Application of Asymmetric Dicationic Ionic Liquids
Application of Asymmetric Dicationic Ionic Liquids
Application of Asymmetric Dicationic Ionic Liquids
ORIGINAL ARTICLE
a
Egyptian Petroleum Research Institute, Egypt
b
Ain Shams University, Egypt
c
King Abdulaziz University, KSA
1. Introduction spills would float and spread on water due to the smaller grav-
ity and surface energy so, the marine ecosystem remarkably
Through the world wide fast development of marine trans- contaminated and the algae primary production decreased
portation and oil exploration, the oil spills became the major because of depletion of light into the water (Penela-Arenaz
contributors to the marine pollution and cause many environ- et al., 2009).
mental catastrophes (Huang et al., 2019; Naser, 2013). Oil The methods of oil spill treatment in aquatic environment
spills may result from the rupture of pipeline and holding have different classifications mechanical, biological and chem-
tanks or well blowout (Komoto and Kobayashi, 2004). Oil ical techniques (Muhd Julkapli et al., 2011). In mechanical
method engineers using skimmers, oil booms, barriers or sor-
bents and need different instruments to physically absorb or
* Corresponding author. suck up oil from water surface. In biological method micro-
E-mail address: raghda_elnagar@yahoo.com (R.A. El-Nagar). organisms could eat or break down the toxic components or
Peer review under responsibility of King Saud University. oil spill into nontoxic materials but this way of remediation
is slow and not adapted in cold areas (Behera and Ray, 2016).
In chemical treatment the dispersion mechanism is to min-
imize the oil droplets size by reducing the interfacial tension
Production and hosting by Elsevier
https://doi.org/10.1016/j.arabjc.2021.103123
1878-5352 Ó 2021 The Author(s). Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 C.E. El shafiee et al.
between oil and water under the effect of wave action as the drop wise, the stirring completed till white precipitate
smaller droplets, the more dispersion efficiency (Kujawinski was formed (about 3hrs). White precipitate (KBr) was
et al., 2011). The usage of chemical dispersants in marine envi- eliminated by filtration and the filtrate vaporized under
ronment is worldwide accepted; however, most of them are vacuum.
toxic and hazardous to the marine habitats. From this point (ii) Compounds [a, b and c] were prepared by stirring 4-
ionic liquids received highly attention because of their techno- methyl pyridine (0.1 mol) with n-di-bromo alkanes
logical and environmental promising (Adeniyi Ogunlaja et al., (0.1 mol) (1,2-dibomoethane, 1,6-dibromohexane and
2018)benefits (low toxicity (Visser et al., 2011), low volatility 1,10-dibromodecane) at room temperature for 3hrs.
(Li et al., 2008; Ezzat et al., 2018; Atta et al., 2018; Atta The products were washed several times with ethyl acet-
et al., 2017; Abdullah et al., 2017), high surface activity and ate to get rid of unreacted materials. White precipitate
thermal stability) (Pandey, 2006; Wilkes, 2002; Li et al., was afforded by filtration and recrystallized from petro-
2009) furthermore the self-assembling properties of amphiphi- leum ether 40–60 (Chang et al., 2010).
lic ionic liquids (Adawiyah et al., 2019; Lotfi et al., 2017; El- (iii) Ia, Ib and Ic dicationic ionic liquids were synthesized by
Nagar et al., 2017). refluxing mixtures of compound I with a, b and c, (1:1),
In this work three amphiphilic asymmetric dicationic ionic for 3 hrs in presence of acetonitrile as a solvent. The
liquids (green compounds) were successfully synthesized and mixtures were concentrated by evaporation of acetoni-
characterized (Table 1). The synthesized series possess high trile and dried under vacuum (Lv et al., 2019) Scheme 1.
surface activity and evaluated as oil spill dispersants.
2.1. Materials and methodology The chemical structures of (Ia – c) were confirmed via.
All chemicals and reagents were purchased from interna- Elemental Analysis: Elemental analysis was performed via
tional chemical companies. They are of analytical grade elemental analyzer Perkin Elmer 240C.
and used directly without further purification. 1- FT-IR Spectroscopy: FT-IR spectra were obtained from
bromododecane (98%), 2-methyl imidazole (99%) and Nicolet Ia-10 in the range of 4000–400 cm1 with suitable
potassium hydroxide (97%), Sigma-Aldrich. 4-Methyl pyr- scan resolution 4 cm and scan rate 32 cm/min.
idine (99%), acetonitrile (97%), 1,2-dibromoethane (99%,) 1H NMR Spectroscopy: 1H NMR spectra for the prepared
1,6-dibromohexane (99%), 1,10-dibromodecane (99%), and materials were obtained using BRUKER 1H NMR spec-
ethyl acetate (98%) Merck. Petroleum ether (40–60) (98%), troscopy. The spectrometer operates at 400.19 MHz and
aluminium hydroxide (neutral), filter paper Whatman No.1 used 5-mm broad band inverse Z-gradient probe in
and chloroform (99%), Alfa Aesar. Sea water (Red Sea) DMSO d6 solvent.
and heavy crude oil from Suez Golf. Thermo-gravimetric Analysis (TGA): TGA analysis was
Synthesis of dicationic ionic liquids (Ia – c): achieved by simultaneous TGA-DSC (model: SDT Q600,
USA) (EPRI).
The mechanisms of synthesis were illustrated as follows:
(i) Compound (I) was prepared before (El-Taib Heakal 2.3. Surface tension measurements of (Ia – c)
et al., 2017)by stirring 2-methyl imidazole (0.1 mol) with
potassium hydroxide in acetonitrile (50 ml). After com- Surface tension measurements were carried out using a Du
plete miscibility 1-bromododecane (0.1 mol) was added Nouy tensiometer with a platinum ring. Freshly prepared
1-(2-(1-dodecyl-2-methyl-1H-imidazol-3-ium-3-yl)ethyl)-4-methylpyridin-1-ium
Ia
bromide
1-(6-(1-dodecyl-2-methyl-1H-imidazol-3-ium-3-yl)hexyl)-4-methylpyridin-1-ium
Ib
bromide
1-(10-(1-dodecyl-2-methyl-1H-imidazol-3-ium-3-yl) decyl)-4-methylpyridin-1-ium
Ic
bromide
Application of asymmetric dicationic ionic liquids for oil spill remediation 3
aqueous solutions of asymmetric dicationic ILs were measured A definite amount of sea water sample (250 ml) is trans-
over a concentration range of 0.01–0.00001 M/L at 25 °C. The ferred to a separating funnel and maintained at required
surface tension of double distilled water was measured to cal- temperature and then (5 ml) of used crude oil was added
ibrate instruments, which was generally 72.00 ± 0.50 mN/m to the water surface and left for 1 min.
(El-Dib et al., 2013; Nessim et al., 2018). A known amount of dispersant was added. After a time of
Interfacial tension measurements using paraffin oil at 2.5 min from the addition of oil, the oil was shacked for two
25 °C. Emulsion stability was measured by vigorously stirring minutes, then 50 ml of the oily water was drown in a 50 ml
a mixture of 10 ml (0.5%) of solution and 10 ml of paraffin oil measuring cylinder in a time not exceeding 10 s. Then, the
at 25 °C (Abdallah et al., 2007). oily water was transferred from the measuring cylinder to
separating funnel.
2.4. Physicochemical properties of the delivered crude oil The measuring cylinder was washed twice with 10 ml
of chloroform. The washing was added to separating
Physicochemical characteristics of the crude oil sample were funnel, and shacked for 1 min. Two phases were
studied according to standard methods (water content (ASTM allowed to separate completely and run off the chloro-
D-95), pour point (ASTM D-97), viscosity & viscosity index form layer through a Whatman filter paper No.1 con-
(ASTM D-445), density (ASTM D-4052), flash point (ASTM taining anhydrous sodium sulphate. Chloroform
D-93), asphaltene content (IP 43) and wax content (UOP 64)). extraction was repeated twice more using 20 ml of
chloroform. The dried extracts and washings were com-
2.5. Evaluation of (Ia – c) as oil spill dispersants bined in 100 ml volumetric flask to mark, stopped and
mixed well.
2.5.1. Efficiency test Calibration, of used crude oil is made at different concen-
trations (0.1, 0.2, 0.3, 0.4 & 0.5 g) in chloroform. The
Studying the efficiency of the prepared ILs as oil spill disper- absorbance of each solution is measured at 580 nm.
sants at different temperatures and concentration as following Fig. 1.
(Deyab et al., 2020):
4 C.E. El shafiee et al.
core, it can reduce free energy, resulting in a lower CMC value where c0 is the surface tension of the pure water and c is the
(Pisárcik et al., 2016; Pal et al., 2017). surface tension of the surfactant solution at CMC (Negm
Effectiveness (pCMC): and Mohamed, 2004).
The difference between the surface tension of Ia-c at their The effectiveness of Ia-c ranged between 38 and 40 dyn/cm
CMC and that of pure water is termed ‘‘effectiveness” (pCMC): at 25 °C (Table 5). It is obvious that Ia-c are efficient in achiev-
ing the maximum reduction of surface tension at cm, Table 5.
pCMC ¼ c0 c
ii. Efficiency (PC20)
For Ia-c, the PC20-values were determined Table 5. These
values commonly characterize the efficiency of them to lower
surface tension.
Values of C20 for Ia-c indicate that they have great effi-
ciency in reducing surface tension of water and showed high
surface activity.
1
Table 4 H NMR spectroscopy.
Chemical shift (d ppm)
Comp. a b c d e f g h i j K
(t) (t) (m) (s) (s) (t) (t) (d) (d) (d) (d)
Ia 0.86 1.24 1.73 2.51 2.63 4.09 5.21 7.71 8.04 8.90 9.14
Ib 0.86 1.29 1.72 2.51 2.63 4.04 4.56 7.74 7.99 8.01 9.01
Ic 0.84 1.23 1.72 2.51 2.62 4.10 4.57 7.59 7.69 8.01 9.00
Ib Concentration, ppm
o
Temp. C 750 1500 2000 3000
Efficiency, %
10 13.47 33.61 23.61 11.57
30 21.90 66.80 61.08 54.32
50 32.69 75.50 70.62 55.22
Ic.
Ic Concentration, ppm
Temp. oC 750 1500 2000 3000
Efficiency, %
10 9.25 12.66 10.95 2.68
30 28.34 36.98 31.24 29.97
50 41.60 51.22 48.73 36.98
8 C.E. El shafiee et al.
Ia Ib Ic
Declaration of Competing Interest Huang, D., Sebastian, R., Zhang, L., Hongfei, X.u., Lei, S., Chen, M.,
Shinde, A., Ma, Rong, Sam Mannan, M., Cheng, Zhengdong,
2019. Biocompatible Herder for rapid oil spill treatment over a
The authors declare that they have no known competing
wide temperature Range. J. Loss Prev. Process Ind. 62, 103948.
financial interests or personal relationships that could have Huanga, D., Sebastianb, R., Zhangc, L., Xub, H., Leic, Sh., Chenc,
appeared to influence the work reported in this paper. M., Shindec, A., Mac, R., Mannanb, M.S., Cheng, Zh., 2019.
Biocompatible Herder for rapid oil spill treatment over a wide
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