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Sulfur extraction from liquid fuels using trihexyl(tetradecyl)phosphonium tetrafluoroborate: as promising solvent

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Abstract

Sulfur extraction from fuel is essential to be done for environmental and industrial point of view. Extractive desulfurization (EDS) is one of the most promising techniques in order to achieve legislative sulfur content requirements. Among numerous extractants and solvents, ionic liquids (ILs) are more capable due to their desirable green solvent properties. This work demonstrated that trihexyl(tetradecyl)phosphonium tetrafluoroborate ([THTDP]BF4) was synthesized, characterized, and employed as extraction solvent for extraction of dibenzothiophene (DBT), thiophene, benzothiophene, and other alkyl-substituted derivatives of sulfur from liquid fuel. Molecular confirmation and purity of synthesized ([THTDP]BF4) were analyzed with FTIR, Raman, NMR, EPR, UV, TG/DSC, and XRD analyses. Also, physical properties of ([THTDP]BF4) were carried out. The effects of extraction time, temperature, sulfur compounds, ultra-sonication, and ([THTDP]BF4) recycling/regeneration on DBT removal from liquid fuel were also examined. DBT removal in n-dodecane was 92.6% using EDS with mass ratio (1:1) in 30 min at 30 °C under the mild reaction conditions. ([THTDP]BF4) could be reused up to ten cycles for sulfur extraction and regenerated for few more cycles with good DBT removal ability. Also, the sulfur extraction from real fuels and multistage extraction performance were tested. The experimental data and results provided in this article discover the remarkable understandings of tetrafluoroborate-based phosphonium ionic liquids as promising solvent for EDS.

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Abbreviations

([THTDP]BF4):

trihexyl(tetradecyl)phosphonium tetrafluoroborate

ILs:

ionic liquids

HDS:

hydrodesulphurization system

EDS:

extractive desulfurization system

ppm:

parts per million

DBT:

dibenzothiophene

TS:

thiophene

BT:

benzothiophene

3-MT:

3-methylthiophene

4-MDBT:

4-methyldibenzothiophene

4,6-DMDBT:

4,6-dimethyldibenzothiophene

K N :

partition coefficient

References

  • Abro R, Abdeltawab A, Al-Deyab S, Yu G, Qazi A, Gao S (2014) A review of extractive desulfurization of fuel oils using ionic liquids. RSC Adv 4:35302–35317

    Article  CAS  Google Scholar 

  • Ahmad O, Mjalli F, Gujarathi A, Alwahaibi T, Al-Wahaibi Y, AlNashef I (2015a) Feasibility of phosphonium-based ionic liquids as solvents for extractive desulfurization of liquid fuels. Fluid Phase Equilib 401:102–109

    Article  CAS  Google Scholar 

  • Ahmad O, Mjalli F, Alwahaibi T, Al-Wahaibi Y, AlNashef I (2015b) Optimum performance of extractive desulfurization of liquid fuels using phosphonium and pyrrolidinium based ionic liquids. Ind Eng Chem Res 54:6540–6550

    Article  CAS  Google Scholar 

  • Alonso L, Arce A, Francisco M, Soto A (2008) (Liquid+liquid) equilibria of [C8mim][NTf2] ionic liquid with a sulfur-component and hydrocarbons. J Chem Thermodyn 40:265–270

    Article  CAS  Google Scholar 

  • Anantharaj R, Banerjee T (2011) COSMO-RS based predictions for the desulfurization of diesel oil using ionic liquids. Fuel Process Technol 92:39–52

    Article  CAS  Google Scholar 

  • Baeza P, Aguila G, Gracia F, Araya P (2008) Desulfurization by adsorption with copper supported on zirconia. Catal Commun 9:751–755

    Article  CAS  Google Scholar 

  • Ban L, Liu P, Ma C, Dai B (2013) Deep extractive desulfurization of diesel fuels by FeCl3/ionic liquids. Chin Chem Lett 24:755–758

    Article  CAS  Google Scholar 

  • Bosmann A, Datsevich L, Jess A, Lauter A, Schmitz C, Wasserscheid P (2001) Deep desulfurization of diesel fuel by extraction with ionic liquids. Chem Commun 7:2468–2469

    Google Scholar 

  • Bradaric C, Downard A, Kennedy C, Robertson A, Zhou Y (2003) Industrial preparation of phosphonium ionic liquids. Green Chem 5:143–152

    Article  CAS  Google Scholar 

  • Carnaroglio D, Gaudino E, Mantegna S, Moreira E, Vicente de Castro A, Flores E, Cravotto G (2014) Ultrasound-assisted oxidative desulfurization/denitrification of liquid fuels with solid oxidants. Energy Fuel 28:1854–1859

    Article  CAS  Google Scholar 

  • Chen X, Liu G, Yuan S, Asumana C, Wang W, Yu G (2012) Extractive desulfurization of fuel oils with thiazolium-based ionic liquids. Sep Sci Technol 47:819–826

    Article  CAS  Google Scholar 

  • Chen X, Yuan S, Abdeltawab A, Al-Deyab S, Zhang J, Yu L, Yu G (2014) Extractive desulfurization and denitrogenation of fuels using functional acidic ionic liquids. Sep Purif Technol 133:187–193

    Article  CAS  Google Scholar 

  • Cun Z, Feng W, Xiao-yu P, Xiao-qin L (2011) Study of extraction-oxidation desulfurization of model oil by acidic ionic liquid. J Fuel Chem Technol 39:689–693

    Article  Google Scholar 

  • Dharaskar S, Wasewar K, Varma M, Shende D, Tadi K, Yoo C (2014) Synthesis, characterization, and application of novel trihexyltetradecyl phosphonium bis (2,4,4-trimethylpentyl) phosphinate for extractive desulfurization of liquid fuel. Fuel Process Technol 123:1–10

    Article  CAS  Google Scholar 

  • Dharaskar S, Wasewar K, Varma M, Shende D, Yoo C (2016) Synthesis, characterization, and application of 1-butyl-3-methylimidazolium tetrafluorobaorate for extractive desulfurization of liquid fuels. Arb J Chem 9:578–587

    Article  CAS  Google Scholar 

  • Domanska U, Wlazlo M (2014) Effect of the cation and anion of the ionic liquid on desulfurization of model fuels. Fuel 134:114–125

    Article  CAS  Google Scholar 

  • Duarte F, Mello P, Bizzi C, Nunes M, Alencar E, Motta H, Dressler V, Flores E (2011) Sulfur removal from hydrotreated petroleum fractions using ultrasound-assisted oxidative desulfurization process. Fuel 90:2158–2164

    Article  CAS  Google Scholar 

  • Fallah R, Azizian S, Dwivedi A, Sillanpaa M (2015) Adsorptive desulfurization using different passivated carboan nanoparticles by PEG-200. Fuel Process Technol 130:214–223

    Article  CAS  Google Scholar 

  • Faridbod F, Ganjali M, Norouzi P, Riahi S, Rashedi H (2011) Application of Room Temperature Ionic Liquids in Electrochemical Sensors and Biosensors, Ionic Liquids: Applications and Perspectives, InTech, ISBN: 978-953-307-248-7. https://doi.org/10.5772/14702

  • Ferreira A, Freire M, Ribeiro J, Lopes F, Crespo J, Coutinho J (2014) Ionic liquids for thiols desulfurization: experimental liquid-liquid equilibrium and COSMO-RS description. Fuel 128:314–329

    Article  CAS  Google Scholar 

  • Freire M, Carvalho P, Gardas R, Luis M, Santos B, Marrucho I, Countinho J (2008) Solubility of water in tetradecyltrihexylphosphonium-based ionic liquids. J Chem Eng Data 53:2378–2382

    Article  CAS  Google Scholar 

  • Gao H, Guo C, Xing J, Liu H (2012) Deep desulfurization of diesel oil with extraction using pyridinium-based ionic liquids. Sep Sci Technol 47:325–330

    Article  CAS  Google Scholar 

  • Hansmeier A, Meindersma G, de haan A (2011) Desulfurization and denitrogenation of gasoline and diesel fuels by means of ionic liquids. Green Chem 13:1907–1913

    Article  CAS  Google Scholar 

  • Holding A, Heikkil M, Kilpelinen I, King A (2014) Amphiphilic and phase-separable ionic liquids for biomass processing. ChemSusChem 1:1–14

    Google Scholar 

  • Huang W, Zhu W, Li H, Shi H, Zhu G, Liu H, Chen G (2010) Heteropolyanion-based ionic liquid for deep desulfurization of fuels in ionic liquids. Ind Eng Chem Res 49:8998–9003

    Article  CAS  Google Scholar 

  • Ibrahim M, Hayyan M, Hashim M, Hayyan A (2017) The role of ionic liquids in desulfurization of fuels: a review. Renew Sustain Energy Rev 76:1534–1549

    Article  CAS  Google Scholar 

  • Kianpour E, Azizian S (2014) Polyethylene glycol as green solvent for effective extractive desulfurization of liquid fuel at ambient conditions. Fuel 137:36–40

    Article  CAS  Google Scholar 

  • Kianpour E, Azizian S, Yarie M, Zolfigol M, Bayat M (2016) A task-specific phosphonium ionic liquid as an efficient extractant for green desulfurization of liquid fuel: an experimental and computational study. Chem Eng J 295:500–508

    Article  CAS  Google Scholar 

  • Kulkarni P, Afonso C (2010) Deep desulfurization of diesel fuel using ionic liquids: current status and future challenges. Green Chem 12:1139–1149

    Article  CAS  Google Scholar 

  • Li M, Zhou Z, Zhang F, Chai W, Zhang L, Ren Z (2016) Deep oxidative extractive desulfurization of fuels using benzyl based ionic liquids. AICHE J 62:4023–4034

    Article  CAS  Google Scholar 

  • Liu W, Etschmann B, Brugger J, Spiccia L, Foran G, Mclnnes B (2006) UV-Vis spectrophotometric and XAFS studies of ferric chloride complexes in hypersaline LiCl solutions at 25–90 C. Chem Geol 231:326–349

    Article  CAS  Google Scholar 

  • Liu X, Zhou G, Zhang S, Yu G (2010) Molecular simulations of phosphonium based ionic liquid. Mol Simul 36:79–86

    Article  CAS  Google Scholar 

  • Liu X, Afsal W, Prausnitz J (2013) Solubility’s of small hydrocarbons in tetrabutylphosphonium bis(2,4,4-trimethylpentyl) phosphinate and in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Ind Eng Chem Res 52:14975–14978

    Article  CAS  Google Scholar 

  • Lu H, Deng C, Ren W, Yang X (2014a) Oxidative desulfurization of model diesel using [(C4H9)4N]6Mo7O24 as a catalyst in ionic liquids. Fuel Process Technol 119:87–91

    Article  CAS  Google Scholar 

  • Lu X, Yue L, Hu M, Cao Q, Xu L, Guo Y, Hu S, Fang W (2014b) Piperazinium-based ionic liquids with lactate anion for extractive desulfurization of fuels. Energy Fuel 28:1774–1780

    Article  CAS  Google Scholar 

  • Maldonado A, Yang F, Qi G, Yang R (2005) Desulfurization of transportation fuels by π-complexation sorbents. Appl Catal B 56:111–126

    Article  CAS  Google Scholar 

  • Manic M, Macedo E, Visak V (2012) Trihexyltetradecylphosphonium bromide: liquid density, surface tension and solubility of carbon dioxide. Fluid Phase Equilib 324:8–12

    Article  CAS  Google Scholar 

  • Marcelis M (2002) Anaerobic biodesulfurization of thiophenes. University of Wageningen, Wageningen

    Google Scholar 

  • McNulty J, Nair J, Cheekoori S, Larichev V, Capretta A, Robertson A (2006) Scope and mechanistic insights into the use of tetradecyl(trihexyl)phosphonium bistriflimide: a remarkably selective ionic liquid solvent for substitution reactions. Chem Eur J 12:9314–9322

    Article  CAS  Google Scholar 

  • Min G, Yim T, Lee H, Huh D, Lee E, Mun J, Oh S, Kim Y (2006) Synthesis and Properties of Ionic Liquids: Imidazolium Tetrafluoroborates with Unsaturated Side Chains. Bull Korean Chem Soc 27:847–852

  • Moghadam F, Azizian S, Kianpour E, Yarie M, Bayat M, Zolfigol M (2017a) Green fuel through green route by using a task-specific and neutral phosphonium ionic liquid: a joint experimental and theoretical study. Chem Eng J 309:480–488

    Article  CAS  Google Scholar 

  • Moghadam F, Azizian S, Bayat M, Yarie M, Kianpour E, Zolfigol M (2017b) 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

    Article  CAS  Google Scholar 

  • Nejad N, Soolari E, Adibi M, Beigi A, Torkestani S (2013) Imidazolium-based alkylsulfate ionic liquids and removal of sulfur content from model of gasoline. Pet Sci Technol 31:472–480

    Article  CAS  Google Scholar 

  • Otsuki S, Nonaka T, Takashima N, Qian W, Ishihara A, Imai T, Kabe T (2000) Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction. Energy Fuel 14:1232–1239

    Article  CAS  Google Scholar 

  • Pawelec B, Mariscal R, Fierro J, Greenwood A, Vasudevan A (2001) Carbon-supported tungsten and nickel catalysts for hydrodesulfurization and hydrogenation reactions. Appl Catal A 206:295–307

    Article  CAS  Google Scholar 

  • Raj J, Magaret S, Matheswaran M, Kallidanthiyil L, Wilfred C, Mutalib M (2017) Extractive desulfurization of model fuel oil using ester functionalized imidazolium ionic liquids. Sep Purification Technol online 22th August 2017

  • Stojanovic A, Morgenbesser C, Kogelnig D, Krachler R, Keppler B (2011) Quaternary ammonium and phosphonium ionic liquids in chemical and environmental engineering In: Kokorin A (ed) Ionic liquids: theory, properties, new approaches, pp 657–680

  • Sun X, Jin Z, Yang L, Hao J, Zu Y, Wang W, Liu W (2013) Ultrasonic-assisted extraction of procyanidins using ionic liquid solution from Larixgmelinii bark. J Chem 1:1–9

    CAS  Google Scholar 

  • Thompson L, Doraiswamy L (1999) Sonochemistry: science and engineering. Ind Eng Chem Res 38:1215–1249

    Article  CAS  Google Scholar 

  • Varma N, Ramalingam A, Banerjee T (2011) Experiments, correlations and COSMO-RS predictions for the extraction of benzothiophene from n-hexane using imidazolium-based ionic liquids. Chem Eng J 166:30–39

    Article  CAS  Google Scholar 

  • Wang Q, Lei L, Zhu J, Yang B, Li Z (2013) Deep desulfurization of fuels by extraction with 4-dimethylaminopyridinium-based ionic liquids. Energy Fuel 27:4617–4623

    Article  CAS  Google Scholar 

  • Wasewar K (2013) Multistage extractive desulfurization of liquid fuel by ionic liquids. J Mech Eng 3:10–15

    Google Scholar 

  • Wolff M, Alexander K, Belder G (2000) Uses of quaternary phosphonium compounds in phase transfer catalysis. Chim Oggi 18:29–32

    CAS  Google Scholar 

  • Wu Z, Ondruschka B (2010) Ultrasound-assisted oxidative desulphurization of liquid fuels and its industrial application. Ultrason Sonochem 17:1027–1032

    Article  CAS  Google Scholar 

  • Zhang S, Zhang Z (2002) Novel properties of ionic liquids in selective sulfur removal from fuels at room temperature. Green Chem 4:376–379

    Article  CAS  Google Scholar 

  • Zhang S, Zhang Q, Zhang Z (2004) Extractive desulfurization and denitrogenation of fuels using ionic liquids. Ind Eng Chem Res 43:614–622

    Article  CAS  Google Scholar 

  • Zhu W, Zhang J, Li H, Chao Y, Jiang W, Yin S, Liu H (2012) Fenton-like ionic liquids/H2O2 system: one-pot extraction combined with oxidation desulfurization of fuel. RSC Adv 2:658–664

    Article  CAS  Google Scholar 

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Funding

This study received financial support from the Science and Engineering Research Board (SERB), Department of Science and Technology, New Delhi, Government of India, India (Grant Number SB/OS/PDF-362/2015-16).

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Authors and Affiliations

  1. Laboratory of Green Chemistry, LUT Savo Sustainable Technologies, Lappeenranta University of Technology, Sammonkatu 12, FI-50130, Mikkeli, Finland

    Swapnil Dharaskar & Mika Sillanpaa

  2. Department of Chemical Engineering, School of Technology, Pandit Deendayal Petroleum, University, Raisan, Gandhinagar, Gujarat, 382007, India

    Swapnil Dharaskar

  3. Department of Civil and Environmental Engineering, Florida International University, Miami, FL, 33174, USA

    Mika Sillanpaa

  4. Institute of Chemistry, Hebrew University of Jerusalem, 9190401, Jerusalem, Israel

    Kiran Kumar Tadi

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  1. Swapnil Dharaskar
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  2. Mika Sillanpaa
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Correspondence to Swapnil Dharaskar.

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Dharaskar, S., Sillanpaa, M. & Tadi, K. Sulfur extraction from liquid fuels using trihexyl(tetradecyl)phosphonium tetrafluoroborate: as promising solvent. Environ Sci Pollut Res 25, 17156–17167 (2018). https://doi.org/10.1007/s11356-018-1789-5

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