Abstract
Pyridine, which is nitrogen containing compounds is commonly found in crude oil and can lead to the production of NOx upon combustion. Liquid–liquid extraction is employed for removing nitrogen containing compounds from oils. In the current study, ternary deep eutectic solvents (TDES) were synthesized and used for the extraction of pyridine from a model fuel. The effect of different experimental parameters such as temperature (20 to 60 °C), time (1 to 60 min), initial pyridine concentration (0.1 to 10wt%), and TDES-to-model fuel ratio (1:5 to 5:5) was studied on extraction performance of TDESs for pyridine. Extraction efficiencies greater than 95% were observed for all single batch liquid–liquid extraction experiments. The value of thermodynamic parameters such as ΔG (KJ/moL), ΔS (J/moL/K) and ΔH (KJ/moL) were determined from the data collected at different temperatures. The efficient removal of pyridine from model fuel was found to be due to protonation of the nitrogen. Furthermore, the removal efficiency of regenerated TDES after 5 cycles was approximately equal to first extraction cycle. Finally the synthesized TDES system was employed for removing pyridine from crude oil. By optimizing process parameters, TDES exhibited remarkable performance in removing these compounds from both model oil and crude oil. The results concluded that TDES can be an efficient, cost effective and environmentally benign solvent for the extractive pyridine and other nitrogen containing compounds from model fuel.
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References
Abbott AP, Al-Murshedi AY, Alshammari OA, Harris RC, Kareem JH et al (2017) Thermodynamics of phase transfer for polar molecules from alkanes to deep eutectic solvents. Fluid Phase Equilib 448:99–104
Abbott AP, Alabdullah SS, Al-Murshedi AY, Ryder KS (2018) Brønsted acidity in deep eutectic solvents and ionic liquids. Faraday Discuss 206:365–377
Ali MC, Yang Q, Fine AA, ** W, Zhang Z et al (2016) Efficient removal of both basic and non-basic nitrogen compounds from fuels by deep eutectic solvents. Green Chem 18:157–164
Alli RD, Kroon MC (2018) Extraction of benzothiazole and thiophene from their mixtures with n-heptane using tetrahexylammonium bromide-based deep eutectic solvents as extractive denitrogenation and desulfurization agents. Fluid Phase Equilib 477:1–11
Alshammari OA, Almulgabsagher GA, Ryder KS, Abbott AP (2021) Effect of solute polarity on extraction efficiency using deep eutectic solvents. Green Chem 23:5097–5105
Asumana C, Yu G, Guan Y, Yang S, Zhou S, Chen X (2011) Extractive denitrogenation of fuel oils with dicyanamide-based ionic liquids. Green Chem 13:3300–3305
Borah HJ, Borah A, Yadav A, Hazarika S (2023) Extraction of malic acid from Dillenia indica in organic solvents and its antimicrobial activity. Sep Sci Technol 58:314–325
Chemat F, Anjum H, Shariff AM, Kumar P, Murugesan T (2016) Thermal and physical properties of (Choline chloride+ urea+ l-arginine) deep eutectic solvents. J Mol Liq 218:301–308
Chen X, Yuan S, Abdeltawab AA, Al-Deyab SS, Zhang J et al (2014) Extractive desulfurization and denitrogenation of fuels using functional acidic ionic liquids. Sep Purif Technol 133:187–193
Costa ARF, Sousa AR, Pinto PC, Passos ML, Saraiva MLM (2022) Ionic liquids impact on the catalysis of glucose oxidase and Cu/luminol/H 2 O 2 system. Chemical Papers:1–8
Cui J, Wang G, Liu W, Ke P, Tian Q et al (2021) Synthesis BiVO4 modified by CuO supported onto bentonite for molecular oxygen photocatalytic oxidative desulfurization of fuel under visible light. Fuel 290:120066
Dhake KP, Qureshi ZS, Singhal RS, Bhanage BM (2009) Candida antarctica lipase B-catalyzed synthesis of acetamides using [BMIm (PF6)] as a reaction medium. Tetrahedron Lett 50:2811–2814
Egorova KS, Ananikov VP (2014) Toxicity of ionic liquids: eco (cyto) activity as complicated, but unavoidable parameter for task-specific optimization. Chemsuschem 7:336–360
Gao S, Fang S, Song R, Chen X, Yu G (2020) Extractive denitrogenation of shale oil using imidazolium ionic liquids. Green Energy Environ 5:173–182
Gorke J, Srienc F, Kazlauskas R (2010) Toward advanced ionic liquids. Polar, enzyme-friendly solvents for biocatalysis. Biotechnol Bioprocess Eng 15:40–53
Hatab FA, Darwish AS, Lemaoui T, Warrag SE, Benguerba Y et al (2020) Extraction of thiophene, pyridine, and toluene from n-decane as a diesel model using betaine-based natural deep eutectic solvents. J Chem Eng Data 65:5443–5457
Ibrahim RK, Hayyan M, AlSaadi MA, Ibrahim S, Hayyan A, Hashim MA (2019) Physical properties of ethylene glycol-based deep eutectic solvents. J Mol Liq 276:794–800
Jafari P, Barzegar-Jalali M, Jouyban A (2023) Effect of temperature and composition on solubility and thermodynamics of salicylic acid in aqueous mixtures of betaine-based deep eutectic solvents. Korean J Chem Eng 40:910–924
Jeong HI, Park Y (2020) Separation of ethanol from a 2-butanone/ethanol mixture using choline chloride based deep eutectic solvents. Korean J Chem Eng 37:1212–1217
Jiao T, Qin X, Zhang H, Zhang W, Zhang Y, Liang P (2019) Separation of phenol and pyridine from coal tar via liquid–liquid extraction using deep eutectic solvents. Chem Eng Res Des 145:112–121
Joarder S, Bansal D, Meena H, Kaushik N, Tomar J, et al (2023) Bioinspired green deep eutectic solvents: preparation, catalytic activity, and biocompatibility. J Mol Liq 121355
Li J-j, **ao H, Tang X-d, Zhou M (2016) Green carboxylic acid-based deep eutectic solvents as solvents for extractive desulfurization. Energy Fuels 30:5411–5418
Lima F, Dave M, Silvestre AJ, Branco LC, Marrucho IM (2019) Concurrent desulfurization and denitrogenation of fuels using deep eutectic solvents. ACS Sustain Chem Eng 7:11341–11349
Park Y (2021) Separation of toluene from a toluene/n-heptane mixture using ethylene glycol containing deep eutectic solvents. Korean J Chem Eng 38:604–609
Pikna Ľ, Heželová M, Demčáková S, Smrčová M, Plešingerová B et al (2014) Effect of support on activity of palladium catalysts in nitrobenzene hydrogenation. Chem Pap 68:591–598
Plechkova NV, Seddon KR (2008) Applications of ionic liquids in the chemical industry. Chem Soc Rev 37:123–150
Serrano MC, Gutiérrez MC, Jiménez R, Ferrer ML, del Monte F (2012) Synthesis of novel lidocaine-releasing poly (diol-co-citrate) elastomers by using deep eutectic solvents. Chem Commun 48:579–581
Shakirullah M, Ahmad I, Ishaq M, Ahmad W (2010a) Catalytic hydro desulphurization study of heavy petroleum residue through in situ generated hydrogen. Energy Convers Manage 51:998–1003
Shakirullah M, Ahmad I, Ahmad W, Ishaq M (2010b) Desulphurization study of petroleum products through extraction with aqueous ionic liquids. J Chil Chem Soc 55:179–183
Solangi NH, Hussin F, Anjum A, Sabzoi N, Mazari SA, et al (2023) A review of encapsulated ionic liquids for CO2 capture. J Mol Liq 121266
Sulthan R, Reghunadhan A, Sambhudevan S (2023) A new era of chitin synthesis and dissolution using Deep Eutectic Solvents-Comparison with Ionic Liquids. J Mol Liq 121794
Tang W, Liu L, Li G, Zhu T, Row KH (2017) Optimal separation of phenol from model oils by forming deep eutectic solvents with quaternary ammonium salts. Korean J Chem Eng 34:814–821
Tu Y-J, You C-F, Chen Y-R, Huang C-P, Huang Y-H (2015) Application of recycled iron oxide for adsorptive removal of strontium. J Taiwan Inst Chem Eng 53:92–97
Ventura SP, Gonçalves AM, Sintra T, Pereira JL, Gonçalves F, Coutinho JA (2013) Designing ionic liquids: the chemical structure role in the toxicity. Ecotoxicology 22:1–12
Wang X, Li Z, Wang X, Wu C, Gates ID et al (2022a) Intermolecular interactions induced desulfurization/denitrification of oil with deep eutectic solvents. J Mol Liq 366:120159
Wang D, Zhang T, Yang L, Zhang L, Xu D et al (2022b) Molecular mechanism and extraction explorations for separation of pyridine from coal pyrolysis model mixture using protic ionic liquid [Hnmp][HSO4]. Fuel 309:122130
Yang Z, Gao S, Cao Z, Chen X, Yu G (2020) Recovery of ionic liquids from methanol by pervaporation with polydimethylsiloxane membrane. Chem Pap 74:1331–1337
Zagajski Kučan K, Rogošić M (2019) Purification of motor fuels by means of extraction using deep eutectic solvent based on choline chloride and glycerol. J Chem Technol Biotechnol 94:1282–1293
Zaid HFM, Chong FK, Mutalib MIA (2017) Extractive deep desulfurization of diesel using choline chloride-glycerol eutectic-based ionic liquid as a green solvent. Fuel 192:10–17
Zhang Y, Sun S (2023) A review on biodiesel production using basic ionic liquids as catalysts. Ind Crops Prod 202:117099
Zhang Q, Vigier KDO, Royer S, Jerome F (2012) Deep eutectic solvents: syntheses, properties and applications. Chem Soc Rev 41:7108–7146
Zhang L, Xu D, Gao J, Zhou S, Zhao L, Zhang Z (2017) Extraction and mechanism for the separation of neutral N-compounds from coal tar by ionic liquids. Fuel 194:27–35
Zhang M, Wang C, Wang K, Han Z, Bello SS et al (2020) Gentle hydrotreatment of shale oil in fixed bed over Ni-Mo/Al2O3 for upgrading. Fuel 281:118495
Zhang J, Li S, Yao L, Yi Y, Shen L et al (2023) Responsive switchable deep eutectic solvents: a review. Chin Chem Lett 34:107750
Zhao J, Gao H (2023) Synthesis and fungicidal activity of imidazole dicyanamide ionic liquids. Chem Pap 77:101–107
Zhu S, Xu J, Cheng H, Gao J, Jiang X et al (2019) Poly (ethylene glycol) diacid-based deep eutectic solvent with excellent denitrogenation performance and distinctive extractive behavior. Energy Fuels 33:10380–10388
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The authors wish to express their gratitude to the National Centre of Excellence in Physical Chemistry, University of Peshawar for all the facilities to conduct this study.
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Malik, T., Naeem, A., Abbott, A.P. et al. Ternary deep eutectic solvents for efficient denitrogenation of a model oil: thermodynamics, extraction efficiency, and recycling performance. Chem. Pap. 78, 2649–2660 (2024). https://doi.org/10.1007/s11696-023-03269-2
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DOI: https://doi.org/10.1007/s11696-023-03269-2