290 Clean – Soil, Air, Water 2012, 40 (3), 290–297

Maysam Gharehbaghi
Farzaneh Shemirani
Research Article

Department of Analytical Chemistry, A Novel Method for Dye Removal:

University College of Science,
University of Tehran, Tehran, Iran
Ionic Liquid-Based Dispersive Liquid–Liquid
Extraction (IL-DLLE)
A novel, simple, fast, and efficient ionic liquid-based dispersive liquid–liquid extraction
(IL-DLLE) has been applied to extract and remove Congo Red (CR; a carcinogenic textile
dye) from aqueous solutions. In this methodology a binary solution, containing the
extraction solvent (1-hexyl-3-methylimmidazolium bis(trifluormethylsulfonyl) imid)
and a suitable disperser solvent, was rapidly injected into the water sample containing
CR dye. Therewith, a cloudy solution was formed, and most of the dye molecules were
extracted into fine IL droplets and removed from aqueous phase. The effects of pH, type,
and amount of IL, initial concentration of the dye, type and volume of the dispersant,
and concentrations of salt on the extraction of the dye were studied. Experimental
surveys were also accomplished for recovery of the IL by applying a reverse dispersive
liquid–liquid extraction using acidic stripping solutions.
Keywords: Azo dye; Congo Red removal; Ionic liquid; Recovery; Saline wastewater
Received: May 11, 2011; revised: August 24, 2011; accepted: September 1, 2011
DOI: 10.1002/clen.201100258

1 Introduction and human and not readily degradable [16]. On the other hand, by-
products of azo dyes degradation have hazardous effects on the
Coloring of products, such as carpet and paper, plastics, leather,
environment because of their chemical structure, which contains
rubber, dyestuffs, textiles, pharmaceutical, food, and cosmetics, is
toxic aromatic amines with low-removal rate during aerobic waste
one of the most important processes in many different industries, in
treatment. Therefore, colored wastes containing such dyes need to
which huge amounts of dyes and significant volumes of water are
be treated before disposal. Wastewaters containing such a type of
used. Consequently, a considerable amount of colored wastewater is
dyes are known to be highly resistant to traditional physical, chemi-
generated. In fact, about 10–15% of the utilized dyes are discharged
cal, and biological degradation methods [17–20].
into wastewater streams [1]. Releasing of these wastes into the
One of these azo dyes, Congo Red (CR) [1-naphthalene sulfonic
environment has caused many significant problems, such as increase
acid, 3,30-(4,40-biphenylenebis (azo)) bis(4-amino-)disodium salt], is a
in toxicity and chemical oxygen demand (COD) of the effluent and
water soluble anionic diazo compound. It is used in various indus-
also decrease of light penetration, which has a derogatory effect on
tries, such as cotton, wool, and silk, to provide red color. Its complex
photosynthetic phenomenon. Moreover, presence of these dyes in
aromatic structure (Fig. 1(a)) affords CR physicochemical, thermal,
water even at a very low concentration is rather observable and
and optical stability. In addition, its high-molecular weight and
undesirable because public perception of water quality is directly
water solubility cause greater environmental persistence. This benzi-
influenced by its color [2]. So the removal of color from waste
dine-based dye is toxic to many organisms and is a suspected carci-
effluents has become essential for the environment [3, 4].
nogen and mutagen. Despite being banned in many countries CR is
Different technologies have been tested for the dye removal,
still widely used in several countries.
including adsorption [5–7], biosorption [8, 9], precipitation, filtra-
In the last years, various methods and materials have been used
tion, flotation, flocculation, ion exchange, reverse osmosis processes
for removal of CR from wastewaters, such as adsorption by activated
[10, 11], and electrochemical treatments [12]. Advantages and dis-
carbon [21, 22], anilinepropylsilica xerogel [23], maghemite nano-
advantages of each method have been extensively reviewed [13, 14].
particles, and perlite [24, 25] as well as cloud point extraction (CPE)
Approximately, half of all known dyes are azo dyes, making them
using TX-100 [26, 27] and others [28]. However, some of these adsorb-
the largest group of synthetic colorants used in textile industries
ents are impractical for use in modern textile industries. Since,
[15]. They have high toxicity and are even carcinogenic for animals
regeneration processes of these spent adsorbents are usually time-
consuming and expensive. Advantages of CPE are medium energy
consumption, lower cost, experimental convenience, as well as use
Correspondence: Professor F. Shemirani, Department of Analytical
Chemistry, University College of Science, University of Tehran, P.O.
of relatively nontoxic surfactants instead of toxic organic solvent.
Box 14155-6455, Tehran, Iran Notwithstanding many benefits of using CPE, phase separation does
E-mail: [email protected] not occur in the presence of over 3% of water-miscible organic
solvents [29]. Furthermore, this method suffers from high content
Abbreviations: CPE, cloud point extraction; CR, Congo Red; DLLE,
dispersive liquid–liquid extraction; IL, ionic liquids; IL-DLLE, ionic of salt, because the enrichment phase becomes more composed of
liquid-based dispersive liquid–liquid extraction aqueous solution. Moreover, to meet the CPE more economically, the

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Clean – Soil, Air, Water 2012, 40 (3), 290–297 A Novel Method for Dye Removal 291

Figure 1. Ionization of CR in aqueous solutions.

surfactant recovery from both separation phases is inevitable. adapted to remove CR, which was selected as a model dyeing pollu-
However, problem arises for non-volatile solutes like dyes. Since, tant, from saline solutions. As a simple, reliable, potent, and fast
unlike volatile solutes, gas, or vacuum stripping operations are not extraction/separation method, ionic liquid-based dispersive liquid–
applicable to recover surfactant from the coacervate phase. For this liquid extraction (IL-DLLE) not only is superior against rather high
reason, solvent extraction (SE) based on organic solvents (hexane, content of salt and water-miscible organic solvents, but also it is
heptane, etc.) has been applied to recover the surfactant after evap- much safer compared with traditional SE methods. Since, relatively
orating the solvent [27]. On the other hand, application of rather small amounts of a ‘‘rather green solvent’’ (IL) are used as the
high temperatures (>708C), to reach cloud point temperature (CPT) extraction phase which can be regenerated to reuse. Operation in
for phase separation and extraction, makes CPE an expensive and continuous-mode is one more important capability of this method.
uneconomical method for industries. The effects of initial dye concentration, pH of aqueous phase, type
Ionic liquids (ILs) have gained an increasing interest in industry and amount of IL, type and volume of dispersant, and concentrations
and academia. They are applied in various fields progressively and of salt on the extraction of CR have been studied. Besides, for the
can replace conventional volatile solvents in many applications. recovery and regeneration of the sedimented IL phase and its recy-
Their most often cited attribute is their negligible vapor pressure cling to the extraction process, two parameters, such as type and
even at elevated temperatures, which offers some advantages like composition of the regenerative solvent have been investigated.
product recovery and recycle. Other pertinent physico-chemical
properties include a broad liquid range, non-flammability, high
thermal and oxidative stability, tunable viscosity, and miscibility 2 Experimental
with water and organic solvents. Moreover, ILs show excellent dis- 2.1 Instrumentation
solution/extractability properties for a wide variety of compounds
like organic species or metal ions. Classical liquid–liquid extraction An UV–Vis light source, optical fibers, and spectrograph (model 2048)
(LLE) [30–34] and various advanced extraction methods [35–46] based were purchased from Avantes (Eerbeek, Netherlands). A quartz
on ILs have been developed for separation and preconcentration of a microcell (Hellma, Mullheim, Germany) and one Universal 320R
variety of species. refrigerated centrifuge (Hettich, Kirchlengern, Germany), equipped
For the first time in 2008, application of ILs in dispersive liquid– with an angle rotor (6-place, 9000 rpm, Cat. No.1620A) were obtained.
liquid microextraction (DLLME) has been reported by our group [47]. PTFE needles were purchased from Iwashita Engineering, Inc. (Tokyo,
Ease of operation, quickness, high-enrichment factor, and recovery Japan).
as well as environmental benignity are advantages of ionic liquid-
based dispersive liquid–liquid microextraction (IL-DLLME). In
2.2 Reagents and solutions
addition, despite wide prospects in trace analysis, it seems to be a
more economical method. All reagents, bases, acids, and used salts were of analytical reagent
In the present work, for the first time by means of an IL as the grade and purchased from Merck (Darmstadt, Germany). Triply dis-
extractant, dispersive liquid–liquid extraction (DLLE) has been tilled water was used throughout the experiment. CR, 1-hexyl-3-

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292 M. Gharehbaghi and F. Shemirani Clean – Soil, Air, Water 2012, 40 (3), 290–297

methylimidazolium bis(trifluoromethylsulfonyl) imide meet the economy of the process. To separate CR dye from the IL
([Hmim][Tf2N]), 1-hexyl-3-methylimidazolium hexafluorophosphate phase and regeneration of this worth extraction solvent for the
([Hmim][PF 6 ]), 1-hexyl-3-methylimidazolium tetrafluoroborate subsequent DLLE process, a series of acidic stripping solutions were
([Hmim][BF4]), 1-ethyl-3-methylimidazolium bis(trifluoromethylsul- investigated.
fonyl) imide ([Emim][Tf2N]), as well as 1-butyl-3-methylimidazolium After the general extraction procedure, centrifugation and
bis(trifluoromethylsulfonyl) imide ([Bmim][Tf2N]) were purchased removal of the upper aqueous phase, one acidic stripping solution
from Merck. was rapidly injected at the end of each conical tube by a syringe
A stock solution (1000 mg L
1) of CR was prepared by dissolving the equipped with a PTFE needle, and another cloudy state was obtained.
proper amount of this dye in water. Working solutions of required The mixtures were then centrifuged for 2 min at 4000 rpm.
concentrations were prepared by appropriate dilution of the dye Consequently, an upper aqueous solution containing a blue-colored
stock solution. A 2.0-mol L
1 buffer solution (pH 5.0) was obtained by layer of CR and an underneath layer of IL phase, which was almost
mixing proper amounts of acetic acid and sodium acetate in triply colorless, were obtained. After separation of two phases, recovery
distilled water. efficiencies of acidic stripping solutions were measured individually
by proper dilutions of colored aqueous phases, adjustment of pH 5.0,
and then determination of the released CR concentration by spectro-
2.3 IL-DLLE general procedure photometer at 501.0 nm.
The schematic view of IL-DLLE experimental setup is shown in Fig. 2.
The extraction process was performed at room temperature 3 Results and discussion
(25  28C) as follows: A total of 200 mL of buffer (pH 5.0,
2.0 mol L
1) and 250 mL of NaNO3 10% w/v were added into a 15-mL Before and after each extraction, concentration of the studied dye in
conical-bottom plastic centrifuge tube containing different concen- the aqueous solution was determined with a fiber optic linear array
trations of CR (up to 250 mg L
1) and the total volume of 10.0 mL was detector spectrophotometer at the maximum absorption wave-
adjusted with triply distilled water. Afterwards, a binary solution length (lmax ¼ 501.0 nm). The extraction efficiencies (E) were calcu-
containing various amounts of IL (extraction solvent, varied in the lated by using Eq. (1):
range of 50–400 mg) and 500 mL of acetone (disperser solvent) was

Ci -Cf
rapidly injected into each sample using a syringe, thereupon, a E¼  100 (1)
Ci
cloudy solution was obtained. The cationic dye was extracted into
fine droplets of IL. The mixture was then centrifuged for 4 min at where Ci and Cf represent initial and final concentrations of the dye
4000 rpm to decrease the sedimentation time. As a result, the fine in the aqueous phase, respectively.
droplets of IL settled at the bottom of the centrifuge tube. In this methodology, some important parameters that would
The remaining concentration of CR dye in the aqueous phase was affect the extraction performance, such as kind and amount of
determined by a fiber optic spectrograph (Avantes; model: 2048) IL, pH, type, and volume of the disperser solvent as well as salt
using a 50-mL quartz cylindrical microcell at 501.0 nm. (Pure CR concentration were investigated and optimized.
solutions in different concentrations were initially calibrated in
terms of absorbance values, which were recorded at the wavelength
of lmax ¼ 501.0 nm.) 3.1 Selection of ionic liquid
Generally, selected IL has to be more immiscible in the sample
2.4 Recovery of Ionic liquid based on reverse solution to reduce consumption of the extraction solvent and so
to meet the process economically; moreover, it must extract analytes
dispersive extraction
of interest efficiently.
When using IL as a rather valuable extractant for the DLLE process, In this work, some ILs containing an imidazolium cation like
recovery, regeneration, and reuse of the IL is of great importance to [Hmim][PF6], [Hmim][BF4], [Emim][Tf2N], [Bmim][Tf2N], as well as

Figure 2. The schematic view of IL-DLLE experimental setup.

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Clean – Soil, Air, Water 2012, 40 (3), 290–297 A Novel Method for Dye Removal 293

[Hmim][Tf2N] were examined for choosing the proportionate extrac-

tant. To assess the difference between extraction capabilities of
these ILs, a series of extraction experiments was performed by using
500-mL binary injection solutions containing 400 mg of each IL and
acetone (as the dispersant), while the concentration of CR and initial
volume of the aqueous phase were 300 mg L
1 and 3.0 mL, respec-
tively. Moreover, pH was adjusted to 6.0.
Partition coefficient (PIL/W) of the CR between ILs and the aqueous
phases was calculated by using Eq. (2) and applied for evaluation of
used ILs.
" #
b a
Ci Vaq
Cf Vaq
VIL Figure 3. Effect of pH on the efficiency of DLLE for CR removal. Utilized
CIL conditions: initial CR concentration 40 mg L
1, [Hmim][Tf2N] 70 mg,
PIL=W ¼ ¼ (2)
Cw Cf acetone (the disperser solvent) 500 mL, and volume of aqueous
solution ¼ 10.0 mL.
As mentioned, Ci and Cf represent initial and final concentrations
b a
of the dye in the aqueous phase, respectively. While Vaq and Vaq are
volumes of the aqueous phase before and after extraction, respec- SO3Na) can be dissociated and converted to anionic form. As pH
tively, and VIL represents the volume of the IL phase. In most cases, it decreases, its azo group (—N — — N—) becomes protonated and the
b a molecule exists in a zwitterionic form as presented in Fig. 1(b).
can be seen that Vaq and Vaq had approximately the same value,
maybe due to low-water solubility of used ILs under aforesaid con- The effect of pH on the removal of CR was investigated in the range
b a of 4.5–8.0 (by adding hydrochloric acid or sodium hydroxide
ditions. With this assumption (Vaq ¼ Vaq ), partition coefficient can be
calculated by using the simpler Eq. (3). solutions), while initial CR concentration, volume of aqueous

 solution, and IL amount were 40 mg L
1 (about 6.0  10
6 mol L
1),
Ci -Cf Vaq 10.0 mL and 70 mg, respectively. The results shown in Fig. 3 reveal
PIL=W ¼ (3)
Cf VIL that the extraction efficiency was initially increased by raising pH up
to 5.0 and after this, pH remained approximately constant. Indeed,
Results indicate that with the increase of length of alkyl substitu- the maximum removal of CR was observed in the range of pH > pKa
ent on the cation of ILs containing same anion, partition coefficients (about 4.9), which indicates that in this range of pH, the anionic
of CR in the ILs/aqueous systems increase and follow the trend given species of CR prefers the ILs phase. In fact, desirable hydrogen-
below: bonding could be formed between
SO
—
3 or/and —N — N— of the
anionic species and the acidic 2H of imidazolium cation of the ILs
P½Emim½Tf 2 N =W < P½Bmim½Tf 2 N =W < P½Hmim½Tf 2 N =W
compared with the zwitterionic species of CR that prevail in the
range of pH < pKa. Thus, pH 5.0 seems to be a proper choice for
Considering the fact that the growth of alkyl chain length on the
subsequent CR removal experiments. On the other hand, the extrac-
cation increases the hydrophobicity of the ILs, trend mentioned
tion of CR into IL is negligible at low pH, especially in the case of
above indicates that the partition coefficients of CR increased with
strong acidic solutions. For this reason, these media seem to be
increase of hydrophobicity of the ILs.
suitable for the stripping and regeneration of IL phase.
Also results indicate that between three ILs containing the same
cation ([Hmim][PF6], [Hmim][BF4], and [Hmim][Tf2N]), the partition
coefficient of CR in [Hmim][Tf2N]/aqueous system is greater than that
3.3 Effect of IL amount
in two other ILs/aqueous systems. Moreover, the below trend is
followed by these partition coefficients: For successful IL-DLLE of dye, it is idealistic to have a minimum
consumption of IL, as well as a maximum extraction yield in the dye
P½Hmim½BF6  =W < P½Hmim½BF4  =W < P½Hmim½½Tf 2 N =W removal. Figure 4 shows the effect of the amount of [Hmim][Tf2N] on
the extraction of CR in different initial concentration for 10.0 mL
This trend signifies that anion of these ILs played an important role
aqueous solutions. It has been observed that for dye concentrations
in the extraction of CR. The difference in the partition coefficients of
higher than 20 mg L
1, extraction of the dye increases when the
CR observed in three mentioned ILs/aqueous systems can be ascribed
amount of the IL increases from 80 to 400 mg. From this Fig. 4 it
to the difference in the hydrogen-bonding strength between CR and
may be concluded that, for quantitative extraction (>95%) of CR at
the anions of these ILs. As previously reported, the strength of hydro-
initial concentrations in the range of 40–250 mg L
1, optimum
gen bonding between –OH group and anions increased in the order
required amounts of IL are varied from about 90 to 400 mg/10 mL
[PF6]
< [BF4]
< [(CF3SO2)2N]
[48]. In accordance with all these results,
and the average extraction capacity of CR into this IL was obtained in
[Hmim][Tf2N] IL was selected as the extractant in this work.
the value of about 6.0 mg/g.

3.2 Effect of pH of the aqueous phase

3.4 The choice of disperser solvent: Type and
It was found that pH of aqueous solution significantly influences the
volume
extraction efficiency; especially for pH sensitive dyes because pH of
the aqueous phase affects the degree of ionization of a dye molecule. Miscibility is the main criterion for the selection of disperser solvent.
For instance, in the aqueous solution, the sulfonate groups of CR (D– Generally, dispersant must be miscible with both extractant and

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294 M. Gharehbaghi and F. Shemirani Clean – Soil, Air, Water 2012, 40 (3), 290–297

Figure 4. Effect of amount of [Hmim][Tf2N] on

the efficiency of DLLE at different CR concen-
trations. Utilized conditions: initial CR concen-
trations: 20–250 mg L
1, pH 5.0, acetone (the
disperser solvent) 500 mL, and volume of aque-
ous solution ¼ 10.0 mL.

3.5 Effect of salt concentration

Dyes and salts are often present together in a textile dye bath
effluent stream. The existence of salts at various concentrations
may directly affect the extraction efficiency and removal of dyes.
To investigate the effect of salt concentration on CR extraction, as
well as robustness of the method against salty solutions, NaNO3 was
chosen in concentration of up to 25% w/v. As a result of salting out
effect and due to the reduction of the degree of hydration of CR in
solutions containing NaNO3, the extraction efficiency slightly
increased to 0.25% w/v salt and then stayed approximately constant,
as shown in Fig. 6. In order to increase the extraction efficiency of CR,
a 0.25% w/v concentration of NaNO3 was selected for further
experiments.
Figure 5. Effect of volume of acetone (the disperser solvent) on the extrac-
tion efficiency of CR at low- and high-level of concentrations. Utilized
conditions: pH 5.0, volume of aqueous solution ¼ 10.0 mL, low-level series:
initial CR concentration 40 mg L
1, [Hmim][Tf2N] 100 mg, and high-level
series: initial CR concentration 200 mg L
1, [Hmim][Tf2N] 400 mg.

aqueous solution. Moreover, the viscosity of the binary solvent is

directly influenced by type of disperser solvent. As a result, it can
regulate droplet production of the extractant and control the effi-
ciency of extraction. For investigation of this effect, two different
solvent (ethanol and acetone) were tested. A series of CR sample
solutions at the concentration of 40 mg L
1 were studied using
500 mL of each disperser solvent with 100 mg of the IL (extraction
solvent). No statistically significant differences between these dis-
persers were shown by their obtained enrichment factors; never-
theless, in this work acetone was selected as the disperser solvent
due to its better ability to dissolve ILs.
The effect of the volume of acetone on the extraction recovery was
also studied. Different volumes of this dispersant in the range of
200–800 mL with the addition of 100 mg [Hmim][Tf2N] were examined
for extraction of CR at the initial concentration of 40 mg L
1 and
similar volumes with the addition of 400 mg [Hmim][Tf2N] were
examined for extraction of CR at the initial concentration of
200 mg L
1 from 10.0 mL aqueous samples. As illustrated in Fig. 5,
for the low-level CR concentration series (40 mg L
1), the extraction
efficiency increased up to 300 mL of acetone and then stayed approxi-
mately constant. Moreover, for the high-level CR concentration
series (200 mg L
1), the extraction efficiency increased up to
450 mL of the dispersant, afterwards it stayed approximately con-
Figure 6. Effect of salt concentration on the efficiency of DLLE. Utilized
stant. Therefore, 500 mL was selected as the proper volume of the conditions: initial CR concentration 40 mg L
1, pH 5.0, [Hmim][Tf2N] 85 mg,
dispersant for both low- and high-level concentrations. acetone 500 mL volume of aqueous solution ¼ 10.0 mL.

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Clean – Soil, Air, Water 2012, 40 (3), 290–297 A Novel Method for Dye Removal 295

This work
3.6 Effect of stripping solutions

Ref.

[51]
[50]

[52]
As discussed previously, pH plays a special role in dye extraction.
According to this fact that partition coefficient of a dye in the
IL/aqueous system extremely depends on pH of the medium, in order

solutions (1.0 mol L
1 of HCl or HNO3)

(1.0 mol L
1), 1-pentanol or isopropyl
to release CR from the IL and for the extractant regeneration, one

Addition of aqueous HCl solution

extraction with acidic stripping

Reverse dispersive liquid–liquid
reverse dispersive back extraction procedure was applied by using

Washing with iso-propyl

alcohol with 0.1 mol L
1
Regenerating method

alcohol/water (1:1 v/v)

acidic stripping solutions. For this reason, two series of 0.5 mL
solutions of HCl and HNO3 at various concentrations (up to
5.0 mol L
1) were tested for regeneration of 200 mg of the settled
IL phase containing CR dye. Results indicate that both types of acidic

–
solution (HCl or HNO3) have the same trends without any significant
differences in the stripping of CR from the extractant, meanwhile,
IL recovery efficiency increased up to 1.0 mol L
1 for both acids
and then stayed approximately constant by increasing the acid
concentration.

3.7 Extraction of CR from real textile effluent

Extraction
sample

(min)
time

>35

<7
60

30
Experiments with a real effluent sample from CR dye bath (used for
cotton dyeing) were performed to evaluate the reliability and appli-
cability of the proposed IL-DLLE method. CR is the first coloring

conc. (mg L
1)

Initial dye

Up to 250
matter of ‘‘direct dyes’’ class (i.e., without the aid of mordants)

0.166
1000

100
and main ingredients present in its dye baths and effluents, apart
from dye, are Glauber’s salt (Na2SO4  10 H2O) and sodium carbonate
Table 1. Characteristic performance data obtained by using IL-DLLE and other IL-based methods for dye removal

[49]. In spite of the presence of these components in the effluent

sample, complete extraction (97  2%) of dye was achieved with fresh

(50–400 mg)
[Hmim][Tf2N] IL at one-step IL-DLLE.
volume

38–300
IL used

1000

1000
(mL)

500
3.8 Comparison of IL-DLLE with some other
methods
volume
Sample

(mL)

5.0

1.0
10.0

10.0
A comparison of the represented IL-DLLE method with other
reported IL-based extraction and removal methods is given in
Tab. 1. In comparison with others, IL-DLLE has a low-IL consumption,
Extraction
efficiency

95–100
85–99

great robustness against rather high content of dye/salt, and short

92.87
60.21
81.59
100
(%)

69

50

25

extraction procedure (<7 min), whereas, in other methods, the IL

consumption and the procedure time are usually higher than those
for the presented method. Moreover, unlike some CPE methods, no
aqueous

3.5–7.5
phase

heating process is needed for two-phase formation [26, 27]. In

pH of

1–12
1–8
6.0

3.0

5.0

addition, removal of the bulk aqueous phase and separation of

two phases are easier due to high viscosity of ILs. All these results
indicate that IL-DLLE is a novel and rather low-cost technique and has
Weak Acid Brilliant Blue

the properties of rapidity, simplicity, as well as efficiency, which can

Acid Yellow RN
Methyl Orange

Reactive Black
Eosin Yellows

be applied for extraction or removal of dyes like CR from waste

Congo Red
Orange G

Blue dye

Red dye

streams and effluents.

Dye

4 Conclusions
In this study, a IL-DLLE was developed and adapted for the separation
and removal of CR (as a model dyeing pollutant and commercial azo
[Hmim][Tf2N]

dyes) from aqueous samples even with rather high content of salt.
(extractant)

[HMIM][BF4]
[HMIM][PF6]

[OMIM][PF6]
[BMIM][PF6]

[BMIM][PF6]

[P14][Tf2N]

The hydrophobic nature of the used IL [Hmim][Tf2N] provides a

IL

perfect extractant for solutes (like CR) that are ionizable but, none-
theless, hydrophobic in nature. Under optimum conditions (pH 5.0
and a 0.25% w/v of salt concentration) and by applying about 90–
400 mg/10 mL of IL with the proper amount of dispersant, quanti-
Method

DLLE

tative extraction (>95%) of CR could be achieved at initial concen-

LLE

LLE

LLE

trations in the range of 40–250 mg L
1 of this dye.

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296 M. Gharehbaghi and F. Shemirani Clean – Soil, Air, Water 2012, 40 (3), 290–297

The simplicity in regeneration of the IL and the dye recovery may [15] K. Selvam, K. Swaminathan, K. S. Chae, Decolourization of Azo Dyes
and a Dye Industry Effluent by a White Rot Fungus Thelephora sp.,
make this IL-DLLE suitable for practical application for some types of
Bioresour. Technol. 2003, 88 (2), 115.
biphasic industrial separations. On the other hand, this method is
[16] E. Forgacs, T. Cserhati, G. Oros, Removal of Synthetic Dyes from
capable of applying for dye determinations and analytical purposes. Wastewaters: A Review, Environ. Int. 2004, 30 (7), 953.
This simple method is fast, safe, as well as robust against a rather [17] I. M. Banat, P. Nigam, D. Singh, R. Marchant, Microbial Decolorization
high content of salt and water-miscible organic solvents. Unlike CPE, of Textile-Dye-Containing Effluents: A Review, Bioresour. Technol. 1996,
by reason of high viscosity of ILs, removal of whole aqueous phase is 58 (3), 217.
easier. IL-DLLE provides a high recovery and low toxicity because only [18] P. C. Vandevivere, R. Bianchi, W. Verstraete, Treatment and Reuse of
small amounts of a ‘‘rather green extraction solvent’’ (IL) is used. The Wastewater from the Textile Wet-Processing Industry: Review of
Emerging Technologies, J. Chem. Technol. Biotechnol. 1998, 72 (4), 289.
operation of IL-DLLE in continuous mode as well as studies about
[19] E. Razo-Flores, M. Luijten, B. Donlon, G. Lettinga, J. Field,
other types of dyes and different ILs, are underway by our group. Biodegradation of Selected Azo Dyes under Methanogenic
Conditions, Water Sci. Technol. 1997, 36 (6–7), 65.
Acknowledgments [20] D. Georgiou, C. Metallinou, A. Aivasidis, E. Voudrias, K. Gimouhopoulos,
Decolorization of Azo-Reactive Dyes and Cotton-Textile Wastewater
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