Chemical Engineering Communications

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Evaluation and mechanism of cationic/anionic

dyes extraction from water by ionic liquids

Suchita Mahajan, Neetu Singh, Jai Prakash Kushwaha & Anita Rajor

To cite this article: Suchita Mahajan, Neetu Singh, Jai Prakash Kushwaha & Anita Rajor (2018):
Evaluation and mechanism of cationic/anionic dyes extraction from water by ionic liquids, Chemical
Engineering Communications, DOI: 10.1080/00986445.2018.1520706

To link to this article: https://doi.org/10.1080/00986445.2018.1520706

Published online: 30 Oct 2018.

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CHEMICAL ENGINEERING COMMUNICATIONS
https://doi.org/10.1080/00986445.2018.1520706

Evaluation and mechanism of cationic/anionic dyes extraction from water by

ionic liquids
Suchita Mahajana, Neetu Singhb, Jai Prakash Kushwahab , and Anita Rajora
a
School of Energy and Environment, Thapar Institute of Engineering & Technology, Patiala, India; bDepartment of Chemical
Engineering, Thapar Institute of Engineering & Technology, Patiala, India

ABSTRACT KEYWORDS
Dispersive liquid–liquid micro-extraction (DLLME) using three different imidazolium-based Anionic dyes; Cationic dye;
ionic liquid (IL) was applied for extraction of recalcitrant dyes, Eriochrome black T (anionic Dispersive liquid–liquid
azo dye), and Crystal Violet (cationic triphenylmethane dye) from aqueous solutions, not extraction; Imidazolium-
based ionic liquids;
previously reported. Effects of process parameters such as initial dye concentration, pH of Regeneration
aqueous phase, amount and type of IL on fraction extracted, and distribution ratio of dyes
were studied. Further, dyes interaction with ILs and extraction mechanism were explored.
Considering the high cost of ILs, regeneration and reuse study for ILs was also performed
using reverse DLLME. The fraction extracted for both the dyes with all the ILs varied signifi-
cantly with pH change. Maximum dyes fraction extracted were observed nearly at neutral
pH (pH ¼7). However, the fraction extracted were different for different IL.

Introduction 2005; Mittal et al., 2005; Yeddou and Bensmaili,

Large volume and high strength colored waste-
water is generated from various industries such
as textile, dyeing, food, leather, pharmaceutical,
paper, and cosmetics industries. Various synthetic
dyes and chemicals are generally used in these
industries depending on products need and
methods adopted. Eriochrome black T (EBT) and
Crystal Violet (CV) are anionic azo dye and cat-
ionic triphenylmethane dye, respectively. These
dyes have been reported to be non-biodegradable,
cancer-causing and noxious (Figure 1) (Bansal
et al., 2013). Moreover, very small amount of azo
dyes produce high color intensity. Therefore,
effluents containing these dyes have been consid-
ered as potential threat to humans and aquatic
life (Horikoshi et al., 2004; Malagutti et al.,
2009). Thus, complete remediation of these dyes
is essential before discharge of such effluents into
water bodies.
Various remediation techniques such as chem-
ical coagulation/precipitation, adsorption, and
membrane filtration (Gupta et al., 1997; Georgiou
et al., 2002; Blackburn, 2004; Al-Ghouti et al.,
2005; Ca~nizares et al., 2006; Meng et al., 2015;
Zhao et al., 2015) have been suggested for dye
removal from water. However, restricted per-
formance and derived pollutants limits the appli-
cation of these methods (Kushwaha et al., 2010).
Advanced oxidation methods (UV-H2O2 or UV-
O3) have been reported as most efficient for
removal of dyes from wastewater (Hsu et al.,
2001), but at low dye concentrations.
Furthermore, degradation by-products of dyes
formed during the oxidation are more toxic and
carcinogenic.
Liquid–liquid extraction (LLE) is the most
widely used separation technique, and has been
generally encouraging for dye separation
(Schweitzer, 1979). However, high amount
requirement of hazardous organic solvents such
as hexane, heptane, etc., large volume of second-
ary pollutants generation and longer extraction
time make the LLE process problematic to the
ecosystem and costly (Rydberg et al., 1992).
Roy et al. (1992) employed colloidal gas aph-
rons (CGA) for the removal of organic dyes from

CONTACT Jai Prakash Kushwaha jps_kag@yahoo.co.in Department of Chemical Engineering, Thapar Institute of Engineering & Technology,
Patiala, India.
ß 2018 Taylor & Francis Group, LLC
2 S. MAHAJAN ET AL.
Figure 1. Chemical structures of (a) Eriochrome black T (EBT),
(b) Crystal Violet (CV).
wastewater. Pandit and Basu (2002, 2004a, 2004b)
studied the extraction of ionic dyes from waste-
water using reverse micelles, and concluded that
solvent extraction with reverse micelles is more
efficient than CGA. A solution of methylene
chloride and tetra butyl ammonium bromide was
used to examine the removal of anionic dyes by
Muthuraman and Palanivelu (2005). Cloud point
extraction (CPE) technique for separation of dyes
has also been reported in literature (Purkait
et al., 2005; Tatara et al., 2005; Duraimurugan
and Arunagiri, 2014; Melo et al., 2014; Dharaiya
et al., 2015). However, high temperature require-
ment and use of traditional organic solvents (hex-
ane, heptanes, etc.) to recover the surfactants
from both separated phases make CPE method
expensive and undesirable. Ban et al. (2018)
reported more than 98% Cu ions removal by
using novel synthesized small molecules, linear
polymers, and hyperbranched polymers using
Cu(I)-catalyzed azide–alkyne cycloaddition
(CuAAC). This method can also be applied to
remove dyes.
The liquid–liquid microextraction (LLME)
technique overcomes the drawbacks associated
with above explained methods by reducing the
amount of organic solvent. In LLME, very high
phase ratio (aqueous volume/solvent volume) val-
ues, generally higher than 100 is obtained
(Carasek et al., 2002). Therefore, very small
amount of selected solvent is sufficient for extrac-
tion. Although, LLME may indicate poorer recov-
ery in comparison to conventional methods,
however, substrate concentration significantly
enhances in the organic phase (Jahromi
et al., 2007).
Dispersive liquid–liquid micro-extraction
(DLLME) is an improved LLME technique based
on ternary systems, which has been demonstrated
to show high substrate fraction extracted (Al-
Saidi et al., 2014). In DLLME process, a suitable
disperser possessing high miscibility in both
aqueous and extraction solvent is rapidly intro-
duced into the sample solution (aqueous phase)
containing extraction solvent. In subsequent pro-
cess, the solvent is dispersed as fine droplets in
aqueous phase producing a cloudy solution.
Thus, due to increased surface area of solvent in
aqueous phase increases the substrate fraction
extracted (Majidi et al., 2011), and equilibrium is
achieved rapidly completing extraction very
quickly. In DLLME process, miscibility of dis-
perser in extracting solvent and aqueous phase is
important, and acetone, acetonitrile, methanol,
and ethanol have been successfully applied for
this purpose (Anthemidis and Ioannou, 2009).
Furthermore, ionic liquids (ILs) as extraction
solvent promises improved selectivity and frac-
tion extracted comparative to conventional sol-
vents. The most prominent features of ILs are
negligible vapor pressure, wide liquid range,
selective viscosity, miscibility with aqueous phase,
and high thermal stability. One important feature
of ILs is their ability to regenerate and recycle
themselves, which directly minimizes the cost
and amount of secondary pollutant generation.
ILs based advanced extraction processes for sep-
aration of various pollutants have been reported
in literature (Blanchard et al., 1999; Welton,
1999; Visser et al., 2000; Fadeev and Meagher,
2001; Vijayaraghavan et al., 2006; Pei et al., 2007;
Gharehbaghi and Shemirani, 2012; Elmoubarki
et al., 2015; Panigrahi et al., 2016). Visser et al.
(2000) reported extraction of anionic thymol blue

dye from aqueous solutions using three different
imidazolium-based ILs. Vijayaraghavan et al. (2006)
used pyrrolic IL for the extraction of acid blue and
acid red anionic dyes. IL based dispersive liquid–li-
quid extraction (IL-DLLE) method with a suitable
disperser was first reported by Gharebhaghi and
Shemirani (2012) for the extraction of Congo red
dye. High dye extraction, IL recovery, rapidity, and
ease in operation was reported.
In this study, three different imidazolium-based
ILs such as 1-hexyl-3-methylimidazolium tetra-
fluoroborate ([C6mim][BF4]), 1-butyl-3-methylimi-
dazolium hexafluorophosphate ([C4mim][PF6]),
and 1-hexyl-3-methylimidazolium hexafluorophos-
phate ([C6mim][PF6]) were used as extraction solv-
ent for the extraction of Eriochrome black T (EBT)
(anionic azo dye) and Crystal Violet (CV) (cationic
triphenylmethane dye) from aqueous solution using
dispersive liquid–liquid micro-extraction (DLLME)
technique. The effects of various process parame-
ters such as initial dye concentration (Co), pH of
aqueous phase and dose of IL on fraction extracted
(E) and Distribution ratio (D) of dyes were studied.
Acetone was used as a disperser (DA) in this study.
On the basis of preliminary experiments, 500 mL
DA dose was fixed for all the experiments.
Furthermore, a comparative evaluation and extrac-
tion mechanism for both cationic EBT dye and
anionic CV dye were explored and explained in
detail. In view of process cost feasibility, experi-
ments were conducted for regeneration/recovery
and reuse of ILs using reverse DLLE process along
with exploration of regeneration mechanism.
Materials and methods
Reagents and solutions
The EBT and CV dye, acetone (99%) and NaNO3
salt solution (10% w/v) were purchased from Loba
Chemicals Private Limited, Mumbai, India. Stock
solution of 250 mg/L each of EBT and CV dye was
prepared by dissolving 250 g of each dye in
one liter of distilled water. It was further diluted to
make working solutions of required concentrations.
Increase in IL cation side alkyl chain length,
increases the hydrophobicity of IL, which
improves its regenerability for its reuse making
the extraction process economical. On this ground,
CHEMICAL ENGINEERING COMMUNICATIONS 3
higher alkyl side chain length imidazolium based
hydrophobic ILs [C6mim][BF4], [C4mim][PF6],
and [C6mim][PF6], supplied by Ionic Liquid
Technologies (GmbH, Germany) having viscosities
224, 213, and 680 cP at 298 K, respectively, were
used for EBT and CV dye extraction from aque-
ous solutions. Furthermore, these classes of ILs
possess both cation as well as anion substituent,
due to which these are capable of removing almost
all classes of dyes including indicator dyes.
An acetate buffer solution (2 M, pH ¼ 5.0) was
prepared by mixing 4.32 g glacial acetic acid with
17.42 g sodium acetate to 100 mL of water. Sodium
acetate and acetic acid were supplied by Qualigens
Fine Chemicals Mumbai, India. HCl and HNO3 5
M solutions purchased from S. D. Fine Chemicals,
Ltd., Mumbai, India, were used as stripping agents
to separate dye and regenerate ILs.
DLLE experimental procedure and analysis
For each experiment, 200 mL of acetate buffer (pH
5.0, 2.0 M) and 250 mL of NaNO3 salt solution
(10% w/v) were introduced into a 10 mL round-
bottom centrifuge tube containing 6 mL EBT and
CV dye solution of known initial concentration
and pH. Afterwards, known amounts of IL and
acetone as dispersant (DA) were quickly introduced
into the tube, which formed a cloudy solution dis-
persing IL into fine droplets. Further, the mixture
was centrifuged (CF15RXII type centrifuge Hitachi
Koki Co. Ltd., equipped with an angle rotor) at
4000 rpm for 5 min, and the IL with extracted dyes
was separated from the clear supernatant aqueous
solution. Supernatant liquid samples were then
analyzed for residual dye concentration using UV-
Vis spectrophotometer (Perkin Elmer Lambda 35)
at kmax ¼ 526 nm for EBT dye and kmax ¼ 589 nm
for CV dye. Fraction extracted (E) and Distribution
ratio (D) of dyes were then calculated by following
equations:


C0 Cf
Fraction extracted ðEÞ ¼ (1)
C0

 
C0 Cf Vaq
Distribution ratio ðDÞ ¼ (2)
Cf VIL
where, Co and Cf are initial and final dye con-
centration; Vaq and VIL are the aqueous phase
volume and IL volume, respectively.
4 S. MAHAJAN ET AL.

The EBT and CV dye are indicator dyes, and

their color intensity in aqueous solution is highly
influenced by the pH of solution. Due to the
dyes extraction from the aqueous phase to
organic phase during the extraction process, the
pH of the aqueous phase is altered. This pH
alteration changes the color intensity in the aque-
ous phase, and calculated E and D values will be
false. This pH change was prevented by the add-
ition of buffer solution to the samples. Further,
the ionic strength of aqueous phase affects the
solubility of dyes and extraction solvent (ILs) in
it, and the solubility is usually decreased with the
increased ionic strength (Mirzaei et al., 2011;
Gharehbaghi and Shemirani, 2012). Therefore,
addition of buffer solution to aqueous phase not
only prevent the pH alteration of the solution,
but also decrease the mutual solubility of water
and IL by increasing the ionic strength.
Effect of EBT and CV dye concentration on E
and D value was studied by varying the initial
dye concentration (Co) up to 250 mg/L at
pH ¼ 7.0, dosage of ILs (VIL) and dispersant
(DA) 200 mL and 500 mL, respectively. To study
the pH effects, extraction experiments were con-
ducted over pH range of 2–12 at Co ¼ 250 mg/L,
(VIL) ¼ 200 mL and DA dosage ¼ 500 mL. The pH
was adjusted using HCl and NaOH solutions. Figure 2. Effect of initial dye concentration on the fraction
The IL dosage (VIL) effects were studied at opti- extracted of (a) EBT (b) CV by the DLLE process (Co:
50–250 mg/L; pH ¼7.0; Ionic liquid and disperser dose: 200 lL
mum pH for best performing IL over a VIL range
and 500 lL, respectively).
of 100–225 mL at Co ¼ 50–250 mg/L and DA
dosage ¼ 500 mL.
All the extraction experiments were performed found true for all the three ILs [C6mim][BF4],
at room temperature (25 ± 2 C). ([C4mim][PF6] and [C6mim][PF6]), and IL
[C6mim][BF4]) studied (Figure 2). Furthermore,
Results and discussion IL [C6mim][BF4] revealed best results for EBT
dye extraction by delivering higher E value over
Effect of dye concentrations
all the C0 studied with maximum E value of
Effect of EBT and CV dyes initial concentration 99.65% (Figure 2(a)). Whereas, for CV dye,
(C0) on dye fraction extracted (E) was studied by higher E value was observed for IL [C4mim][PF6]
varying the Co up to 250 mg/L at pH ¼7.0, dos- over all the C0 values with maximum E value of
age of ILs (VIL) and dispersant (DA) 200 and 98.3% (Figure 2(b)).
500 mL, respectively, and the results are shown in Extraction processes are limited either by lim-
Figure 2. iting the analyte concentration or by limiting
It can be seen that, with increase in Co up to amount of extracting solvent. Increasing E value
125 mg/L, the E value for both the EBT and CV with increased Co up to Co ¼ 125 mg/L, reveals
dyes increases, however, marginal change was the high extraction capacity of ILs. This shows
observed beyond C0 ¼ 125 mg/L. This trend was that the process is limited due to the non-
 CHEMICAL ENGINEERING COMMUNICATIONS 5

Table 1. Distribution ratio (D) values for EBT and CV dyes at different Co values studied with various ILs (Ionic liquid dose:
200 mL; pH ¼ 7; Disperser dose ¼ 500 mL).
IL [C6mim][BF4] [C4mim][PF6] [C6mim][PF6]
C0 (mg/L) 31.25 62.5 125 250 31.25 62.5 125 250 31.25 62.5 125 250
D EBT 1061.3 2185 9538 14531.7 265.1 410.2 1221.2 1250 405.6 731.4 2261 2292
CV 8.4 47.9 152 150.3 21.4 88.7 316.6 848 27.3 123.3 1937 2127.8
Relative combined uncertainty (rc,r) in dye distribution ratio ¼ ±0.058.

the D values are high at high C0 but very low at

lower C0 values, and observed true for all the
three ILs used. Therefore, it may be concluded
that all the three ILs used performed very effect-
ively for EBT (anionic) dye extraction from lower
to very high C0 range, while for CV (cationic)
dye extraction ILs used performed well only at
high C0 values. Furthermore, very high D values
of ILs for IL-water system for EBT and CV dye
extraction, shows high affinity and capacity of ILs
for dye extraction.
The mechanism of anionic (EBT) and cationic
(CV) dyes extraction can be explained by the
Equations (3) and (4), respectively (Dai et al.,
1999; Visser et al., 2001; Li et al., 2007).
Cn mimþ B  þ  
IL þ EBTaq $ Cn mim EBTIL þ Baq (3)
Cn mimþ B  þ  
IL þ CVaq $ Cn mim CVIL þ Baq (4)

Here, CnmimþB IL represents IL in aqueous

Figure 3. Effect of pH on the Fraction extracted of (a) EBT (b)
CV by the DLLE process (pH: 2–12; Co ¼ 250 mg/L; Ionic liquid
and disperser dose: 200 mL and 500 mL, respectively).
Relative combined uncertainty (rc,r) in dye fraction
extracted ¼ ±0.0034.
availability of extractable dye in the solution. At
all C0 >125 mg/L, nearly constant E values were
observed revealing extraction process is limited
by limiting extraction solvent dose.
Table 1 shows the distribution ratio (D) values
for EBT and CV dyes at various Co values
studied for various ILs used. It can be seen that
D values are always higher for EBT dye at all C0
studied with all the three ILs used. For CV dye,
solution, respectively.
From the above mechanism (Equations (3) and
(4)), it can be inferred that for higher extraction
of anionic dyes, the hydrophobicity and hydro-
philicity of cationic and anionic component of
IL, respectively, should be high. Whereas, for the
cationic dye extraction, the hydrophobicity and
hydrophilicity of anionic and cationic component
of IL, respectively, should be high. It has been
reported that, as the alkyl chain length of cationic
component of IL increases, cationic component’s
hydrophobicity increases, which in turn improves
the anionic dye extraction from aqueous solution
of dye. At the same time, hydrophobicity of
anionic component [BF4]– of the selected ILs was
reported to be less as compared to [PF6]–
(Chapeaux et al., 2007; Gharehbaghi and
Shemirani, 2012). On the basis of above facts, it
was observed that, for anionic dyes, maximum
and minimum extraction efficiencies were
attained using [C6mim][BF4] and [C4mim][PF6]
ILs, respectively, and for cationic dyes, maximum
and minimum extraction efficiencies were
6 S. MAHAJAN ET AL.
attained using [C4mim][PF6] and [C6mim][BF4]
ILs, respectively.
Effect of pH on dye fraction extracted
pH of the aqueous solution is highly significant
parameter for the extraction processes. Therefore,
the pH dependency of fraction extracted for vari-
ous dyes (EBT and CV) were investigated, and
results are shown in Figure 3. For this purpose,
extraction experiments were conducted over pH
range of 2–12 at Co¼250 mg/L (for both the EBT
and CV dyes). To adjust the pH, HCl and NaOH
solutions were used. The ILs ([C6mim][BF4],
[C4mim][PF6], and [C6mim][PF6]) and DA dos-
age were kept constant at 200 mL and 500 mL,
respectively.
It can be noted that, for both the dyes (EBT
and CV), the E value varies significantly with
change in the pH of aqueous phase, and max-
imum attained E value were found different EBT
and CV dye, but at nearly neutral pH (pH ¼7)
value (Figure 3). This was found true for all the
three ILs studied. It was observed that the E
value of EBT dye increased with increasing pH
from 2 to 6, showing maximum E value at
pH ¼ 6 (Figure 3). For all the pH >6 and with all
the three ILs studied, the E value decreased
sharply. For CV dye extraction, it was found that
with increase in pH from 2 to 8, for all ILs
studied, E value increased being maximum at
pH ¼ 8. Further increase in pH, for all the pH
>8, the extraction behavior was observed oppos-
ite to EBT dye extraction behavior, and E value
was found to be nearly constant.
The extraction behavior of the system can be
explained with the hydrogen bonding and ioniza-
tion degree/charged state of the dyes with pH
(Pei et al., 2007). The EBT dye contains sulfonate
group and azo group. In the aqueous solution,
sulfonate group converted to be anionic. At lower
pH, azo group is protonated and EBT dye mol-
ecule becomes zwitterionic (Li et al., 2007).
Further, at pH > pKa (pKa ¼ 6.2 for EBT),
anionic form dominates, whereas at pH < pKa
zwitterionic form. Therefore, increase in the
dominance of anionic form for EBT dye due to
increase in pH (from acidic to neutral), the E
value was found to be increased up to neutral pH
via mechanism shown as Equation (3).
Furthermore, hydrogen bonding between OH
group of EBT dye and fluoro group (F) of PF6/
BF4 of ILs enhances the E value for EBT dye.
Therefore, it can be concluded that the EBT dye
molecules in the anionic form becomes hydro-
phobic and prefer to be partitioned in ILs phase,
and hydrogen bonding between OH group of
EBT dye and F (fluoro) of PF6/BF4 of ILs enhan-
ces the E value of EBT dye.
The ionic state of CV dye (cationic) also
changes with change in pH. In the pH range 0–2
and 2–9, the form of CV is CV3þ3Cl and
CV2þ2Cl, respectively, while it is in the form
of CV-OH at pH >9 (Cotoruelo et al., 2012).
Therefore, dominance of cationic form of CV dye
increases with decrease in pH and vice versa.
Hence, due to the decrease in the cationic form
dominance of CV dye with the increase in pH
from 2 to 8, E value was found increasing via
mechanism shown as Equation (4). For pH >9,
the E value was observed nearly constant con-
cluding that CV-OH form of CV dye favored the
extraction. Therefore, it can be concluded that
the CV dye molecules hydrophobicity increases
with decrease in cationic dominance of CV dye
(opposite to anionic dye) and prefer to be parti-
tioned in ILs phase.
The maximum E value for EBT dye with the
ILs: [C6mim][BF4], [C6mim][PF6], and
[C4mim][PF6] were found to be 99.17, 97.09, and
94.93%, respectively, and for CV dye 85.27, 95.28,
and 98.27%, respectively (Figure 3). A compara-
tive observation showed higher fraction extracted
for EBT dye with all the three ILs studied due to
the additional EBT dye extraction via hydrogen
bonding, as discussed above, which enhances the
E value of EBT dye in comparison to CV dye.
The decrease in E value of EBT dye with all the
three ILs studied at pH >6 may be elucidated by
absence of hydrogen bonding due to the removal
of H from OH group of EBT dye, and dye
removal is only due to hydrophobic nature of
dye molecules.
From this study, it was concluded that for EBT
dye (anionic), the highest fraction extracted was
observed in the range of acidic to neutral pH of
aqueous solution, while for CV dye (cationic) the
highest fraction extracted was observed in neutral

Figure 4. Effect of Ionic liquid dose on the Fraction extracted
by DLLE process at various initial dye concentrations (a) IL:
[C6mim][BF4]; Dye: EBT (b) IL: [C4mim][PF6]; Dye: CV (Ionic
liquid dose: 100–225 mL; pH ¼ 7; Co: 50–250 mg/L; Disperser
dose ¼ 500 mL). Relative combined uncertainty (rc,r) in dye
fraction extracted¼ ±0.0034.
to basic pH of aqueous solution. Therefore,
pH ¼ 7 was selected as optimum pH for further
study. Also, ILs C6mim][BF4] and C4mim][PF6]
were found to be best performing for EBT and
CV dyes removal, respectively.
Effect of IL dosage on dye fraction extracted
The effect of IL dosage (VIL) on dye extraction
was studied in the range of 100  VIL  225 mL at
optimum pH¼ 7, while Co ¼ 50-250 mg/L and DA
dosage ¼ 500 mL. This study was conducted only
for best performing IL (C6mim][BF4]) for EBT
and C4mim][PF6] for CV dye, as concluded in the
Section “Effect of pH on dye fraction extracted”.
As the VIL was increased, a rapid increase in
the E value was observed for both EBT and CV
CHEMICAL ENGINEERING COMMUNICATIONS 7
dyes extraction, thereafter, nearly constant E
value was found for all values of Co studied
(Figure 4). It can be seen that E value of both the
EBT and CV dyes reaches equilibrium value at
VIL values of 150, 175, and 200 mL for Co values
of 50, 125, and 250 mg/L, respectively.
Furthermore, increasing VIL values beyond equi-
librium E values at any CO did not improve the
E value. This imply that the extraction process is
limited by the limiting dye concentration. It can
also be observed that increasing Co at any VIL
value, increases the E value, and was found true
for both the EBT and CV dyes, which concludes
that the EBT and CV dye extraction by IL
C6mim][BF4] and C4mim][PF6], respectively, is lim-
ited by dyes concentration. Furthermore, it can
also be inferred that, optimum VIL required
should be between 150 and 200 mL for both EBT
and CV dyes, respectively, in the studied
Co range.
IL regeneration based on reverse
dispersive extraction
In view of cost of IL and DLLE process economy,
regeneration, and reuse study of the IL was con-
ducted. Different acid stripping solutions (5 M
solutions of HCl and HNO3) were examined to
regenerate ILs from IL-dyes complex for succes-
sive DLLE processes. Best performing IL
C6mim][BF4] and C4mim][PF6] for EBT and CV
dyes, respectively, with VIL ¼ 200 mL was selected
for this study.
After removal of the upper clear aqueous
phase formed during the DLLE process, 0.5 mL
acid stripping solutions were rapidly injected to
the centrifuge tubes containing dye loaded IL
with help of a syringe arrayed with a PTFE nee-
dle followed by the centrifugation of mixtures for
2 min at 4000 rpm. This resulted in the formation
of upper aqueous layer containing dye leaving
behind colorless layer of IL. In subsequent pro-
cess, upper layer was separated, and regenerated
IL were again used as solvent for extraction of
EBT and CV dyes in DLLE process at Co¼
250 mg/L, Acetate buffer ¼ 200 mL, salt
(NaNO3) ¼ 250 mL (10% w/v), DA ¼ 500 mL. This
regeneration-reuse cycle was repeated three times,
and the results are shown in Figure 5.
8 S. MAHAJAN ET AL.

Figure 5 reveals that both the stripping solu-

tions HCl and HNO3 were found suitable for IL
regeneration, showing nearly same E value for
regenerated IL for both the EBT and CV dyes.
The E value was found to decrease from 99.2 to
90.25% for EBT dye, and from 98.23 to 96.23%
for CV dye using HCl as stripping solutions;
while, using HNO3 as stripping solution, the E
value was decreased from 98.93 to 89.76% for
EBT dye, and 98.4 to 96.7% for CV dye for 1–3
regeneration-reuse cycles. Clearly, the decrease in
E value between fresh and regenerated IL used
for EBT extraction is larger than CV dye.
However, the gap in E value is marginal in CV
dye extraction. This was found true for both the
stripping solutions HCl and HNO3.
The stripping of dyes from IL-Dye complex
can be explained by the reverse ion exchange
mechanism in opposite to Equations (3) and (4).
As explained in the Section “Effect of IL dosage
on dye fraction extracted”, the anionic form of
EBT dye molecule dominates in pH > pKa (pKa
value for EBT 6.2) and zwitterionic (ZW) at
pH < pKa. While, the dominance in the cationic
form of CV dye increases with decrease in pH
and vice versa. Addition of HCl and HNO3 as
stripping solution in IL-Dye complex produces Figure 5. Fraction extracted of dyes after various regener-
ation-reuse cycle with (a) HCl (b) HNO3 (Ionic liquid dose:
highly acidic pH environment. Therefore, in 200 mL; pH ¼ 7; Co: 250 mg/L; Disperser dose ¼ 500 mL).
highly acidic pH, due to dominance of zwitter- Relative combined uncertainty (rc,r) in dye fraction
ionic (ZW) and cationic form of EBT and CV extracted ¼ ±0.0034.
dye, respectively, the dye molecules are stripped
out in the acids used by the following mechanism NMR spectra for best performing IL
(Equations (5) and (6)), in reverse way to the ([C6mim][BF4]) and regenerated IL from IL-EBT
extraction mechanism described by Equations (3) Dye complex with HCl and HNO3 are shown in
and (4). Figure 6. The 1H NMR analysis for the IL
Cn mimþ EBTIL
 
þ Claq $ Cn mimþ ClIL

þ EBTaq
ZW
(5) [C6mim][BF4] and regenerated using HCl and
Cn mimþ CVIL

þ NO3  þ  þ HNO3 are given below:
aq $ Cn mim NO3 IL þ CVaq
[C6mim][BF4] 1H NMR (CDCl3, d ppm): 8.521
(6)
(1H, t), 7.2898 (1H, d), 7.2429 (1H, q), 4.6712
From the above mechanism, it can be seen (3H, P), 4.0103 (2H, Sx), 3.7457 (2H, p), 2.0561
that after stripping of dyes from IL-Dye complex (2H, t), 1.687 (2H, Sx), 1.1214 (2H, t), 0.6964
with HCl and HNO3, regenerated IL must be (3H, t). HCl regenerated IL 1H NMR (CDCl3,
[C6mim][Cl] and [C6mim][NO3] in place of d ppm): 8.5 (1H, t), 7.2681 (1H, t), 7.2233 (1H,
([C6mim][BF4]. In order to confirm this, 1H t), 4.6928 (3H, P), 3.9874 (2H, Sx), 3.6861 (2H,
NMR spectra were recorded on Jeol-400 (1H, p), 2.0492 (2H, t), 1.66 (2H, Sx), 1.095 (2H, t),
400 MHz) spectrometer at ambient temperature 0.66 (2H, t). HNO3 regenerated IL 1H NMR
using CDCl3 as solvent, and chemical shifts are (CDCl3, d ppm): 8.356 (1H, t), 7.124 (1H, d),
reported in ppm from the solvent resonance. 1H 7.0983 (1H, d), 4.7531 (3H, P), 3.8832 (2H, Sx),

Figure 6. 1HNMR spectra of the fresh Ionic liquid [C6mim][BF4] and regenerated IL using HCl and HNO3.
3.5352 (2H, P), 1.9 (2H, t), 1.5 (2H, Sx), 0.9563
(2H, t), 0.523 (3H, t).
From the comparison of 1H NMR analysis,
shifted resonance peaks for IL regenerated with
HCl and HNO3 IL from IL [C6mim][BF4] reson-
ance peaks can be seen, confirming the formation
of new IL possibly [C6mim][Cl] or [C6mim][NO3].
Therefore, it can be concluded that after the extrac-
tion of dyes with ILs, due to ion exchange between
dye and ILs, the basic structure of ILs is destroyed.
The regenerated ILs which were further used for
dye extraction in first and second regeneration-
reuse cycle are [Cnmim][Cl] or [Cnmim][NO3] in
place of [Cnmim][BF4]/[Cnmim][PF6]. Further, the
regenerated ILs ([Cnmim][Cl] or [Cnmim][NO3])
showed good performance.
Conclusions
The following conclusions are drawn from the
present study:
1. “Effect of initial dye concentration” study
revealed that used ILs possess high extraction
CHEMICAL ENGINEERING COMMUNICATIONS 9
capacity, and the extraction process is limited
by limiting dye concentration.
2. Maximum dye fraction extracted for EBT
(anionic) dye was observed for IL
[C6mim][BF4] due to high hydrophobicity
and hydrophilicity of cationic [C6mim] and
anionic [BF4] components, respectively. For
CV (cationic) dye, IL [C4mim][PF6] revealed
highest extraction capacity due to [C4mim]
being highly hydrophilic and [PF6] highly
hydrophobic.
3. EBT dye in the anionic form becomes hydropho-
bic and prefer to be partitioned in ILs phase.
While, CV dye molecules hydrophobicity increases
with decrease in cationic dominance of CV dye
(opposite to anionic dye) and prefer to be parti-
tioned in ILs phase.
4. Comparatively, for all the three ILs, higher E
values were observed for EBT dye due to add-
itional dye extraction by hydrogen bonding
between OH group of EBT and fluoro (F)
group of PF6/BF4 of ILs.
5. In highly acidic pH, due to dominance of zwitter-
ionic (ZW) and cationic form of EBT and CV
10 S. MAHAJAN ET AL.
dye, respectively, the dye molecules are stripped
out in the stripping acids (HCl/HNO3).
6. During the extraction, due to ion exchange
between dye and ILs, the basic structure of ILs is
destroyed and IL-Dye complex is formed. The
regenerated ILs which were further used for dye
extraction in first and second regeneration-reuse
cycle are [Cnmim][Cl] or [Cnmim][NO3] in place
of [Cnmim][BF4]/[Cnmim][PF6].
Disclosure statement
Authors declare no conflict of interest.
Funding
Authors are thankful to School of Energy and Environment,
Thapar Institute of Engineering & Technology, Patiala,
Punjab, India, for providing financial assistance.
ORCID
Jai Prakash Kushwaha http://orcid.org/0000-0003-
4077-8805
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