Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 82:196–204 (2007)

Study on the extraction of dyes into

a room-temperature ionic liquid and their
mechanisms
Changping Li,1 Baoping Xin,2∗ Wenguo Xu1∗ and Qi Zhang2
1 School of Science, Beijing Institute of Technology, Beijing 100081, China
2 School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, China

Abstract: The investigation of liquid–liquid extraction of dyes is carried out by using ionic liquid – 1-butyl-
3-methylimidazolium hexafluorophosphate ([BMIM][PF6 ]) – as extraction phase. The effects of its process
parameters are studied in detail, such as extraction phase ratio, pH of the aqueous phase, and concentration
of dicyclohexyl-18-crown-6 (DCH-18C6) in the organic phase. Important results are obtained as follows: acid dyes
can be extracted with [BMIM][PF6 ] quantitatively; the removal of reactive dyes is low; however, it can be greatly
increased by the addition of DCH-18C6. The pH value has a great impact on the removal of the acid dye and the
reactive dye. However, it does not influence the extraction of the weak acid dye. It is found that the extraction
process of acid dyes adopts the form of anion exchange and the soluble part of the ionic liquid plays an important
role as counter-ions.
 2007 Society of Chemical Industry

Keywords: room-temperature ionic liquids; extraction; dye wastewater; mechanisms

INTRODUCTION (VOCs). The costs of solvents and disposal of spent

Dye wastewaters stem mainly from dyeing, carpet extractants diluents are so high, estimated to be of the
manufacturing, textile and papermaking industries. order of billions of dollars each year.14
They constitute one of the most problematic wastew- In recent years, room-temperature ionic liquids
aters to be treated not only for their high chemical (RTILs) have attracted much attention in different
oxygen demands and suspended solids but also for areas of chemistry due to their novel chemical and
content of toxic compounds, which may be toxic to physical properties such as non-volatility, thermal
some aquatic life owing to the presence of aromatics, stability, wide liquid range, non-flammability, and
metals, chlorides etc.1 – 6 Many methods are used to wide electrochemical window.15,16 RTILs have shown
treat dye wastewaters, such as flocculation, chemical significant promise as media for organic synthesis,17,18
oxidation, air flotation processes, adsorption by resin biphasic catalysis,19 and separations.20 – 22 RTILs can
or activated carbon, electrolysis, and anaerobic and be used as solvent media for a wide range of industrially
aerobic two-stage biological process.7 – 11 Conventional important chemical processes to replace traditional
engineering techniques, however, have been found to solvents as they have no detectable vapor pressure
be inadequate and not cost effective in removing dyes and are relatively thermostable.14 At the same time, a
from water. subset of ionic liquids retains important properties of
Liquid–liquid extraction has often been a good certain conventional, molecular organic solvents, such
choice for the process engineer in the development of as immiscibility with water. Studies have demonstrated
separation processes.12 One of biggest problems, how- that the mechanisms of numerous synthetic reactions
ever, for traditional solvent extraction is employing are the same in molecular solvents and in RTILs,23,24
organic solvents, which evaporate into the atmo- but this is not universally true.25
sphere with detrimental effects on the environment Application of RTILs in separation and their
and human health.13 The development trend of envi- mechanisms have been extensively investigated in
ronmental protection puts much emphasis on the several research groups during the past few years.26 – 35
adoption of clean manufacturing processes and envi- Rogers and coworkers have done some pioneer
ronmentally benign technologies, which make solvent work using RTILs in the extraction of metal ions.
extraction processes anachronistic because of their They28 incorporated thiourea, thioether, and urea
use of toxic, flammable, volatile organic compounds into derivatized imidazolium cations and used these

∗
Correspondence to: Baoping Xin, School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, China
E-mail: [email protected]
Wenguo Xu, School of Science, Beijing Institute of Technology, Beijing 100081, China
E-mail: [email protected]
Contract/grant sponsor: National Natural Science Foundation of China; contract/grant number: 20307002
(Received 1 August 2006; revised version received 31 October 2006; accepted 8 November 2006)
Published online 12 January 2007; DOI: 10.1002/jctb.1656

 2007 Society of Chemical Industry. J Chem Technol Biotechnol 0268–2575/2007/$30.00

 Extraction of dyes into a room-temperature ionic liquid

functionized RTILs as the extractant in liquid–liquid Green GS, Acid Brilliant Red B) were commercial
extraction of Hg2+ and Cd2+ . They found that low products (Tianjin Chemical & Dyes Company, Tian-
distribution ratios were obtained with less expensive jin, China). The structures of typical dyes studied
RTILs such as [BMIM][PF6 ] as extractant for in this paper are shown in Fig. 1 (Acid Yellow RN
Hg2+ and Cd2+ ; the distribution ratios were highly (b), Weak Acid Brilliant Blue RAW(c), Reactive Black
improved when functionized RTILs were mixed with KN-G2RC (d), Reactive Yellow M-5R (e)). Except
[BMIM][PF6 ]. Therefore, functionized RTILs played for dicyclohexyl-18-crown-6 (a mixture of stereoiso-
the roles of extractant and hydrophobic phase. Dai mers), all were of chemical purity grade (Fig. 1f).
et al.29 demonstrated that highly efficient extraction Other chemicals were analytical-grade products and
of strontium ions from water (Dsr > 104) can be used without further purification. Water was freshly
achieved when DCH-18C6 was combined with deionized and distilled before use. The pH value of
various water-immiscible 3-methylimidazolium-based aqueous solutions was adjusted by H2 SO4 or NaOH
RTILs. Jensen et al.34 reported the mechanisms of and measured using a laboratory digital pH meter
metal ion transfer into RTILs. Unlike conventional PHS-3C (Leici, Shanghai, China). The concentration
organic solvents, cation transfer into an RTIL of dyes in the aqueous phase was measured by UV-
in the presence of a neutral complexing agent visible spectrophotometer DR/4000U (Hach, Love-
may not require anion coextraction. If the ion land, CO, USA; 4 cm quartz cells). The description
transfer properties of ionic liquid-based systems of the new complexes was indicated through the 1 H
cannot be predicted from the established behavior NMR spectrum obtained by Varian Mercury 400 MHz
1
of conventional organic solvents, the rational design of H NMR (Varian Inc., Palo Alto, CA, USA).
RTIL-based separation processes will only be possible
when the mechanisms of ion transfer and the solvation Extraction procedure
state of ions dissolved in ionic liquids are understood The extraction process was performed at room
at a fundamental level. temperature (25 ± 2 ◦ C) as follows: 10 mL aliquots
With this in mind, we report the removal of a set of dye solution with a known concentration (100 mg
of dyes from an aqueous phase and their mecha- L−1 ) were placed in stoppered vessels and were
nisms. The ionic liquid 1-butyl-3-methylimidazolium contacted with 1 mL of [BMIM][PF6 ]. The vessels
hexafluorophosphate is selected as a typical example were placed in a mechanical vortex for 60 min.
of an RTIL, forming a biphasic liquid system with After equilibrium was established, the phases were
water. The distributions between the ionic liquid and separated. In the above-mentioned procedure, the pH
the aqueous phases with different dyes will be studied of the dye solution was adjusted with NaOH and
in detail. Importantly, quantitative acid dyes can be H2 SO4 . The concentration of dyes in the aqueous
extracted into RTIL proceeding through the pathway phase after extraction was determined at their peak
of anion exchange. However, the ultimate recovery of absorbance wavelengths (Acid Yellow RN 434 nm,
the acid Yellow RN from the RTIL phase and regen- Weak Acid Brilliant Blue RAW 626 nm, Reactive
erating the ionic liquid as part of a separation cycle Black KN-G2RC 600 nm, Reactive Yellow M-5R
would eventually become difficult because the struc- 400 nm, Reactive Golden Yellow KN-G 398 nm,
ture of the acid Yellow RN and ionic liquid would Reactive Reddish Violet X-2R 560 nm, Reactive
have been destroyed. For reactive dyes, removal effi- Brilliant Red X-3B 538 nm, Reactive Blue BE-
ciency is very low, but the addition of DCH-18C6 2GF 600 nm, Reactive Brilliant Blue X-BR 606 nm,
will eventually enhance the recovery efficiency pro- Reactive Red BE-3BF 526 nm, Reactive Red M-8B
ceeding through the pathway of the hydrogen bonding 542 nm, Reactive Brilliant Orange X-GN 478 nm,
mechanism. Reactive Yellow BE-4RF 420 nm, Weak Acid Green
GS 640 nm, Acid Brilliant Red B 524 nm) by a
spectrophotometric method.
As for the extraction of dyes with octanol, the above
EXPERIMENTAL
procedure was also adopted.
Reagents and apparatus
In the experiments concerning the effect of DCH-
1-Butyl-3-methylimidazolium hexafluorophosphate
18C6, a concentration of 0.03 × 10−3 –268.46 ×
was synthesized as described in other literature.20 Its
10−3 mol L−1 dicyclohexyl-18-crown-6 (DCH-18C6
purity was checked by elemental analysis to be greater
in [BMIM][PF6 ]) was used.
than 95%. Its structure is shown in Fig. 1(a). All
All the experiments in this study were done
investigated dyes (Acid Yellow RN (C.I. Acid Yellow
in duplicate to determine reproducibility, and the
25), Weak Acid Brilliant Blue RAW (C.I. Acid Blue
experimental errors were within 3%.
80), Reactive Black KN-G2RC (C.I. Reactive Black 5
Removal efficiency (R, %) and experimental
mix), Reactive Yellow M-5R (C.I. Reactive Yellow),
distribution coefficient (D) values of dyes between
Reactive Golden Yellow KN-G, Reactive Reddish
ionic liquid and aqueous phases were calculated using
Violet X-2R, Reactive Brilliant Red X-3B, Reactive
the following equations:
Blue BE-2GF, Reactive Brilliant Blue X-BR, Reactive
Red BE-3BF, Reactive Red M-8B, Reactive Brilliant Caq,o − Caq
R= × 100 (1)
Orange X-GN, Reactive Yellow BE-4RF, Weak Acid Caq,o

J Chem Technol Biotechnol 82:196–204 (2007) 197

DOI: 10.1002/jctb
C Li et al.

H3C

NH
N N CH3
S
O
H3C O
N
N N CH3 HO N
F +

F F
-
P
F
F
F O S O
-
(a) PF6 BMIM+ (b) O Na
- +

O O
Na+O- -
O Na
+

S S
O O

H3C CH3 N N
O HN
NH NH
O
O HN S O
- + O
O Na S
CH3 O
S
O
O
O
H3C O O
-
O Na
+ O S O
+
O Na
-
O HN S O S O
+
O- Na
O

(c) H3C CH3 (d)

O O- Na+
- +
O O S O Na O S O
O OH
S +
-
O S O Na O
OH
NH O O
N N

N N O S O
O O
+
NH O- Na O
Cl N NH O CH3

(e) (f)

Figure 1. The structure of the ionic liquid and the typical dyes in this study: (a) ionic liquid; (b) Acid Yellow RN; (c) Weak Acid Brilliant Blue RAW;
(d) Reactive Black KN-G2RC; (e) Reactive Yellow M-5R; (f) dicyclohexyl-18-crown-6.

(Caq,o − Caq ) × Vaq Effect of phase ratio (Vaq /Vo )

D=
Caq × Vo Generally, the removal efficiency of dyes decreases
with the increase of phase ratio (Vaq /Vo ). However, the
Vaq R R
= × =K× (2) optimum extraction phase ratio must be determined
Vo 100 − R 100 − R from the results of experiments. As shown in Fig. 2, the
where Caq,o and Caq are the concentration of dyes removal efficiency of dyes after extraction decreases
in the aqueous phase before and after extraction; with the increase of phase ratio Vaq /Vo . When the
and Vaq and Vo are the aqueous and organic phase phase ratio Vaq /Vo increases to 10, the removal
volumes, respectively. Denote K = Vaq /Vo , where efficiency and distribution coefficients (D) of Acid
Vaq /Vo (extraction phase ratio) is the volume ratio Yellow RN, Weak Acid Brilliant Blue RAW and
of aqueous and organic phases. Reactive Black KN-G2RC are 92.87% and 130.25,
60.21% and 15.13, 31.48% and 4.59, respectively. To
achieve the balance of highest distribution coefficient,
RESULTS AND DISCUSSION best extraction efficiency of dyes and smallest amount
There are many exaction parameters that influence used of ionic liquids, the optimal phase ratio was
the extraction process, such as extraction phase ratio selected as 10. The experiments show that under this
and the pH of the aqueous phase. As preliminary phase ratio Vaq /Vo , the removal efficiency, distribution
experiments show that all the equilibria of extraction coefficient and extractant efficiency were relatively
processes can be achieved within 60 min, 60 min of optimal. As a result, a phase ratio Vaq /Vo = 10 : 1
equilibration was used in all experiments. was adopted in all experiments.

198 J Chem Technol Biotechnol 82:196–204 (2007)

DOI: 10.1002/jctb
 Extraction of dyes into a room-temperature ionic liquid

100

80

60

R(%)
40

20

0
0 5 10 15 20 25 30 35
Vaq/Vo
Acid Yellow RN
Weak Acid Brilliant Blue RAW
Reactive Black KN–

Figure 2. Effect of extraction phase ratio on removal efficiency of dyes.

Octan-1-ol-water distribution coefficients (P)

Acid Brilliant Red B

10 Acid Yellow RN
Weak Acid Green GS
Weak Acid Brilliant Blue RAW
Reactive Black KN-G2RC
Reactive Golden Yellow KN-G
Reactive Yellow BE-4RF
Reactive Brilliant Orange X-GN
Reactive Red M-8B
Reactive Red BE-3BF
1 Reactive Brilliant Blue X-BR
Reactive Yellow M-5R
Reactive Blue BE-2GF
Reactive Brilliant Red X-3B
Reactive Reddish Violet X-2R

0.1 1 10 100
Distribution ratios (D) in [BMIM][PF6]–water system

Figure 3. Comparison of partitioning coefficient between [BMIM][PF6 ] – water and octanol–water biphasic systems.

Distribution coefficients of dyes than acid dyes. This shows the weaker hydrophobic
To evaluate the potential application of RTILs in property of acid dyes than of reactive dyes.
the area of liquid–liquid extraction of dyes, the
distribution coefficients of ionic liquids and classical
octanol–water system (a frequently used empirical Effect of pH
hydrophobicity scale) were compared. The partition of dyes dissolved in neutral solution has
The relationship of distribution ratio between the been studied; however, the effect of pH on the partition
two systems is shown in Fig. 3. The difference between should also be researched to probe the influence of
the two systems is due to the different solvation ionization. The relationship of pH value and the
properties of the different solvent systems.36,37 For partitioning of dyes (Acid Yellow RN, Weak Acid
the acid dyes (Acid Yellow RN, Acid Brilliant Brilliant Blue RAW, and Reactive Black KN-G2RC)
Red B, Weak Acid Brilliant Blue RAW, Weak is illustrated in Fig. 4. The partition coefficient of
Acid Green GS), the distribution coefficients in the Acid Yellow RN is higher in acidic or near-neutral
[BMIM][PF6 ]–water system were higher than those conditions than in basic solution. That of weak Acid
in the octanol–water system. For the reactive dyes, Brilliant Blue RAW is not influenced by the adjustment
in most cases, their distribution coefficients in the of pH. That of reactive Black KN-G2RC rises to its
ionic liquid system were also higher than that in the summit around pH 6.
octanol–water system. These results imply that the The effect of pH on the partition coefficient can
ionic liquid is a better extracting phase than octanol, be explained in terms of their ionization states.38
and ionic liquid has the potential to be used in the At low pH value, Acid Yellow RN is in a neutral
treatment of dye wastewater. zwitterionic state, which makes the dye have the trend
In Fig. 3 it is also shown that for this solute species of being partitioned into the RTIL phase. As the pH
reactive dyes have much lower partition coefficients is increased, this dye is much easier to dissolve in the

J Chem Technol Biotechnol 82:196–204 (2007) 199

DOI: 10.1002/jctb
C Li et al.

100

80

60

R / (%)
40

20

0
0 2 4 6 8 10 12 14
pH
Acid Yellow RN
Weak Acid Brilliant Blue RAW
Reactive Black KN-G2RC

Figure 4. Effect of pH of the aqueous phase on removal efficiency of dyes.

aqueous phase. When the pH increases above 10, it is As for the mechanism of the extraction process,
then partitioned quantitatively into the aqueous phase. further proof of the formation of new complexes can
As Weak Acid Brilliant Blue RAW has an electro- be seen from the results of 1 H NMR (Fig. 5(a) and
symmetrical structure, it should be noted that the (b)). Acid Yellow RN proceeds through the pathway
charge transfer in the Weak Acid Brilliant Blue RAW of anion exchange, which can be seen from the
moiety does not change its anionic character in the comparison of the 1 H NMR (CD3 OD, δ ppm): 7.520
presence of the acid or alkali. Therefore its removal (S, H), 7.460 (S, H), 4.663 (S, H), 4.173 (t, 2H),
efficiency is not influenced by the adjustment of 3.891 (S, 3H), 1.855 (m, 2H), 1.356 (m, 2H), 0.952
pH value. Reactive Black KN-G2RC is in a neutral (t, 3H), and 1 H NMR (CD3 OD, δ ppm): 8.715 (S,
zwitterionic state in the neutral solutes, which prefers 2H), 7.514 (S, 2H), 4.752 (S, H), 4.182 (t, 4H), 3.868
the RTIL phase. However, under acidic or basic (S, 6H), 1.858 (m, 4H), 1.364 (m, 4H), 0.963 (t, 6H).
conditions, the charge distribution of the Reactive The exchange of Acid Yellow RN anion (AY− ) for the
Black KN-G2RC molecule is changed. It has more RTIL’s PF6 − anion implies that the [BMIM][AY]
tendency to dissolve in the aqueous phase. complex is more than a solute in the ionic liquid. By
displacing anions from the RTIL phase, the anionic
Extraction mechanism of Acid Yellow RN (AY) [AY− ] complex becomes part of the ionic liquid. The
The organic phase is in the electroneutral state. ultimate recovery of Acid Yellow RN from the RTIL
The transfer of the extracted cation or anion is phase and regeneration of ionic liquid as part of a
accompanied by an equal number of counter-ions separation cycle will eventually become impossible
(Ani− or Cat+ )38,39 as shown in the following: because the structures of the Acid Yellow RN and the
ionic liquid have been destroyed.
Another proof of anion exchange can be obtained
Aniaq − + DYEaq − = Aniorg − + DYEorg − (3)
from the experimental study of the influence of
+ + + +
Cataq + DYEaq = Catorg + DYEorg (4) system temperature (Table 1). Removal efficiency
increases with increase of system temperature, which
As no other counter-ion (Ani− or Cat+ ) is introduced, demonstrates that the removal of dyes by ionic liquids
it is expected that the removal efficiency should be is an endothermic process. This is characteristic of
very low. However, the removal efficiency of some an ion-exchange reaction, which proves again that the
dyes is rather high. It is suggested that the ions extraction of dyes using ionic liquid agrees with the
from RTIL ([BMIM]+ or [PF6 ]− which come from mechanism of anion exchange.
[BMIM][PF6 ] due to its partial solubility in water, From the above-mentioned, the conclusion can be
0.13% v/v) act as counter-ions. The presence of Cl− drawn that the extraction of dyes proceeds through
has no influence on the removal efficiency of dyes at a the following pathway of anion exchange:
given dye concentration. If counter-ions are necessary
AYaq − + PF6org − = AYorg − + PF6aq − (5)
for the extraction, an increase in its concentration
in the aqueous phase will lead to an increase in the Table 1. Effect of temperature on Acid Yellow RN extraction process
removal efficiency of dyes. However, the addition of
a Cl− dose not result in an increase of extraction Temperature (◦ C) 5 25 35 50
efficiency. This proves our suggestion that the RTIL’s
R (%) 83.2 92.87 98.47 98.98
own ions act as counter-ions.

200 J Chem Technol Biotechnol 82:196–204 (2007)

DOI: 10.1002/jctb
 Extraction of dyes into a room-temperature ionic liquid

Figure 5. 1 H NMR spectra of ionic liquid and new complex after extraction: (a) [BMIM][PF6 ]; (b) ionic liquid–Acid Yellow RN complex.

J Chem Technol Biotechnol 82:196–204 (2007) 201

DOI: 10.1002/jctb
C Li et al.

When dyes are transferred into the organic phase, an agent and plays an important role in the extraction of
equal amount of the RTIL’s anion is transferred to the reactive dyes. The proposed reason is that hydrogen
aqueous phase. bonds are formed between the sulfone ethyl reactive
Notably, this ion-exchange mechanism has also group (SO2 C2 H4 –) of the reactive dyes and polyether
been proposed by other groups27 – 31 in the exaction as in non-polar media.34,40 The equilibrium of this
of amino acid extraction, phenolic compounds and extraction is described by the following equations
strontium cations. However, this is the first time that (assuming electroneutrality):
the mechanism has been proposed to apply in the
extraction of dyes by ionic liquid. DYEaq − + DCH-18C6 + BMIM+
Recently, Vijayaraghavan et al.35 successfully extr- = DYEaq − . DCH-18C6. BMIMorg + (6)
acted acid blue dye and acid red dye into a neutral ionic
liquid, recovered two kinds of commercial dyes, and DYEaq − + DCH-18C6 + PF6org −
reused the ionic liquids. However, it is not universally = DYEorg − . DCH-18C6 + PF6aq − (7)
true for all the dyes. As part of the separation cycle, the
recovery of ionic liquids is very important, but from Equation (6) corresponds to ion-pair extraction with
the above extraction mechanisms the recovery of ionic dialkylimidazolium (BMIM+ ) as the counter-ion for
liquids after extraction is very difficult. Thus the use the reactive dye anion. Equation (7) corresponds to
of ionic liquids as extractants should be more careful an anion-exchange reaction in which the reactive dye
in future studies; the rational design of the new task- anions are transferred into the organic phase and the
specific ionic liquids based on the above mechanism hexafluorophosphate (PF6 − , RTIL component) into
can be of great importance during the use of ionic the aqueous phase.
liquids to replace traditional solvents, especially for The dependence of extraction of reactive dyes on
large-scale applications. DCH-18-crown-6 concentration is shown in Fig. 6.
The slope of the linear part of the curve (log
The role of dicyclohexyl-18-crown-6 D = f (log CDCH18C6 )) for Reactive Black KN-G2RC
The relationship of removal efficiency of reactive is twice as that of Reactive Yellow M-5R. This means
dyes (Reactive Black KN-G2RC and Reactive Yellow that twice the amount of Reactive Black KN-G2RC as
M-5R) and concentration of DCH-18-crown-6 in that of Reactive Yellow M-5R (Fig. 1d) is transferred
the organic phase is shown in Table 2. Their into DCH-18-crown-6 under the same conditions.
removal efficiencies increase with the increase in This agrees with the bonding mechanism of the
the concentration of DCH-18-crown-6. Removal reactive dyes to DCH-18-crown-6.26 The sulfone ethyl
efficiency of reactive dyes by ionic liquid is about reactive group (SO2 C2 H4 –) of each Reactive Black
5.4–31.5% in the absence of DCH-18-crown-6. KN-G2RC molecule (as shown in Fig. 1d) in DCH-
However, their removal efficiencies increase with the 18-crown-6 is 2 and that of Reactive Yellow M-5R
increase of DCH-18-crown-6 concentration, which is 1 (Fig. 1e). This higher number for the sulfone
shows that DCH-18-crown-6 acts as a complexing ethyl reactive group (SO2 C2 H4 –) of Reactive Black
KN-G2RC allows its higher bonding tendency to the
Table 2. Effect of concentration of DCH-18-crown-6 on removal DCH-18-crown-6 molecule than to Reactive Yellow
efficiency of dyes M-5R.
Conc. of R of dyes
Dye ABS DCH-18C6 after
(nm) (×10−3 mol L−1 ) (%) extraction CONCLUSIONS
A liquid–liquid extraction process using ionic liquid as
Reactive Yellow 400 0 5.45
extraction phase has been employed for the extraction
M-5R
0.03 58.56
of dyes from water solution. This ionic liquid,
0.13 59.34 [BMIM][PF6 ], is shown to be able to extract dyes
0.27 62.06 quantitatively. However, the anion-exchange process
1.34 62.65 is predominantly responsible for the extraction of
2.68 70.04 Acid Yellow RN. The difficulty in recovering the
26.85 74.12 dyes and regenerating ionic liquids may make this
268.46 82.68 RTIL unsuitable for practical application for some
Reactive Black 600 0 31.48 types of biphasic separation. The increase of DCH-
KN-G2RC 18-crown-6 concentration in aqueous phases results in
0.03 43.36 enhancement of the removal efficiency of the reactive
0.13 44.00 dyes. Similar to conventional non-polar media, the
0.27 45.82 formation of hydrogen bonds between the reactive
1.34 57.64 dyes and polyether allows the increase of removal
2.68 68.18
efficiency, which demonstrates that the use of DCH-
26.85 70.36
268.46 81.59
18-crown-6 is effective in improving the extraction of
reactive dyes. The experimental results give promise of

202 J Chem Technol Biotechnol 82:196–204 (2007)

DOI: 10.1002/jctb
 Extraction of dyes into a room-temperature ionic liquid

100

log(D)
10

Reactive Yellow M5R

Reactive Black KN-G2RC

1
0.01 0.1 1 10 100
log(CDCH-18C6)

Figure 6. Dependence on DCH-18-crown-6 concentration of extraction of reactive dyes into [BMIM][PF6 ] (log D = f(log CDCH18C6 )).

this novel separation route for the extraction of some 9 Malik PK and Saha SK, Oxidation of direct dyes with hydrogen
water-soluble dyes and have significant implications peroxide using ferrous ion as catalyst. Sep Purif Technol
31:241–250 (2003).
for the application of RTILs in separation processes. 10 Yasui H, NaKamura K, Sakuma S, Iwasaki M and Sakai Y, A
Taking into account the extraction ability of ionic full-scale operation of a novel activated sludge process without
liquids and the recovery of dyes and regeneration excess sludge production. Wat Sci Technol 34:395–404
of ionic liquids after extraction, the rational design (1996).
of RTIL-based separation processes based on this 11 Vlyssides AG, Loizidou M, Karlis PK, Zorpas AA and
Papaioannou D, Electrochemical oxidation of a textile dye
mechanism is very important. Studies related to the wastewater using a Pt/Ti electrode. J Hazard Mater 70:41–52
design of the new ionic liquids suitable for separation (1999).
process are still ongoing in this laboratory. 12 Schweitzer PA, Handbook of Separations Techniques for Chemical
Engineers. McGraw-Hill, New York (1996).
13 Rydberg J, Musikas C and Choppin GR, Principles and Practices
of Solvent Extraction. Marcel Dekker, New York (1992).
ACKNOWLEDGEMENT 14 Seddon KR, Ionic liquids for clean technology. J Chem Technol
Biotechnol 68:351–356 (1997).
Financial support from the National Natural Science
15 Anthony JA, Maginn EJ and Brennecke JF, Solubilities and
Foundation of China (grant no. 20307002) is thermodynamic properties of gases in the ionic liquid 1-
acknowledged. n-butyl-3-methylimidazolium hexafluorophosphate. J Phys
Chem B 106:7315–7320 (2002).
16 Huddleston JG, Visser AE and Rogers RD, Characterization
and comparison of hydrophilic room temperature ionic liquids
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