01496395.2011.637281
Chen X, Song D, Asumana C, GS Yu (2012b) Deep oxidative desulfurization of diesel fuels by Lewis acidic ionic liquids based on 1-n-butyl-3-methylimidazolium metal chloride. J Mol Catal A Chem 359:8–13. https://doi.org/10.1016/j.molcata.2012.03.014
Chen X, Yuan S, Abdeltawab AA, Al-Deyab SS, Zhang J, Yu L, Yu GS (2014) Extractive desulfurization and denitrogenation of fuels using functional acidic ionic liquids. Sep Purif Technol 133:187–193. https://doi.org/10.1016/j.seppur.2014.06.031
Dharaskar SA, Wasewar KL, Varma MN, Shende DZ, Yoo CS (2016) Synthesis, characterization and application of 1-butyl-3-methylimidazolium tetrafluoroborate for extractive desulfurization of liquid fuel. Arab J Chem 9(4):578–587. https://doi.org/10.1016/j.arabjc.2013.09.034
Dumeignil F, Sato K, Imamura M, Matsubayashi N, Payen E, Hs Shimada (2006) Characterization and hydrodesulfurization activity of CoMo catalysts supported on boron-doped sol–gel alumina. Appl Catal A 315:18–28. https://doi.org/10.1016/j.apcata.2006.08.034
Eßer J, Wasserscheid P, As Jess (2004) Deep desulfurization of oil refinery streams by extraction with ionic liquids. Green Chem 6(7):316–322. https://doi.org/10.1039/b407028c
Ferrari M, Maggi R, Delmon B, Ps Grange (2001) Influences of the hydrogen sulfide partial pressure and of a nitrogen compound on the hydrodeoxygenation activity of a CoMo/carbon catalyst. J Catal 198(1):47–55. https://doi.org/10.1006/jcat.2000.3103
Fry SE, Pienta NJ (1985) Effects of molten salts on reactions. Nucleophilic aromatic substitution by halide ions in molten dodecyltributylphosphonium salts. J Am Chem Soc 107(22):6399–6400. https://doi.org/10.1021/ja00308a045
Gao H, Luo M, Xing J, Wu Y, Li Y, Li W, Liu Q, Hs Liu (2008) Desulfurization of fuel by extraction with pyridinium-based ionic liquids. Ind Eng Chem Res 47(21):8384–8388. https://doi.org/10.1021/ie800739w
Gao S, Chen X, Abro R, Abdeltawab AA, Al-Deyab SS, Gs Yu (2015) Desulfurization of fuel oil: conductor-like screening model for real solvents study on capacity of ionic liquids for thiophene and dibenzothiophene. Ind Eng Chem Res 54(38):9421–9430. https://doi.org/10.1021/acs.iecr.5b01385
Gao S, Chen X, Abro R, Su Z, Abdeltawab AA, Al-Deyab SS, Yu G (2016) Mutual solubility of acidic ionic liquid and model gasoline of n-octane+ 1-octene+ toluene. J Taiwan Inst Chem Eng 69:78–84. https://doi.org/10.1016/j.jtice.2016.10.008
Gao J, Zhu S, Dai Y, Xiong C, Li C, Yang W, Xs Jiang (2018a) Performance and mechanism for extractive desulfurization of fuel oil using modified polyethylene glycol. Fuel 233:704–713. https://doi.org/10.1016/j.fuel.2018.06.101
Gao S, Li J, Chen X, Abdeltawab AA, Yakout SM, Gs Yu (2018b) A combination desulfurization method for diesel fuel: oxidation by ionic liquid with extraction by solvent. Fuel 224:545–551. https://doi.org/10.1016/j.fuel.2018.03.108
Gates BC, Topsøe HS (1997) Reactivities in deep catalytic hydrodesulfurization: challenges, opportunities, and the importance of 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. Polyhedron 16(18):3213–3217. https://doi.org/10.1016/s0277-5387(97)00074-0
Geng Y, Wang T, Yu D, Peng C, Liu H, Hu Y (2008) Densities and viscosities of the ionic liquid [C4mim][PF6] + N,N-dimethylformamide binary mixtures at 293.15 K to 318.15 K. Chin J Chem Eng 16(2):256–262. https://doi.org/10.1016/s1004-9541(08)60072-5
Girgis MJ, Gates BC (1991) Reactivities, reaction networks, and kinetics in high-pressure catalytic hydroprocessing. Ind Eng Chem Res 30(9):2021–2058. https://doi.org/10.1021/ie00057a001
Gutberlet LC, Bertolacini RJ (1983) Inhibition of hydrodesulfurization by nitrogen compounds. Ind Eng Chem Prod Res Dev 22(2):246–250. https://doi.org/10.1021/i300010a016
Hernández-Maldonado AJ, Yang RT (2003) Desulfurization of liquid fuels by adsorption via π complexation with Cu(I) − Y and Ag − Y zeolites. Ind Eng Chem Res 42(1):123–129. https://doi.org/10.1021/ie020728j
Hernández-Maldonado AJ, Yang RT (2004) Desulfurization of transportation fuels by adsorption. Catal Rev 46(2):111–150. https://doi.org/10.1081/cr-200032697
Huang C, Chen B, Zhang J, Liu Z, Ys Li (2004) Desulfurization of gasoline by extraction with new ionic liquids. Energy Fuels 18(6):1862–1864. https://doi.org/10.1021/ef049879k
Ibrahim JJ, Gao S, Abdeltawab AA, Al-Deyab SS, Yu L, Yu G, Chen X, Yong XS (2014) Extractive desulfurization of fuel oils with dicyano(nitroso)methanide-based ionic liquids. Sep Sci Technol 50(8):1166–1174. https://doi.org/10.1080/01496395.2014.960051
Jha D, Haider MB, Kumar R, Balathanigaimani MS (2016) Extractive desulfurization of dibenzothiophene using phosphonium-based ionic liquid: modeling of batch extraction experimental data and simulation of continuous extraction process. Chem Eng Res Des 111:218–222. https://doi.org/10.1016/j.cherd.2016.05.006
Jiang W, Zhu W, Li H, Wang X, Yin S, Chang Y, Hs Li (2015) Temperature-responsive ionic liquid extraction and separation of the aromatic sulfur compounds. Fuel 140:590–596. https://doi.org/10.1016/j.fuel.2014.09.083
Jiang W, Dong L, Liu W, Guo T, Li H, Yin S, Zhu W, Hs Li (2017) Biodegradable choline-like deep eutectic solvents for extractive desulfurization of fuel. Chem Eng Process 115:34–38. https://doi.org/10.1016/j.cep.2017.02.004
Jian-long W, Zhao DS, Zhao E-P, Dong ZS (2007) Desulfurization of gasoline by extraction with N-alkyl-pyridinium-based ionic liquids. J Fuel Chem Technol 35(3):293–296. https://doi.org/10.1016/s1872-5813(07)60022-x
Keskin S, Kayrak-Talay D, Akman U, Hortaçsu Ö (2007) A review of ionic liquids towards supercritical fluid applications. J Supercrit Fluids 43(1):150–180. https://doi.org/10.1016/j.supflu.2007.05.013
Khan NA, Bhadra BN, Jhung SH (2018) Heteropoly acid-loaded ionic liquid@metal-organic frameworks: effective and reusable adsorbents for the desulfurization of a liquid model fuel. Chem Eng J 334:2215–2221. https://doi.org/10.1016/j.cej.2017.11.159
Kim JH, Ma X, Zhou A, 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(1–2):74–83. https://doi.org/10.1016/j.cattod.2005.10.017
Kwak C, Lee JJ, Bae JS, Choi K, Moon SH (2000) Hydrodesulfurization of DBT, 4-MDBT, and 4,6-DMDBT on fluorinated CoMoS/Al2O3 catalysts. Appl Catal A 200(1–2):233–242. https://doi.org/10.1016/s0926-860x(00)00635-9
Landau MV, Herskowitz M, Hoffman T, Fuks D, Liverts E, Vingurt D, Froumin N (2009) Ultradeep hydrodesulfurization and adsorptive desulfurization of diesel fuel on metal-rich nickel phosphides. Ind Eng Chem Res 48(11):5239–5249. https://doi.org/10.1021/ie9000579
Lee JJ, Han S, Kim H, Koh JH, Hyeon T, Moon SH (2003) Performance of CoMoS catalysts supported on nanoporous carbon in the hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene. Catal Today 86(1–4):141–149. https://doi.org/10.1016/s0920-5861(03)00408-5
Li W, Liu Q, Xing J, Gao H, Xiong X, Li Y, Li X, Liu HS (2007) High-efficiency desulfurization by adsorption with mesoporous aluminosilicates. AIChE J 53(12):3263–3268. https://doi.org/10.1002/aic.11319
Li F-T, R-h Liu, Jin-hua W, Zhao D-S, Sun Z-M, Liu Y (2009) Desulfurization of dibenzothiophene by chemical oxidation and solvent extraction with Me3NCH2C6H5Cl·2ZnCl2 ionic liquid. Green Chem 11(6):883. https://doi.org/10.1039/b815575e
Lissner E, Souza WF, Ferrera B, Dupont JS (2009) Oxidative desulfurization of fuels with task-specific ionic liquids. Chemsuschem 2(10):962–964. https://doi.org/10.1002/cssc.200900171
Lu H, Gao J, Jiang Z, Jing F, Yang Y, Wang G, Li C (2006) Ultra-deep desulfurization of diesel by selective oxidation with [C18H37N(CH3)3]4[H2NaPW10O36] catalyst assembled in emulsion droplets. J Catal 239(2):369–375. https://doi.org/10.1016/j.jcat.2006.01.025
Lu X, Yue L, Hu M, Cao Q, Xu L, Guo Y, Hu S, Fang WS (2014) Piperazinium-based ionic liquids with lactate anion for extractive desulfurization of fuels. Energy Fuels 28(3):1774–1780. https://doi.org/10.1021/ef402154j
Moghadam FR, Azizian S, Bayat M, Yarie M, Kianpour E, Zolfigol MA (2017) Extractive desulfurization of liquid fuel by using a green, neutral and task specific phosphonium ionic liquid with glyceryl moiety: a joint experimental and computational study. Fuel 208:214–222. https://doi.org/10.1016/j.fuel.2017.07.025
Mokhtar WNAW, Bakar WAWA, Ali R, Kadir AAA (2014) Deep desulfurization of model diesel by extraction with N,N-dimethylformamide: optimization by Box-Behnken design. J Taiwan Inst Chem Eng 45(4):1542–1548. https://doi.org/10.1016/j.jtice.2014.03.017
Nie Y, Li C, Sun A, Meng H, Wang ZS (2006) Extractive desulfurization of gasoline using imidazolium-based phosphoric ionic liquids. Energy Fuels 20(5):2083–2087. https://doi.org/10.1021/ef060170i
Nie Y, Li C-X, Wang Z-H (2007) Extractive desulfurization of fuel oil using alkylimidazole and its mixture with dialkylphosphate ionic liquids. Ind Eng Chem Res 46(15):5108–5112. https://doi.org/10.1021/ie070385v
Nie Y, Li C, Meng H, Wang ZS (2008) N, N-dialkylimidazolium dialkylphosphate ionic liquids: their extractive performance for thiophene series compounds from fuel oils versus the length of alkyl group. Fuel Process Technol 89(10):978–983. https://doi.org/10.1016/j.fuproc.2008.04.003
Otsuki S, Nonaka T, Takashima N, Qian W, Ishihara A, Imai T, Ts Kabe (2000) Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction. Energy Fuels 14(6):1232–1239. https://doi.org/10.1021/ef000096i
Pawelec B, Mariscal R, Fierro JLG, Greenwood A, Vasudevan PT (2001) Carbon-supported tungsten and nickel catalysts for hydrodesulfurization and hydrogenation reactions. Appl Catal A 206(2):295–307. https://doi.org/10.1016/s0926-860x(00)00605-0
Pham TP, Cho CW, Yun YS (2010) Environmental fate and toxicity of ionic liquids: a review. Water Res 44(2):352–372. https://doi.org/10.1016/j.watres.2009.09.030
Rodríguez-Cabo B, Rodríguez H, Rodil E, Arce A, Soto AS (2014) Extractive and oxidative-extractive desulfurization of fuels with ionic liquids. Fuel 117:882–889. https://doi.org/10.1016/j.fuel.2013.10.012
Romero A, Santos A, Tojo J, Rodriguez AS (2008) Toxicity and biodegradability of imidazolium ionic liquids. J Hazard Mater 151(1):268–273. https://doi.org/10.1016/j.jhazmat.2007.10.079
Shan G, Xing J, Zhang H, Liu HS (2005) Biodesulfurization of dibenzothiophene by microbial cells coated with magnetite nanoparticles. Appl Environ Microbiol 71(8):4497–4502. https://doi.org/10.1128/AEM.71.8.4497-4502.2005
Sipma J, Henstra AM, Parshina SM, Lens PN, Lettinga G, Stams AJ (2006) Microbial CO conversions with applications in synthesis gas purification and bio-desulfurization. Crit Rev Biotechnol 26(1):41–65. https://doi.org/10.1080/07388550500513974
Song C (2003) An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catal Today 86(1–4):211–263. https://doi.org/10.1016/s0920-5861(03)00412-7
Srivastava VC (2012) An evaluation of desulfurization technologies for sulfur removal from liquid fuels. RSC Adv 2(3):759–783. https://doi.org/10.1039/c1ra00309g
Tam PS, Kittrell JR, Eldridge JW (1990) Desulfurization of fuel oil by oxidation and extraction. 1. Enhancement of extraction oil yield. Ind Eng Chem Res 29(3):321–324. https://doi.org/10.1021/ie00099a002
Wang J, Zhao D, Ks Li (2009) Oxidative desulfurization of dibenzothiophene catalyzed by brønsted acid ionic liquid. Energy Fuels 23(8):3831–3834. https://doi.org/10.1021/ef900251a
Xu P, Yu B, Li FL, Cai XF, Ma CQ (2006) Microbial degradation of sulfur, nitrogen and oxygen heterocycles. Trends Microbiol 14(9):398–405. https://doi.org/10.1016/j.tim.2006.07.002
Xu H, Zhang D, Wu F, Wei X, Js Zhang (2018) Deep desulfurization of fuels with cobalt chloride-choline chloride/polyethylene glycol metal deep eutectic solvents. Fuel 225:104–110. https://doi.org/10.1016/j.fuel.2018.03.159
Xun S, Zhu W, Zheng D, Li H, Jiang W, Zhang M, Qin Y, Zhao Z, Hs Li (2015) Supported ionic liquid [Bmim]FeCl4/Am TiO2 as an efficient catalyst for the catalytic oxidative desulfurization of fuels. RSC Adv 5(54):43528–43536. https://doi.org/10.1039/c5ra00999e
Yang J, Marison IW (2005) Two-stage process design for the biodesulphurisation of a model diesel by a newly isolated Rhodococcus globerulus DAQ3. Biochem Eng J 27(1):77–82. https://doi.org/10.1016/j.bej.2005.08.012
Zhang SG, Zhang QL, Zhang ZC (2004) Extractive desulfurization and denitrogenation of fuels using ionic liquids. Ind Eng Chem Res 43(2):614–622. https://doi.org/10.1021/ie030561+
Zhao H, Xia S, Ps Ma (2005) Use of ionic liquids as ‘green’ solvents for extractions. J Chem Technol Biotechnol 80(10):1089–1096. https://doi.org/10.1002/jctb.1333
Zhao Z, Xing X, Tang Z, Zhao Y, Fei W, Liang X, He Z, Zhang S, Ds Guo (2017) Solubility of CO 2 and H 2 S in carbonates solvent: experiment and quantum chemistry calculation. Int J Greenhouse Gas Control 59:123–135. https://doi.org/10.1016/j.ijggc.2017.02.011
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Kiran, N., Abro, R., Abro, M. et al. Extractive desulfurization of gasoline using binary solvent of bronsted-based ionic liquids and non-volatile organic compound. Chem. Pap. 73, 2757–2765 (2019). https://doi.org/10.1007/s11696-019-00828-4
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DOI: https://doi.org/10.1007/s11696-019-00828-4