Bioresource Technology 90 (2003) 193–198

Studies on adsorption of dyes on beta-cyclodextrin polymer

Gregorio Crini *

Centre de Spectrom
etrie, Universit
e de Franche-Comt
e, CR 3103 16 Route de Gray, 25000 Besancßon, France
Received 11 September 2002; received in revised form 7 February 2003; accepted 24 March 2003

Abstract
Beta-cyclodextrin (b-CD) polymers are used for the removal of various dyes from aqueous solutions. Three insoluble polymers
with different degrees of b-CD were used. Results of adsorption experiments showed that these polymers exhibited high sorption
capacities toward dyes. The mechanism of adsorption was both physical adsorption and hydrogen bonding due to the polymer and
the formation of an inclusion complex due to the b-CD molecules through host–guest interactions.
Ó 2003 Elsevier Ltd. All rights reserved.

Keywords: Cyclodextrin; Dyes; Adsorption; Sorbents; Polymers

1. Introduction electrochemical techniques, ozonation, coagulation,

precipitation, adsorption, fungal decolorization, etc., are
Dyes have been the subject of much interests in recent used for the removal of dyes from an effluent. Amongst
years because of increasingly stringent restrictions on these numerous techniques of dye removal, adsorption is
the organic content of industrial effluents. Recent and a procedure of choice for the removal of organic com-
continuing interest in these molecules is evident from the pounds from wastewater, and so, a useful tool for
number of papers that appear each year in the literature protecting the environment (Dabrowski, 2001). In par-
(see for examples: Crini and Morcellet, 2002; Delval ticular, adsorption is an effective process for the removal
et al., 2002; Namasivayam and Kavitha, 2002; Robin- of colors from waste effluents. Currently, the most
son et al., 2002a,b,c; Fu and Viraraghavan, 2001; Juang common procedure involves the use of activated carbons
et al., 2001; Chern and Wu, 2001). as adsorbents because of their excellent adsorption
Many industries (plastics, paper, textile and cosmet- ability (Namasivayam and Kavitha, 2002; Juang et al.,
ics) use dyes in order to color their products. These 2001; Chern and Wu, 2001; Choy et al., 1999; Walker
molecules are common water pollutants and they may and Weatherley, 1997). However, their use is limited to
be frequently found in trace quantities in industrial its high costs (Fu and Viraraghavan, 2001). For this
wastewater. Their presence in water, even at very low reason, several workers have attempted to use low cost
concentrations, is highly visible and undesirable. In materials, such as waste orange peel (Namasivayam
addition, many dyes are difficult to degrade due to their et al., 1996), peat (Dusart et al., 1991; Ho and McKay,
complex aromatic structure and thus tend to persist in 1998), corncob and barley husk (Robinson et al.,
the environment, creating serious water quality and 2002b), apple pomace and wheat straw (Robinson et al.,
public health problems. Therefore, it would be advan- 2002c), starch-enriched flour (Delval et al., 2002), clay
tageous to develop technologies to eliminate them. material (Bagane and Guiza, 2000).
Methods of dye wastewater treatment have been re- In our group, experiments are being conducted to
viewed by Robinson et al. (2001), Fu and Viraraghavan evaluate the possibility of the use of polysaccharides, in
(2001), Slokar and Majcen Le Marechal (1998) and particular starch and starch derivatives, as sorbents in
Banat et al. (1996). Physical, chemical and biological wastewater treatment (Crini and Morcellet, 2002; Delval
methods, such as flocculation, membrane-filtration, et al., 2002). In recent publications (Crini and Morcellet,
2002; Crini et al., 1998a,b, 1999, 2002; Janus et al.,
1999), we proposed the use of polymers containing beta-
*
Tel.: +33-3-81-66-65-64; fax: +33-3-81-66-61-72. cyclodextrin as new sorbents to sorb benzene deriva-
E-mail address: gregorio.crini@univ-fcomte.fr (G. Crini). tives. Beta-cyclodextrin (cyclomaltoheptaose or b-CD)

0960-8524/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0960-8524(03)00111-1
194 G. Crini / Bioresource Technology 90 (2003) 193–198

which is a natural molecule derived from starch is a Table 1

torus-shaped cyclic oligosaccharide with an internal Characteristics of polymers
hydrophobic cavity (Szejtli, 1998). It is well known that Polymer Amount of b-CDa
this structure gives rise to a remarkable capacity to form Starch 0
inclusion complexes with organic molecules, through Polymer 1 150
Polymer 2 200
host–guest interactions (Shieh and Hedges, 1996; Li and
Polymer 3 420
Purdy, 1992). a
From spectrophotometric method, in mg per g of polymer.
In order to extend the sorption properties of these
polymers, we propose, in this paper, the use of the same
polymers for the sorption of dyes. The adsorption The method used for the determination of the amount of
properties, in terms of adsorption capacity, are de- b-CD immobilized onto the beads has been the deter-
scribed. The influence of several parameters (kinetics, mination of reducing sugars with tetrazolium blue, as
contact time, concentration, NaCl amount, b-CD con- described earlier (Crini et al., 1998a,b).
tent, and pH) on the adsorption capacity of these
polymers is evaluated and discussed. 2.2. Adsorption method

The sorption capacity was investigated using C.I.

2. Methods Acid Blue 25 (AB 25), C.I. Reactive Blue 19 (RB 19),
C.I. Disperse Blue 3 (DB 3), C.I. Basic Blue 3 (BB 3) and
2.1. Procedure for the beta-cyclodextrin polymer C.I. Direct Red 81 (DR 81) as model guest solutes.
These dyes were commercial products and used without
The polymers have been prepared in one step by re- purification (see Fig. 1 for the structural formulae).
ticulation of b-CD or starch using epichlorohydrin as The results were determined by the following method:
crosslinking agent to obtain insoluble cyclodextrins 20 mg of polymer was mixed with 4 ml of a NaCl 0.1
polymers. The synthetic procedure has already been mol l
1 aqueous solution of dye at a known concentra-
described in detail (Crini et al., 1998b). Three polymers tion in a tightly closed flask. The solution was then
used in the study have different b-CD content, respec- stirred on a rotating shaker at room temperature. The
tively 150 mg (Polymer 1), 200 mg (Polymer 2) and 420 residual concentration of the dye solute was determined
mg (Polymer 3) of b-CD per gram of sorbent (Table 1). by spectrophotometry. The experiments were performed

O NH2
SO3Na N
Cl-
Et
N O N+ Et
O NH Et Et

C.I. Acid Blue 25 (AB 25) C.I. Basic Blue 3 (BB 3)

O NH2 O NHCH3
SO3Na

O NH SO3CH2CH2SO3Na O NHCH2CH2OH

C.I. Reactive Blue 19 (RB 19) C.I. Disperse Blue 3 (DB 3)

NaSO3 N N N N SO3Na

HO

O
C.I. Direct Red 81 (DR 81)
NH C

Fig. 1. Chemical structure of dyes.

 G. Crini / Bioresource Technology 90 (2003) 193–198 195

in triplicate. The sorbent was removed by centrifugation apart from the interactions of the dye with the polymer
or filtration before measurements. Absorbance values network (physical adsorption, hydrogen bonding), the
were recorded at kmax for each solution: at 605 nm for b-CD molecules played a major role.
AB 25, 592 nm for RB 19, 629 nm for DB 3, 654 nm for The difference in the chemical structure between these
BB 3 and 512 nm for DR 81. The adsorption capacity five dyes can also explain the obtained values. BB 3
was then calculated and expressed in percentage uptake (R ¼ 8%) did not interact with Polymer 3: the capacity
(R in %) which represents the ratio between the amount was very low due to poor physical adsorption interac-
of adsorbed dye and the starting amount of dye tion, poor hydrogen bonding and probably no inclusion
(McKay, 1982; El-Geundi, 1991). complex with b-CD. BB 3 is a basic dye containing
cationic functions that are not efficient for the dye-
polymer interaction. This result was in agreement with
literature data published by Delval et al. (2002). Using
3. Results
these results, it was assumed that the formation of an
inclusion complex due to the b-CD molecules and the
3.1. Adsorption of dyes on cyclodextrin polymer
presence of other interactions (hydrogen bonding and
physical surface adsorption), were involved in the
Fig. 2 shows the sorption capacity of five dyes on two
mechanism of sorption.
polymers, Polymer 3 and starch, respectively with and
without b-CD. Starch polymer without b-CD exhibited
lower sorption capacities. In this case, the adsorption is 3.2. Kinetics of dye adsorption on cyclodextrin polymer
based only on the presence of physical adsorption in the
polymer network and hydrogen bonding between the Fig. 3 shows the adsorption capacity of Polymer 3
hydroxyalkyl groups of the polymer and the dye. For versus the contact time (stirring time) toward four dyes.
Polymer 3, which contained b-CD molecules, an in- The kinetics of sorption were fast: the maximum ca-
crease of the sorption capacity was observed. This pacity was obtained after 1 h. The capacity increased
showed that b-CD molecules contributed to the sorption with contact time and this confirmed strong interactions
mechanism through inclusion complex formation. This between the dye, the b-CD molecules and the polymer
polymer showed adsorption of AB 25 (R ¼ 100%), RB network. Using Polymers 1 and 2, we found similar
19 (R ¼ 89%), DB 3 (R ¼ 80%) and DR 81 (R ¼ 62%). trends for the curves: 2 h was found to be sufficient for
In particular, for AB 25, we noted that Polymer 3 ex- reaching the plateau.
hibited very high sorption capacity: all the dye present in Table 2 shows the adsorption capacity of Polymer 3
the solution was adsorbed. This result confirmed that versus starting concentration of dye solution using a
the presence of b-CD molecules in the polymer strongly contact time of 2 h. The quantity of polymer was kept
increased the sorption values. constant while the molar concentration of the dye was
This conclusion was particularly demonstrated in the varied between 1  10
5 and 9  10
5 M. The order of
case of DB 3 where we found R ¼ 18% using starch and sorption for the five dyes was always the same: AB
R ¼ 83% using Polymer 3. This clearly showed that, 25 > RB 19 > DB 3 > DR 81  BB 3; the order was

AB 25
Starch RB 19
Polymer 3 DR 81
100 DB 3

90 100

80 90
Adsorption capacity

Adsorption capacity

70 80

60 70

50 60

40 50

30
40

20
30

10
20

10
0
AB 25 DR 81 RB 19 DB 3 BB 3 0
0 20 40 60 80 100 120 140 160 180 200
Fig. 2. Comparison between adsorption capacity (R in %) of five dyes Contact time
on Polymer 3 and starch. Polymer 3 contains beta-cyclodextrin mole-
cules while starch does not (dye concentration 3  10
5 mol l
1 ; contact Fig. 3. Kinetics of adsorption capacity (R in %) of four dyes by a beta-
time 2 h). cyclodextrin polymer (Polymer 3; concentration 3  10
5 mol l
1 ).
196 G. Crini / Bioresource Technology 90 (2003) 193–198

Table 2 3.4. Influence of the pH on the adsorption capacity

Influence of the dye concentration on adsorption capacity (R in %) by
Polymer 3 (contact time 2 h)
To evaluate the influence of the pH on the sorption of
Concentrationa AB 25 DR 81 RB 19 DB 3 BB 3 the dye, tests were carried out in buffer solutions at pH
9  10
5 98 52 82 72 10 5, 6, 7, 8 and 9 in addition to water (Fig. 5). The values
6  10
5 99 55 87 78 7
of the adsorption capacity for AB 25 and DR 81 de-
3  10
5 100 62 89 80 8
1  10
5 100 60 92 88 12 creased with the pH but no evident correlation can be
a found. This decrease can be explained by the different
in mol l
1 .
ionization degree of the dye at the various pH used. In
addition, it is well known that the inclusion complex
with b-CD and aromatic derivatives depend on pH. It is
independent of the starting concentration. The quantity likely that the capacities depend on ionic strength more
of the retained solute depended on the concentration of than pH of the solution. Probably, NaCl minimizes
the aqueous solution. Among these dyes, BB 3, which is electrical charge on the surface of the polymer and in-
more basic, presented the lowest interaction with the b- creases the adsorption. This point needs a more detailed
CD polymer for all concentrations used. For AB 25, the investigation using other dyes.
results showed that the adsorbed quantity was practi-
cally identical (R near 100%) in this concentration range.
3.5. Effect of particle size on dye removal
If the adsorption capacity was expressed in lmol ad-
sorbed per gram of polymer, the capacity increased with
The influence of varying the polymer particle size
concentration: this confirmed strong interactions be-
range (in mm) was investigated with AB 25 and DR 81.
tween the solute and the b-CD molecules.
The results showed an increase in the adsorption ca-
pacity as the mean diameter of the polymer decreased,
probably due to the increase in surface area as suggested
3.3. Influence of the NaCl concentration on the adsorption
by McKay (1982) and Robinson et al. (2002c) (Fig. 6).
capacity

Fig. 4 shows the influence of the amount of NaCl on 3.6. Influence of the b-CD content on the adsorption
the adsorption capacity of cyclodextrin polymer toward capacity
DR 81, DB 3 and RB 19 dyes. The molar concentration
of NaCl was varied between 0 and 0.1 mol l
1 . Addition Tests were carried out using three polymers contain-
of sodium chloride to aqueous solutions produced an ing different amount of b-CD. Fig. 7 shows the influence
increase of the performance of the b-CD polymer. In the of the amount of b-CD on the adsorption capacity of
case of DR 81, we found R ¼ 62% for the distilled water polymers in water toward the five dyes. As expected, the
solution and R ¼ 84% for the same solution containing overall trend was an increase in the adsorption capacity
NaCl 0.1 mol l
1 . The capacities depended on ionic with increasing amounts of b-CD, corresponding to
strength of the solution. Similar results have been pub- increasing interactions between b-CD and the dyes. This
lished by Shao et al. (1996). clearly showed that the inclusion phenomena played a

DR 81
DB 3
RB 19

100
AB 25
90 DR 81

100
Adsorption capacity

80
90
70
Adsorption capacity

80
60
70
50 60

40 50

40
30
30
20
20
10
10
0 0
0 0.01 0.03 0.05 0.08 0.1 5 6 7 8 9 distilled water
NaCl concentration pH

Fig. 4. NaCl (in mol l
1 ) effect on the adsorption capacity (R in %) Fig. 5. pH effect on the adsorption capacity (R in %) (Polymer 3;
(Polymer 3; contact time 2 h; concentration 3  10
5 mol l
1 ). contact time 2 h; concentration 1  10
5 mol l
1 ).
 G. Crini / Bioresource Technology 90 (2003) 193–198 197

stability of the polymers and reproducibility of the val-

ues.

4. Conclusions

Results of adsorption showed that b-CD polymers

derived from starch exhibited good adsorption proper-
ties towards dyes. These polymers were found to be ef-
fective adsorbents. The proposed adsorption mechanism
involved several kinds of interactions: physical adsorp-
tion in the polymer network, hydrogen bonding and
formation of an inclusion complex due to the b-CD
molecules through host–guest interactions. The b-CD
molecules played the most important role in the mech-
anism.
Fig. 6. Effect of particle size on the adsorption capacity (R in %)
(Polymer 3; contact time 2 h; concentration 3  10
5 mol l
1 ).
References

Bagane, M., Guiza, S., 2000. Removal of a dye from textile effluents by
adsorption. Ann. Chim. Sci. Mater. 25, 615–626.
Banat, I.M., Nigam, P., Singh, D., Marchant, R., 1996. Microbial
decolorization of textile-dye containing effluents: a review. Biore-
sour. Technol. 58, 217–227.
Chern, J.M., Wu, C.Y., 2001. Desorption of dye from activated carbon
beds: effects of temperature, pH, and alcohol. Water Res. 35, 4159–
4165.
Choy, K.K.H., McKay, G., Porter, J.F., 1999. Sorption of acid dyes
from effluents using activated carbon. Res. Conserv. Recycl. 27,
57–71.
Crini, G., Morcellet, M., 2002. Synthesis and applications of adsor-
bents containing cyclodextrins. J. Sep. Sci. 25, 1–25.
Crini, G., Morin, N., Rouland, J.C., Janus, L., Morcellet, Bertini, S.,
2002. Adsorption de beta-naphtol sur des gels de cyclodextrine-
carboxymethylcellulose reticules. Eur. Polym. J. 38, 1095–
1103.
Crini, G., Janus, L., Morcellet, M., Torri, G., Morin, N., 1999.
Sorption properties toward substituted phenolic derivatives in
Fig. 7. Influence of the beta-cyclodextrin content on the adsorption
water using macroporous polyamines beta-cyclodextrins polymers.
capacity (R in %) of five dyes (contact time 2 h; concentration 3  10
5
J. Appl. Polym. Sci. 73, 2903–2910.
mol l
1 ).
Crini, G., Bertini, S., Torri, G., Naggi, A., Sforzini, D., Vechhi, C.,
Janus, L., Lekchiri, Y., Morcellet, M., 1998a. Sorption of aromatic
compounds in water using insoluble cyclodextrin polymers. J.
major role in the adsorption mechanism. This was es- Appl. Polym. Sci. 68, 1973–1978.
pecially clear for RB 19 and DB 3. Crini, G., Cosentino, C., Bertini, S., Naggi, A., Torri, G., Vechhi, C.,
Janus, L., Morcellet, M., 1998b. Solid state NMR study of
molecular motions in cyclomaltoheptaoses (beta-cyclodextrins)
crosslinked with epichlorohydrin. Carbohyd. Res. 308, 37–45.
Dabrowski, A., 2001. Adsorption, from theory to practice. Adv.
3.7. Reproducibility of the adsorption capacity Colloid Int. Sci. 93, 135–224.
Delval, F., Crini, G., Morin, N., Vebrel, J., Bertini, S., Torri, G., 2002.
The long term stability and reproducibility of the The sorption of several types of dye on crosslinked polysaccharides
derivatives. Dyes Pigments 53, 79–92.
sorption properties is of utmost importance. Since the Dusart, O., Marmier-Dussoubs, D., Serpaud, B., 1991. Elimination de
interaction between the dye and the polymer were driven colorants industriels sur tourbe, celluloses greffees, sciure et
mainly by inclusion complexes, organic solvents could charbons de bois. Tribune de lÕEau., 55415–55422.
be good candidates for the regeneration of the adsor- El-Geundi, M.S., 1991. Colour removal from textile effluents by
adsorption techniques. Water Res. 25, 271–273.
bents. After saturation, the polymers were easily re-
Fu, Y., Viraraghavan, T., 2001. Fungal decolorization of dye
generated using ethanol as washing solvent by soxhlet wastewaters: a review. Bioresour. Technol. 79, 251–262.
extraction. The sorption capacity value remained un- Ho, Y.S., McKay, G., 1998. Sorption of dye from aqueous solution by
changed after this treatment. This showed the chemical peat. Chem. Eng. J. 70, 115–124.
198 G. Crini / Bioresource Technology 90 (2003) 193–198

Janus, L., Crini, G., El-Rezzi, V., Morcellet, M., Cambiaghi, A., Torri, Robinson, T., Chandran, B., Nigam, P., 2002b. Removal of dyes from
G., Naggi, A., Vecchi, C., 1999. New sorbents containing beta- an artificial textile dye effluent by two agricultural waste residues,
cyclodextrin. Synthesis, characterization and sorption properties. corncob and barley husk. Environ. Int. 28, 29–33.
React. Funct. Polym. 42, 173–180. Robinson, T., Chandran, B., Nigam, P., 2002c. Removal of dyes from
Juang, R.S., Tseng, R.L., Wu, F.C., 2001. Role of microporosity of a synthetic textile dye effluent by biosorption on apple pomace and
activated carbons on their adsorption abilities for phenols and wheat straw. Water Res. 36, 2824–2830.
dyes. Adsorption 7, 65–72. Robinson, T., McMullan, G., Marchant, R., Nigam, P., 2001.
Li, S., Purdy, W.C., 1992. Cyclodextrins and their applications in Remediation of dyes in textile effluent: a critical review on current
analytical chemistry. Chem. Rev. 92, 1457–1470. treatment technologies with a proposed alternative. Bioresour.
McKay, G., 1982. Adsorption of dyestuffs from aqueous solutions Technol. 77, 247–255.
with activated carbon I: Equilibrium and batch contact-time Shao, Y., Martel, B., Morcellet, M., Weltrowski, M., Crini, G., 1996.
studies. J. Chem. Tech. Biotechnol. 32, 759–772. Sorption of textile dyes on beta-cyclodextrin–epichlorhydrin gels. J.
Namasivayam, C., Kavitha, D., 2002. Removal of congo red from Inclus. Phenom. Mol. Recogn. Chem. 25, 209–212.
water by adsorption onto activated carbon prepared from coir pith, Shieh, W.J., Hedges, A.R., 1996. Properties and applications of
an agricultural solid waste. Dyes Pigments 54, 47–58. cyclodextrins. J.M.S. Pure Appl. Chem. A 33, 673–683.
Namasivayam, C., Muniasamy, N., Gayatri, K., Rani, M., Rangana- Slokar, Y.M., Majcen Le Marechal, A., 1998. Methods of decoloration
than, K., 1996. Removal of dyes from aqueous solutions by of textile wastewaters. Dyes Pigments 37, 335–356.
cellulosic waste orange peel. Bioresour. Technol. 57, 37–43. Szejtli, J., 1998. Introduction and general overview of cyclodextrin
Robinson, T., Chandran, B., Nigam, P., 2002a. Studies on desorption chemistry. Chem. Rev. 98, 1743–1753.
of individual textile dyes and a synthetic dye effluent from dye- Walker, G.M., Weatherley, L.R., 1997. Adsorption of acid dyes on to
adsorbed agricultural residues using solvents. Bioresour. Technol. granular activated carbon in fixed beds. Water Res. 31, 2093–
84, 299–301. 2101.