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Abstract
Application of chitinous products in wastewater treatment has received considerable attention in recent years in the
literature. In particular, the development of chitosan-based materials as useful adsorbent polymeric matrices is an
expanding eld in the area of adsorption science. This review highlights some of the notable examples in the use of chitosan
and its grafted and crosslinked derivatives for dye removal from aqueous solutions. It summarizes the key advances and
results that have been obtained in their decolorizing application as biosorbents. The review provides a summary of recent
information obtained using batch studies and deals with the various adsorption mechanisms involved. The effects of
parameters such as the chitosan characteristics, the process variables, the chemistry of the dye and the solution conditions
used in batch studies on the biosorption capacity and kinetics are presented and discussed. The review also summarizes and
attempts to compare the equilibrium and kinetic models, and the thermodynamic studies reported for biosorption onto
chitosan.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Chitosan; Biosorption; Dyes; Batch process; Modeling and thermochemistry of biosorption
Abbreviation: AB, acid blue; AB 1, acid black 1; AB 15, acid blue 15; AB 25, acid blue 25; AB 40, acid blue 40; AB 62, acid blue 62; AB
113, acid blue 113; AG 25, acid green 25; AG 27, acid green 27; AO 7, acid orange 7; AO 10, acid orange 10; AO 12, acid orange 12; AO
51, acid orange 51; AR, acid red; AR 1, acid red 1; AR 14, acid red 14; AR 18, acid red 18; AR 73, acid red 73; AR 27, acid red 27; AR 87,
acid red 87; AR 88, acid red 88; AR 138, acid red 138; AV 5, acid violet 5; AY 25, acid yellow 25; BB, basic blue; BB 1, basic brown 1; BB
3, basic blue 3; BB 9, basic blue 9; BR, brilliant red M5BR2; BY 45, basic yellow 45; CV, crystal violet; DB, direct blue; DB 14, direct blue
14; DB 71, direct blue 71; DO, direct orange; DR, direct red; DR 2, direct red 2; DR 81, direct red 81; DS, direct scarlet B; DY 4, direct
yellow 4; IC, indigo carmine; IR, iragalon rubine RL; MB, maxilon blue 4GL; MB 29, mordant blue 29; MB 33, mordant brown 33; MO,
methyl orange; MO 10, mordant orange 10; MY, metanil yellow; MY 30, mordant yellow 30; O II, orange II; Rb 5, reactive blue 5; RB,
reactive blue RN; RB 5, reactive black 5; RB 2, reactive blue 2; RB 15, reactive blue 15; RB 19, reactive blue 19; RB 222, reactive blue 222;
RO, reactive orange; RO 16, reactive orange 16; R 6G, rhodamine 6G; RR, reactive red; RR B, reactive red RB; RR 2, reactive red 2; RR
141, reactive red 141; RR 189, reactive red 189; RR 195, reactive red 195; RR 222, reactive red 222; RTB, reactive T-blue; RY, reactive
yellow GR; RY 2, reactive yellow 2; RY 86, reactive yellow 86; RY 145, reactive yellow 145.
Corresponding author. Tel.: +33 3 81 66 57 01; fax: +33 3 81 66 57 97.
E-mail address: gregorio.crini@univ-fcomte.fr (G. Crini).
0079-6700/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2007.11.001
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400
Contents
1.
2.
3.
4.
5.
6.
7.
8.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
General considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
2.1. Batch experiments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
2.2. Why to use chitosan as raw material? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
2.3. Considerations on dye adsorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
2.4. Why to use chitosan as a biosorbent for dye removal? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
2.5. Raw chitosan and chitosan-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
A brief review of the recent literature on the adsorption of dyes by chitosan . . . . . . . . . . . . . . . . . . . . . . . 412
Control of adsorption performances of chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
4.1. Inuence of the chitosan characteristics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
4.1.1. Chitosan origin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
4.1.2. Physical nature of the chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
4.1.3. Chemical structure of chitosan. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418
4.2. Activation conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
4.2.1. Chitosan preprotonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
4.2.2. Grafting reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
4.2.3. Inuence of crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
4.2.4. Chitosan-based composite beads . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
4.3. Inuence of process variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
4.3.1. Effect of chitosan dosage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
4.3.2. Effect of initial dye concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
4.3.3. Effect of contact time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
4.3.4. Effect of stirring rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
4.3.5. Effect of dryness. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
4.4. Chemistry of the dye . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
4.5. Effect of the solution conditions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
4.5.1. Effect of pH. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
4.5.2. Effect of pH variation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
4.5.3. pH sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
4.5.4. Effect of ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
4.5.5. Effect of competitive molecules and ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428
4.6. Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428
4.7. Desorption of dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
Adsorption mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
6.1. Equilibrium isotherm models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
6.2. Kinetic modeling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
6.3. Thermochemistry of biosorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
6.3.1. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
6.3.2. Thermodynamic parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 440
Economic aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
1. Introduction
Many industries, such as textile, paper, plastics
and dyestuffs, consume substantial volume of water,
and also use chemicals during manufacturing and
dyes to color their products. As a result, they
generate a considerable amount of polluted waste-
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Nomenclature
k2
aL
C
ki
Ce
Co
DG
DH
DS
Ea
KF
KL
k0
k1
qe
qt
qmax
m
nF
R
T
t
te
V
x
401
Coagulation/oculation
Precipitation/oculation
Electrocoagulation/
electrootation
Biodegradation
Adsorption on activated carbon
Established removal
methods
Emerging recovery
technologies
Advanced oxidation
Selective bioadsorption
Biomass
Oxidation
Electrochemical treatment
Membrane separation
Ion-exchange
Incineration
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402
2. General considerations
2.1. Batch experiments
The change in the concentration of a pollutant
(adsorbate) in the surface layer of the material
(adsorbent) in comparison with the bulk phase with
respect to unit surface area is termed adsorption.
The term biosorption is given to adsorption
processes, which use biomaterials as adsorbents
(or biosorbents). The assessment of a solid-liquid
adsorption system is usually based on two types of
investigations: batch adsorption tests and dynamic
continuous-ow adsorption studies. The present
review only presents data obtained using batch
studies. When studying adsorption from solutions
on materials it is convenient to differentiate between
adsorption from dilute solution and adsorption
from binary and multicomponent mixtures covering
the entire mole fraction scale. To judge by the
number of papers published annually on adsorption
from dilute solution, this subject is more important
than adsorption from binary mixtures. Therefore,
reference will be made hereafter to adsorption from
dilute aqueous solutions.
Batch studies use the fact that the adsorption
phenomenon at the solid/liquid interface leads to a
change in the concentration of the solution.
Adsorption isotherms are constructed by measuring
the concentration of adsorbate in the medium
before and after adsorption, at a xed temperature.
For this, in general, adsorption data including
equilibrium and kinetic studies are performed using
standard procedures consisting of mixing a xed
volume of dye solution with an known amount of
chitosan in controlled conditions of contact time,
agitation rate, temperature and pH. At predetermined times, the residual concentration of the dye is
determined by spectrophotometry at the maximum
absorption wavelength. Dye concentrations in solution can be estimated quantitatively using linear
regression equations obtained by plotting a calibration curve for each dye over a range of concentrations. The adsorption capacity (adsorption uptake
rate) is then calculated and is usually expressed in
milligrams of dye adsorbed per gram of the (dry)
adsorbent. For example, the amount of dye
adsorbed at equilibrium, qe, is calculated from
the mass balance equation given by Eq. (1). The
symbols used in the equation are dened in the
Nomenclature section. In general, the experiments are conducted in triplicate under identical
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403
qe
CH2OH
CH2OH
O
O
O
OH
OH
n
n
NHCOCH3
NH2
Chitin
Chitosan
CH2OH
NH2
O
O
OH
OH
O
O
DA
NHCOCH3
1-DA
CH2OH
glucosamine unit
Commercial Chitosan
Fig. 1. Chemical structure of chitin [poly(N-acetyl-b-D-glucosamine)], chitosan [poly(D-glucosamine)] and commercial chitosan (a copolymer
characterized by its average degree of acetylation (DA)).
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404
Shellfish wastes
demineralization
deproteinization
decoloration
hydrolysis
carb oxymethylation
Chitin
glucosamines
oligosaccharides
deacetylation
carb oxymethylchitin
Chitosan
derivatization
oligosaccharides
glucosamines
salts
chitosan derivatives
acetylation
N-acetyl-D-glucosamines
Fig. 2. Simplied representation of preparation of chitin, chitosan and their derivatives.
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Table 2
Intrinsic properties of chitosan
Physical and
chemical properties
Biological
properties
Biocompatibility
J
J
J
Non-toxic
Biodegradable
Adsorbable
Bioactivity
J
J
J
J
Bioadhesivity
405
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406
300
Number of articles
250
200
150
100
50
0
1998
1999
2000
2001
2002
2003
2004
2005
4%
7%
coagulation
3%
precipitation
flocculation
adsorption
53%
28%
flotation
filtration
membranes
1%
4%
Fig. 3. A Scopus database literature survey of the wastewater applications of chitosan and chitin: (a) research articles published from 1998
to 2005 (the survey did not include patents) and (b) main domains of chitosan and chitin in the removal of pollutants from solutions.
low cost,
readily available,
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Table 3
Applications of chitin and chitosan
Fields
Applications
Agriculture
Protection of plants
Increase of crop yields (reduces the growth
of phytopathogenic fungi)
Seed and fertilizer coating; soil treatment
Biomedical
engineering
Biotechnology
Chemical
industry
Cosmetics and
toiletries
Food industry
Pharmaceutics
Others
407
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408
NHCH3
NHCH3
Disperse Blue 14
N
NaO3SOCH2CH2O2S
SO3Na
HO
Reactive Black 5
H2N
N
NaO3SOCH2CH2O2S
SO3Na
(C2H5)2N
Cl+
N(C2H5)2
O
Basic Blue 3
NH2
N+
SO3Na
HO
-O
Basic Green 4
O
HN
Reactive Blue 19
SO2CH2CH2OSO3Na
N(CH3)2
to industrial applications [10,11,18,20]. The adsorption properties depend on the different sources of
chitin (the quality of commercial chitin available is
not uniform) and performance is also dependent on
the type of material used. Another important
criterion to be taken into account concerns the
variability and heterogeneity of the polymer (the
difculty of controlling the distribution of the acetyl
groups along the backbone makes it difcult to get
reproducible initial polymers). There is a need for a
better standardization of the production process to
be able to prepare reproducible initial polymers
having the same characteristics. Changes in the
specications of the polymer may signicantly
change adsorption performance. Another problem
with chitosan derivatives is their poor physicochemical characteristics, in particular low surface area
and porosity. In addition, although chitosan is
much easier to process than chitin or other low-cost
adsorbents, the stability of chitosan materials is
generally lower, owing to their more hydrophilic
character and, especially, pH sensitivity. Being a
biopolymer, chitosan is biodegradable and this may
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Table 4
Advantages and disadvantages of chitosan and chitosan-based
materials used as biosorbent for the removal of dyes from
aqueous solutions
Advantages
Low-cost hydrophilic
biopolymer
Very abundant material
and widely available in
many countries
Renewable resource
Cationic polysaccharide (in
acidic medium)
Environmentally friendly,
publicly acceptable
material
Extremely cost effective
Outstanding dye-binding
capacities of a wide range
of dyes
Fast kinetics
High selectivity in
decolorizing both very
dilute or concentrated
solutions
Versatile biosorbent
Disadvantages
409
for a wide range of dyes, although several contradictory observations have been reported. However,
a few review articles on the potential of chitosan for
dye removal have been published. The application
of the adsorption of pollutants including dyes onto
chitosan has been reviewed by Ravi Kumar [21] and
No and Meyers [22]. Various chitosan-based composites and membranes have been also developed
and proposed for adsorption and separation purposes [33,42]. To avoid repetition, in the following
chapters, only raw, grafted and crosslinked chitosans will be discussed. This review focuses on the
recent developments related to decolorizing applications of the chitosan-based materials and reports the
main advances published over the last 10 years. This
is an ambitious project since the very large number
of groups working around the world forces us to
make a selection from the most signicant results.
Table 5 lists some of the researchers whose results
are discussed in this review and the dyes they
investigated [58116].
2.5. Raw chitosan and chitosan-based materials
Practical use of chitosan has been mainly
conned to the unmodied forms. For a breakthrough in its utilization, chemical derivatization
onto polymer chains has been proposed to produce
new materials. Derivatization is a key point which
will introduce the desired properties to enlarge the
eld of its potential applications. Chitosan has three
types of reactive functional groups, an amino group
as well as both primary and secondary hydroxyl
groups at the C-2, C-3 and C-6 positions, respectively (Fig. 1). Its advantage over other polysaccharides is that its chemical structure allows specic
modications without too many difculties, especially, at the C-2 position [11]. These functional
groups allow direct substitution reactions and
chemical modications, yielding numerous useful
materials for different domains of application.
The most commonly used chemical activations are
carboxymethylation, acetylation and grafting. The
variety of groups which can be attached to
the polymer is almost unlimited. To control both
the physical, mechanical and chemical properties,
various techniques can be used, and often, the
methods are adapted from the cellulose world [11].
The chitosan derivatives can be classied into four
main classes of materials: modied polymers, crosslinked chitosans, chitosan-based composites and
membranes (Table 6).
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410
Table 5
Authors of recent research on dye removal by chitosan (selected papers)
Corresponding author
Country
Dye(s)
Reference(s)
Airoldi C.
Annadurai G.
Cestari AR.
Chen DH.
Chen L.
Chiou MS.
Brazil
Iran
Brazil
Taiwan
China
Taiwan
[58]
[59,60]
[6163]
[64]
[65]
[6670]
Cho SY.
Crini G.
de Favere VT.
Dutta PK.
El-Tahlawy KF.
Fahmy HM.
Guibal E.
Korea
France
Brazil
India
Egypt
Egypt
France
Guha AK.
Hebeish R
Juang RS.
Li HY.
Martel B.
Manolova N.
McKay G.
Miyata K.
Prado AGS.
Saha TK.
Shimizu Y.
Shyu SS.
Stevens WF.
Thiravetyan P.
Szeto YS.
Uzun I.
Wen YZ.
India
Egypt
Taiwan
Taiwan
France
Bulgaria
Hong Kong
Japan
Brazil
Bangladesh
Japan
Taiwan
Thailand
Thailand
Hong Kong
Turkey
China
BB 9
BB 9, DS
IC, RB, RN, RR, RY
AG 25, AO 12
AB, BB
AO 7, AO 12, AR 14, DR 81 MY, RB 2, RB 15, RR 2,
RR 189, RR 222, RY 2, RY 86
RB 5
BB 3, BB 9
RO 16
DB
BR, IR, MB
DR
AB 1, AB 113, AG 25, AV 5, AY 25, DB 14, DB 71,
DY 4, MB 29, MB 33, MO 10, RB 5
AR 87
AR, BY 45, DO, RO
AO 51, BB 9, RB 222, RR 222, RY 145, R 6G
RR 189
AB 15, AB 25, AB 62, DR 81, MY 30, RB 5, RB 19
RR
AG 25, AO 10, AO 12, AR 18, AR 73
AB 40, AR 18, AR 88, DR 2
IC
azo dye
AO 7, AR 1, AR 88, AR 138, BB 9, CV
BB 1, BB 3
BB 9, CV, MO, O II
RR 141
AG 27
CV, O II, Rb 5, RB 5, RY 2
RR 195
[71]
[72,73]
[74]
[75]
[76,77]
[78]
[7982]
[83]
[84,85]
[8693]
[94]
[95]
[96]
[9799]
[100]
[101]
[102]
[103105]
[106]
[107,108]
[109]
[110,111]
[112115]
[116]
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Table 6
The four main classes of chitosan derivatives
Table 7
Some methods for preparation of chitosan particles
I. Modied polymers
Carboxymethylchitosans
Alkylated chitosans
Chitosan sulfate derivatives
Carbohydrate-branched chitosans
Grafted chitosans
Ligand-bound chitosan
411
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412
chitosan aqueous
solution
oil phase
emulsification
crosslinking agent
stirring
hardening of
droplets
separation
particles
Fig. 5. Schematic representation of preparation of chitosan
particles by emulsion crosslinking.
Table 8
Results of batch studies for various dyes using chitosan
Dye
Effective pretreatment of
chitosan
Particle size
protonation
450900mm
355500 mm
Crab shell
Sspa
Protonation
Powder (crab)
Wet bead
Dried bead
Powder (crab)
Flake
Bead (crab)
Swollen bead
Flake
Bead (lobster)
20
25
4h
24 h
4 days
24 h
5 days
24 h
5 days
24 h
3 days
3 days
5 days
24 h
24 h
Crosslinking
355500 mm
Crosslinking
355500 mm
355500 mm
Protonation
Grafting
450900 mm
25
Grafting
25
10
0.99
Crosslinking
0.206
60100 mesh
Crosslinking
Crosslinking
Crosslinking
Crosslinking
Crosslinking
Crosslinking
Crosslinking
Crosslinking
Crosslinking
Crosslinking
Crosslinking
0.24
2 mm
2.8 mm
11.41 mm
0.715 mm
25 mm
850 mm1 mm
850 mm1 mm
850 mm1 mm
2.32.5 mm
2.32.5 mm
2.52.7 mm
3.53.8 mm
2.32.5 mm
350
3
4
4
6
9.6
3
3
9.5
5.5
6
3
8.47
6
4
2
3
3
6
4
11.8
12.3
2
3
11
11
11
3
3
3
3
6
25
30
25
30
25
30
30
30
25
25
30
20
25
30
30
25
60
25
26
30
47.5
35
30
30
25
30
30
30
30
25
30
60
40
20
30
30
30
30
30
4h
40 min
3 days
3 days
40 min
24 h
3h
5h
5 days
24 h
2h
5 days
60200 min
5 days
2 days
5 days
5 days
4 days
4 days
24 h
5 days
24 h
24 h
24 h
5 days
5 days
5 days
5 days
5 days
Equilibrium
model
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
qmb
296
645.1
525
2103.6
1940
922.9
1954
973.3
656
494
1940
693.2
728.2
76
50
166.5
222
202
121.9
Kinetic model
2383
37.18
Reference
Diffusionc
[65]
[9799]
[81]
[110]
[67]
[9799]
[67]
[9799]
[86]
[86]
[67]
[9799]
[9799]
[83]
[65]
[73]
[86]
[86]
[72]
[59]
[58]
[75]
[67]
[60]
[63]
[66]
[62]
[67]
[79]
[71]
[66]
[90]
[90]
[89]
[74]
[67]
[109]
[109]
[109]
[94]
[68]
[94]
[94]
[94]
Lagergren
Ho and McKay
Lagergren
Ho and McKay
Lagergren
Elovich
Elovich
Ho and McKay
Lagergren
Lagergren
Ho and McKay
Ho and McKay
Elovich
Elovich
Lagergren
Langmuir
Langmuir
Langmuir
Adsorption
mechanism
Chemisorption
Chemisorption
Chemisorption
Diffusionc
Chemisorption
Chemisorption
Chemisorption
Chemisorption
Diffusionc
Lagergren
Ho and McKay
Langmuir
1334
Langmuir
Langmuir
Freundlich
2498
1100
Langmuir
Langmuir
722
1009
199
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
30.4
2422
156
110
68
1936
1834
1686
1642
1189
Ho and McKay
Avrami
Ho and McKay
Diffusionc
Ho and McKay
Ho and McKay
Ho and McKay
Diffusionc
Chemisorption
Chemisorption
Diffusionc
Ho and McKay
Ho
Ho
Ho
Ho
Ho
and
and
and
and
and
McKay
McKay
McKay
McKay
McKay
Chemisorption
Diffusionc
Chemisorption
Chemisorption
Chemisorption
413
Bead (crab)
Shrimp shell
Shrimp shell
Shrimp shell
Bead
Bead
Bead
Bead
Bead
3.6
4
3
4
4
3
4
355500 mm
Grafting
Shrimp shell
Bead (crab)
Bead
Bead (crab)
Equilibrium
time
180 nm
Crosslinking
0.177
Bead (crab)
T (1C)
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Nanoparticle
Bead (crab)
Crab shell
Bead (crab)
Crab shell
Wet bead
Dried bead
Bead (crab)
Crab shell
Crab shell
Bead (shrimp)
pH
AB
AG 25
AG 25
AG 27
AO 7
AO 10
AO 12
AO 12
AO 51
AO 51
AR 14
AR 18
AR 73
AR 87
BB
BB 3
BB 9
BB 9
BB 9
BB 9
BB 9
DB
DR 81
DS
IC
MY
RB
RB 2
RB 5
RB 5
RB 15
RB 222
RB 222
RB 222
RO 16
RR 2
RR 141
RR 141
RR 141
RR 189
RR 189
RR 189
RR 189
RR 189
Chitosan
414
Table 8 (continued )
Dye
2
86
145
145
145
Bead
Bead
Swollen bead
Wet bead
Dried bead
Bead (crab)
Bead (shrimp)
Bead (lobster)
Flake (shrimp)
Flake (lobster)
Flake
Flake (crab)
Bead
Bead (lobster)
Bead
Bead (crab)
Bead (crab)
Swollen bead
Flake
Bead (lobster)
Crosslinking
Sspa
2.32.5 mm
pH
T (1C)
Equilibrium
time
Equilibrium
model
qmb
Kinetic model
Adsorption
mechanism
Reference
6
3
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
5
2
5
4
3
3
5
5
5
5
5
4
5
3
Langmuir
Langmuir
Freundlich
Langmuir
Freundlich
Freundlich
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Langmuir
Freundlich
950
2252
1965
1653
1498
1215
1106
1026
1037
494
398
339
293
Ho and McKay
Ho and McKay
Lagergren
Ho and McKay
Elovich
Elovich
Diffusionc
Chemisorption
Diffusionc
Chemisorption
Chemisorption
Chemisorption
Diffusionc
Diffusionc
Diffusionc
Diffusionc
Diffusionc
Chemisorption
Diffusionc
[68]
[69]
[87]
[90]
[86]
[86]
[91]
[91]
[91]
[91]
[91]
[90]
[91]
[88]
[89]
[62]
[67]
[67]
[90]
[90]
[89]
2.8 mm
3.11 mm
2.39 mm
2.93 mm
1630 mesh
1630 mesh
11.41 mm
1630 mesh
3040
3040
3040
46
46
11.8
46
0.715 mm
12.3
0.24
Crosslinking
4.01
Crosslinking
Crosslinking
Crosslinking
Particle size
2.8 mm
11.41 mm
0.715 mm
11.8
12.3
2
4
3
30
30
30
30
30
days
days
days
days
days
days
days
days
days
days
days
days
days
days
Ho and McKay
Diffusionc
60200 min
5 days
5 days
4 days
4 days
Langmuir
Langmuir
Langmuir
Langmuir
2436
1911
885
188
Avrami
Ho and
Ho and
Ho and
Ho and
McKay
McKay
McKay
McKay
Chemisorption
Chemisorption
Diffusionc
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189
222
222
222
222
222
222
222
222
222
222
222
222
222
222
Effective pretreatment of
chitosan
RR
RR
RR
RR
RR
RR
RR
RR
RR
RR
RR
RR
RR
RR
RR
RY
RY
RY
RY
RY
RY
Chitosan
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these effects increased dye adsorption [85]. However, Cestari et al. [62] recently noted that after the
crosslinking reaction, there is a small increase in the
crytallinity of chitosan beads with increased access
to the small pores of the material.
Among the other parameters that have a great
impact on dye adsorption is particle type. Chitosan
can be presented as gels, akes, powders and
particles. Chitosan beads are preferred since ake
and powder forms of polymer are not suitable for
use as adsorbents due to their low surface area and
lack of porosity, as indicated by Varma et al. [19].
Beads are usually prepared by dropping highviscosity chitosan salt solutions into a basic solution
with slow stirring. The diameters of the drops as
well as the solution ow rate control the diameter of
the beads. Wu et al. [91] reported that bead-type
chitosan gives a higher capacity for dye adsorption
than the ake type by a factor of 24 depending on
the source of shery waste. For example, a
comparison of the maximum adsorption capacity
(qmax) for RR 222 by chitosan akes and beads
prepared from a crab source showed 293 mg/g for
akes and 1103 mg/g for beads. The authors
explained this result by the fact that the beads
possessed a greater surface area (i.e., more loose
pore structure) than the akes. They also reported
that the adsorption capacity of chitosan depends on
its source. The qmax were determined to be 1106,
1037 and 1026 mg of dye per gram of bead-type of
chitosan for crab, lobster and shrimp, respectively
[91]. Again, it can be noted that the order of qmax for
the different sources is exactly identical to that of
the surface area of the whole animal, i.e., crab4
lobster4shrimp. Chang and Juang [86] also noted
that chitosan in the bead form signicantly improves the adsorption performance of RR 222, AO
51 and BB 9 compared to that in the ake form.
Guibal et al. [82] indicated that it would be
interesting to use chitosan gel beads instead of
akes since the production of gel beads decreases
the residual crystallinity of polymer which enhances
both the porosity and the diffusion properties of the
material, due to the expansion of the chitosan
network and the increase in the specic surface area.
Crini et al. [72] observed that compared to chitosan
akes, chitosan beads exhibited a twofold or more
increase in the adsorption capacity for BB 9. One of
chitosans most promising features is its excellent
ability to be processed into nanostructures. These
nanochitosans can also be used in batch studies, as
reported by Hu et al. [110]. They noted that an
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417
of the adsorbent particles. This means that intraparticle diffusion greatly inuences the accessibility
of dye molecules to internal sites. With raw
chitosan, the differences were more marked than
with protonated material [80]. Due to resistance to
intraparticle mass transfer in raw chitosan, it is
usually necessary to use very small particles to
improve adsorption kinetics. When the dyes have
strong interactions with chitosan, this allows larger
adsorbent particle sizes to be used to get the same
adsorption rate. They concluded that this was
especially interesting for large-scale applications
since it was easier to manage large adsorbent
particles rather than ne powders [82]. Juang et al.
[93] also observed that the adsorption capacity
strongly depended on the particle size of chitosan.
At a chitosan particle size of 250420 mm, the values
were 380, 179 and 87 mg/g for RR 222, RY 145 and
RB 222, respectively. These results were signicantly greater than those obtained using adsorbents
such as CAC, natural clay, bagasse pith and maize
cob, in which the capacity for reactive dyes was
often less than 30 mg/g. They concluded than the
smaller the chitosan particles, the greater the
capacity for dye. Li and co-worker [94] reported
similar conclusions for the adsorption of basic dyes
on the adsorption of RR 189 on crosslinked beads.
For example, the adsorption capacity of particles
with diameters 2.32.5, 2.52.7 and 3.53.8 were
1936, 1686 and 1642 mg/g, respectively, at pH 3 and
30 1C. They also concluded that the dye uptake
increased with a decrease in the particle size
since the effective surface area was higher for the
same mass of smaller particles. Chiou and Chuang
[66], using crosslinked chitosan for the removal of
dye from solutions, indicated that the increase in
adsorption capacity with decreasing particle size
suggests that the dye preferentially adsorbed on the
outer surface and did not fully penetrate the particle
due to steric hindrance of large dye molecules.
Recently, Trung et al. [108] reported that no effect
of the difference in particle size of decrystallized
chitosan on the decolorization capacity was observed. The size of particles has been shown to be a
key parameter in the control of adsorption performances of several dyes on chitosan, in particular
this may be the main parameter to control dye
adsorption equilibrium. However, the relationship
of adsorption capacity to particle size also principally depends on two criteria: (i) the chemical
structure of the dye molecule (its ionic charge) and
its chemistry (its ability to form hydrolyzed species)
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stronger mechanical resistance than the raw chitosan powder. The chemical, physical and mechanical behavior of the beads and also adsorption
properties were enhanced by crosslinking with
functional groups. The materials had a strong
adsorption capacity for RY, RB and RR below
pH 5.5. The authors also noted that crosslinking can
change the crystalline nature of chitosan, as
suggested by the XRD diffractograms. After the
crosslinking reaction, there was a small increase in
the crytallinity of the chitosan beads and also
increased accessability to the small pores of the
material.
4.2.4. Chitosan-based composite beads
Practical industrial applications of raw chitosan
in xed-bed systems or packed in adsorption
columns are also limited. The characteristics of the
polymers can introduce hydrodynamic limitations
and column fouling, which limits their use for largescale columns. For example, the aked or powdered
form swells (the crosslinked beads have lower
swelling percentage [120]) and crumbles easily, and
does not function ideally in packed-column congurations common to pump-and-treat adsorption
processes. Various chitosan-based composites have
been designed to overcome these problems. Chang
and Juang [87] proposed the addition of activated
clay to chitosan to prepare composite beads in order
to improve its mechanical properties. Cestari et al.
[61] also proposed the use of silica/chitosan hybrid
for the removal of anionic dyes from aqueous
solutions: these materials are of interest because
they combine the structure, strength and chemical
properties of the silica with the specic characteristics of chitosan. Chang and Chen [64] proposed
the use of chitosan-conjugated Fe3O4 nanoparticles
for the removal acid dyes from aqueous solutions.
The adsorption capacities were 1883 and 1471 mg of
dye/g of chitosan for AO 12 and AG 25. Paneva
et al. [96] also proposed a novel effective route for
incorporating magnetic material into chitosan beads
by capillary extrusion. They concluded that the
material might be used for wastewater treatment in
the textile industry.
4.3. Influence of process variables
The amount of dye that can be removed from a
solution by chitosan also depends on process
variables used in batch systems such as chitosan
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sites is low and subsequently the fractional adsorption becomes independent of initial concentration
[67,68,75,83]. At higher concentrations, however,
the number of available adsorption sites becomes
lower and subsequently the removal of dyes depends
on the initial concentration. At the high concentrations, it is not likely that dyes are only adsorbed in a
monolayer at the outer interface of chitosan. As a
matter of fact, the diffusion of exchanging molecules within chitosan particles may govern the
adsorption rate at higher initial concentrations.
Recently, Gaffar et al. [77] reported that the
adsorption percentage decreases on increasing
the dye concentration. This could be ascribed to
the accompanying increase in dye aggregation
and/or depletion of accessible active sites on the
material.
4.3.3. Effect of contact time
Contact time is another important variable in
adsorption processes. Generally speaking, the adsorption capacity and the removal efciency of dyes
by chitosan become higher on prolonging the
contact time. However, in practice, it is necessary
to optimize the contact time, considering the
efciency of desorption and regeneration of the
adsorbent.
During the process, the adsorbent surface is
progressively blocked by the adsorbate molecules,
becoming covered after some time. When this
happens, the adsorbent cannot adsorb any more
dye molecules. As each particle puries a certain
volume of liquid, increasing the dosages rapidly
promotes an equilibrium between adsorbate and
adsorbent because the number of particles to treat
the same volume of liquid is increased. In general,
the adsorption capacity increases with time and, at
some point in time, reaches a constant value where
no more dye is removed from the solution. At this
point, the amount of dye being adsorbed onto the
material is in a state of dynamic equilibrium with
the amount of dye desorbed from the adsorbent.
The time required to attain this state of equilibrium
was termed the equilibrium time (te) and the amount
of dye adsorbed at te reected the maximum dye
adsorption capacity of the adsorbent under these
conditions.
Chatterjee et al. [83] reported an equilibrium time
of 20 h for eosin adsorption onto chitosan. They
observed that the process was initially very fast and
then slowly reached equilibrium. Dutta et al. [75]
noted that the maximum accumulation occurred
423
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between monomer units of different chains (intermolecular bonds) decrease their reactivity. The
weakly porous structure of the polymer and its
residual crystallinity are critical parameters for the
hydratation and the accessibility to adsorption sites.
4.5.2. Effect of pH variation
To date it remains difcult to establish clear
trends in the adsorption properties of chitosan
materials for the recovery of dyes. The variability in
published results may deter potential users. There
are many reasons for this difculty in comparing
adsorption performances such as differences in
chitosan and above all experimental conditions
(equilibrium time, adsorbent dose), and also underestimation of the inuence of pH, especially pH
variation effects during the process [81]. Indeed,
frequently, batch systems used in the literature do
not take into account the change in pH.
Few studies have been published on the interpretation of the pH variation during adsorption
process. Sakkayawong et al. [109] reported that the
system pH changed during RR 141 adsorption by
chitosan. The explanation for this was that under
acidic conditions hydrogen atoms in the solution
could protonate the amine groups of the polymer
and thus causes the increased pH. In addition, the
adsorption efciency was systematically greater for
solutions whose pH was controlled during the
adsorption than for solutions for which pH varied
along the uptake process. At increasing adsorbent
dosage, Gibbs et al. [81] observed that the addition
of chitosan to the solution strongly increased its pH
and noted that the pH variation increased exponentially. The authors interpreted this phenomenon as
related to the increase of the number of amine
groups available for protonation, consequently
causing a marked increase in the pH. Increasing
adsorbent dose also reduced polymer saturation.
To diminish the inuence of pH change on the
interpretation and modeling of adsorption performance, chitosan can be conditioned by contact with
a solution of sulfuric acid [81] or other chemicals
[83], as shown below.
4.5.3. pH sensitivity
It is well known that chitosan hydrobeads lose
their integrity as a result of partial dissolution in
acidic solvent, since protonation of amine groups
causes the polymer to dissolve, making them
unsuitable for reuse. Crosslinking of the chitosan
beads has been proposed but can result in poor
427
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NH3+
NH2
protonation
chitosan
H2O
dye
SO3Na
dye
SO3-
Na+
dissociation
NH3+
chitosan
+ dye
SO3-
NH3+ -O3S
dye
electrostatic interaction
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planar structure and readily tend to form intermolecular interactions that facilitate permanent
aggregation under certain experimental conditions
(presence of surfactant, pH).
Numerous authors concluded that the binding
was a chemisorption reaction and the adsorption
phenomenon mainly depended on the interactions
between the surface of the adsorbent and the
adsorbed species. However, all the studies arrive at
contrasting conclusions showing the difculty of
using simple models for the interpretation of the
interactions of these polymeric materials with dyes.
Much work is necessary to clearly demonstrate the
adsorption mechanism for the different types of
chitosan-based materials.
6. Modeling
6.1. Equilibrium isotherm models
Adsorption properties and equilibrium data,
commonly known as adsorption isotherms, describe
how pollutants interact with adsorbent materials
and so, are critical in optimizing the use of
adsorbents. In order to optimize the design of an
adsorption system to remove dye from solutions, it
is important to establish the most appropriate
correlation for the equilibrium curve. An accurate
mathematical description of equilibrium adsorption
capacity is indispensable for reliable prediction of
adsorption parameters and quantitative comparison
of adsorption behavior for different adsorbent
systems (or for varied experimental conditions)
within any given system.
Adsorption equilibrium is established when the
amount of dye being adsorbed onto the adsorbent is
equal to the amount being desorbed. It is possible to
depict the equilibrium adsorption isotherms by
plotting the concentration of the dye in the solid
phase versus that in the liquid phase. The distribution of dye molecule between the liquid phase and
the biosorbent is a measure of the position of
equilibrium in the adsorption process and can
generally be expressed by one or more of a series
of isotherm models [122126]. The shape of an
isotherm may be considered with a view to
predicting if a sorption system is favorable or
unfavorable. The isotherm shape can also provide qualitative information on the nature of the
solutesurface interaction. In addition, adsorption
isotherms have been developed to evaluate the
capacity of chitosan materials for the adsorption
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and Dubinin-Radushkevich isotherms. These equilibrium isotherm equations are used to describe
experimental adsorption data. The different equation parameters and the underlying thermodynamic
assumptions of these models often provide insight
into both the adsorption mechanism, and the
surface properties and afnity of the adsorbent.
Therefore, it is important to establish the most
appropriate correlation of equilibrium curves to
optimize the condition for designing adsorption
systems.
Various researchers have used these isotherms to
examine the importance of different factors on dye
molecule sorption by chitosan. However, the two
most frequently used equations applied in solid/
liquid systems for describing sorption isotherms are
the Langmuir [123] and the Freundlich [124] models
and the most popular isotherm theory is the
Langmuir one which is commonly used for the
sorption of dyes onto chitosan (see Table 8). Table 9
reports the corresponding equations that can be
used for tting experimental data. The symbols used
in the equations are dened in the Nomenclature
section. Linear regression was frequently used to
determine the most frequently used model throughout the years.
The Langmuir model was found to be the most
appropriate to describe the adsorption process in
the case of (i) RB 5 [79,81], BB 9 [73], DB [75], eosin
[83], AG 27 [110], O II [115] and CV [115] on
Table 9
The two most popular equilibrium isotherm equations and their linear forms and equation parameters
Isotherm
Equation
Langmuir
qe
x
K LCe
m 1 aL C e
Assumptions
Monolayer adsorption
The sorption takes place at specic sites within the
Linear form
Ce
1
aL
Ce
KL KL
qe
adsorbent
F
qe K F C 1=n
e
Multilayer adsorption
The model applies to adsorption on heterogeneous surfaces
with interaction between adsorbed molecules
ln qe ln K F
1
ln C e
nF
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Table 10
The three most popular kinetic model and their linear forms
Model
Lagergren
Ho and McKay
Equation
qe
k1
t
log
qe qt
2:303
Linear form
1
1
k2 t
qe qt qe
t
1
1
t
qt k2 q2e qe
logqe qt log qe
qt ki t1=2 C
k1
t
2:303
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The dye accumulates at the surface and a (pseudo)equilibrium is established, and further adsorption of
dye can take place only at the same rate as the
surface concentration is depleted by inward adsorption. The dye uptake can be correlated to the square
of time over a large adsorption zone to get
diffusivity of the dye in adsorbent particles. In
diffusion studies, it is possible to dene a rate
parameter by plotting the adsorption capacity as a
function of the square root of time [47,93]. The root
time dependence may be expressed by the equation
proposed by Weber and Morris [129], assuming that
the mathematical dependence is obtained if the
process is considered to be inuenced by simple
diffusion in the particles and convective diffusion in
the solution. If intraparticle diffusion is involved in
the adsorption process, then the plot of the square
root of time versus the uptake would result in a
linear relationship, and intraparticle diffusion
would be the rate-limiting step if this line passed
through the origin. When the plots do not pass
through the origin, this is indicative of some degree
of boundary layer control and further shows that
the intraparticle diffusion is not the only ratecontrolling step, but that other processes may
control the rate of adsorption. The WebberMorris
plot is also an empirically relationship but widely
used in the literature.
Several different steps in the process have been
characterized by this simple mathematical model
and different linear sections have been identied in
the adsorption of dyes on chitosan as reported by
numerous authors [59,66,68,73,87,89,91]. All the
studies showed that the kinetics results can be used
to determine if particle diffusion is the rate-limiting
step for dye adsorption onto a material. In general,
the WebberMorris plots present a multilinearity,
which indicates that two or more steps occur in the
process. In the plots, there are three different
portions, representing the different stages in adsorption: an initial curved portion followed by
linear portion and then a plateau. The initial curve
portion is due to surface adsorption and rapid
external diffusion (boundary layer diffusion). The
second linear portion is the gradual adsorption
stage where the intraparticle diffusion is ratecontrolled. The plateau (third portion) is the nal
equilibrium stage, where the intraparticle diffusion
starts to slow down due to the low solute
concentration in solution. Juang and co-workers
[90,91,93] reported that adsorption kinetics were
controlled by different mechanisms, the most
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Table 11
Thermodynamic equations and their parameters
Expression
Arrhenius
ln kads
Gibbs
DG RT ln K L
vant Hoff
ln K L
Clausius-Clapeyron
RT 1 T 2
ln C 2 ln C 1
DH
T2 T1
Parameters
Ea
ln ko
RT
DH DS
RT
R
Enthalpy change
Entropy change
Enthalpy change
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441
Table 12
Thermodynamics and rate parameters for various dyes using chitosan
Dye
Material
T (1C)
pH
AB
AR 87
Azo
BB
BB 1
BB 3
BB9
BV 3
CV
CV
CV
IC
IC
O II
RR 141
RR 189
RR 189
Chitosan
20
30
30
20
30
25
25
30
20
20
60
35
25
20
20
30
30
3.6
Chitosan
Grafted chitosan
Grafted chitosan
Grafted chitosan
Grafted chitosan
Chitosan
Modied chitosan
Modied chitosan
Chitosan
Crosslinked bead
Crosslinked bead
DG (kJ/mol)
5.46
4.97
6.9
3
11
3
3
11.89
6.4
22.1
11.67
10.51
11.72
10.17
9.1
2.55
3.35
7.10
6.6
DH (kJ/mol)
72.87
17.10
2.17
47.46
DS (J/molK)
k0 (kg/g min)
Ea (kJ/mol)
Reference
75.7
43
[65]
[83]
[102]
[65]
[106]
[73]
[58]
[106]
[114]
[114]
[114]
[63]
[101]
[114]
[109]
[68]
[94]
51.8
9.25
2.47
1.09
23.05
23.05
23.2
29.25
5.68
18.20
52.9
32.14
38.66
38.65
45.8
90
7.94
37.88
153.1
8.11 107
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442
of protable processes to recover chitin and byproducts such as proteins and pigments. It is
important to note that the recovery of these
products from waste is an additional source of
revenue Crustacean shells contains considerable
quantities of carotenoids which so far have not
been synthesized, and which are marketed as a
sh food additive in aquaculture, mainly for
salmon [21]. In addition, calcium carbonate
which is another major component of crab shells,
is converted to calcium oxide and sodium
carbonate [12]. Pigments may be also recovered
as high value side products.
The production of the chitosan-based materials is
economically feasible because they are easy to
prepare with relatively inexpensive chemical
reagents under mild conditions. The procedures
also require relatively harmless chemicals.
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The works reviewed above indicate that bioadsorption onto chitosan is becoming a promising
alternative to replace conventional adsorbents
used for decolorization purposes. Outstanding
progress has been made, demonstrating the
application of chitosan and crosslinked chitosan
in dye bioadsorption. These materials are
efcient in dye removal with the additional
advantage of being cheap, non-toxic and biocompatible.
There is abundant literature concerning the
evaluation of adsorption performances of chitosan, especially in terms of adsorption capacity
(amount of dye adsorbed). At least 100 dyes
have been studied so far. All the studies showed
that chitosan had an extremely high afnity for
many classes of dyes. In particular, it has
demonstrated outstanding removal capacities
for acid, reactive and direct dyes. However,
dependencies in relation to the chemical structure
of the dyes were not clearly identied and there
is, as yet, little information in the literature on
this topic.
Chitosan is characterized by its easy dissolution
in many dilute mineral acids, with the remarkable
exception of sulfuric acid. It is thus necessary to
stabilize it chemically for the recovery of dyes in
acidic solutions. Several methods have been
developed to reinforce chitosan stability. The
advantage of chitosan over other polysaccharides
is that its polymeric structure allows specic
modications without too many difculties. The
chemical derivatization of the polymer by grafting new functional groups onto the chitosan
backbone may be used to increase the adsorption
efciency, to improve adsorption selectivity, and
also to decrease the sensitivity of adsorption
environmental conditions.
It is interesting to note the relationships between
physicochemical properties and/or sources of
chitosan and the dye-binding properties. Most
of the properties and potential of chitosan as
adsorbent can be related to its cationic nature,
which is unique among abundant polysaccharides and natural polymers, and its high charge
density in solution.
While adsorption on activated carbons is largely
independent of the pH, the adsorption of dyes on
chitosan is controlled by the acidity of the
443
ARTICLE IN PRESS
444
Acknowledgements
The authors wish to thank Nadia Morin-Crini
and Brigitte Jolibois (LBE, University of FrancheComte) and gratefully acknowledge the nancial
support of the OSEO ANVAR of Franche-Comte.
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