Log in

Ternary deep eutectic solvents for efficient denitrogenation of a model oil: thermodynamics, extraction efficiency, and recycling performance

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

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.

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

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

    CAS  Google Scholar 

  • Abbott AP, Alabdullah SS, Al-Murshedi AY, Ryder KS (2018) Brønsted acidity in deep eutectic solvents and ionic liquids. Faraday Discuss 206:365–377

    CAS  PubMed  Google Scholar 

  • 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

    Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  PubMed  Google Scholar 

  • 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

    Google Scholar 

  • Gorke J, Srienc F, Kazlauskas R (2010) Toward advanced ionic liquids. Polar, enzyme-friendly solvents for biocatalysis. Biotechnol Bioprocess Eng 15:40–53

    CAS  PubMed  PubMed Central  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Plechkova NV, Seddon KR (2008) Applications of ionic liquids in the chemical industry. Chem Soc Rev 37:123–150

    CAS  PubMed  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  PubMed  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    Google Scholar 

  • 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

    Google Scholar 

  • Zhang Y, Sun S (2023) A review on biodiesel production using basic ionic liquids as catalysts. Ind Crops Prod 202:117099

    CAS  Google Scholar 

  • Zhang Q, Vigier KDO, Royer S, Jerome F (2012) Deep eutectic solvents: syntheses, properties and applications. Chem Soc Rev 41:7108–7146

    CAS  PubMed  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

  • Zhao J, Gao H (2023) Synthesis and fungicidal activity of imidazole dicyanamide ionic liquids. Chem Pap 77:101–107

    CAS  Google Scholar 

  • 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

    CAS  Google Scholar 

Download references

Acknowledgements

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.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Tabassum Malik or Abdul Naeem.

Ethics declarations

Conflict of interest

The authors declare no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11696-023-03269-2

Keywords

Navigation