Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.

)
_______________________________________________________________________________________________

Applications of polymeric materials as adsorbents for dyes removal from

aqueous medium
D. Suteu*1 and S. Coseri2
1
Faculty of Chemical Engineering and Environment Protection,“Gheorghe Asachi” Technical University of Iasi, 73 D.
Mangeron Blv., Iasi, 700050, Romania
2
“Petru Poni” Institute of Macromolecular Chemistry, 41A, Gr. Ghica Voda Alley, 700487 Iasi, Romania

The scientific literature contains some valuable information about the applicability of polymeric materials, such as ion
exchange resins or cellulosic materials in removal of harmful, pollutants organic compounds (i.e. dyes) from aqueous
medium, probably due to their advantages related to ease of use in dynamic systems with increased adsorption efficiency,
the possibility of being employed in several consecutive cycles of sorption - desorption and high performance in terms of
degree of discoloration and treatment of aqueous effluents. The aim of this chapter is to review the latest developments of
the authors in the field of using polymeric materials (ion-exchange resins, cellulose ion exchange, cellulose functionalized
or modified physical / chemical) for retaining dyes textile from diverse aqueous media.

Keywords: adsorption, aqueous medium, cellulose, dyes, ion exchange resin

1. Organic dyes in aqueous media

Dyes represent a class of organic compounds, which could have a pollutant action of aquatic ecosystems. These
compounds originating from effluents of different industries, such as textile and leather, production of pharmaceuticals
and cosmetics, printing, food processing, paper and pulp. Besides from the aesthetic problems related to colored
effluents, the presence of dyes in aquatic environment can reduce light penetration affecting photosynthetic activity and
oxygen transfer in the water. Generally, dyes are synthetic chemical compounds with complex aromatic structures,
which determine their low degree of biodegradability or even non-biodegradability, the long time presence in
environment and accumulation in sediments but especially in fishes or other aquatic organisms. Most of dyes are risky
substances to living organisms causing allergies, dermatitis, skin irritation or different tissular changes. Moreover,
aromatic amines, benzidine, naphthalene and other aromatic compounds resulted as by-products of azo dyes
degradation by microorganisms have been reported to be toxic, carcinogenic and mutagenic to humans [1,2].
In this context, the removal of dyes from industrial effluents before their discharge into aquatic ecosystems is of
considerable concern. Therefore, in many countries strict laws and regulations have been introduced and more stringent
standard about discharge limits of colored industrial effluents, what makes necessary the introduction a stage for
discoloring the industrial effluent before their discharge.
There is a diversity of methods and technologies for treatment of colored wastewater such as chemical oxidation,
coagulation/flocculation, ozonation, ion exchange, adsorption, electrochemical reduction, membrane processes,
biological degradation; the advantages and the limitations of each method were highlighted by different authors.
Adsorption (process that consists in the transfer of soluble organic dyes (solutes) from wastewater to the surface of
solid, highly porous, particles (the adsorbent), represents even now a viable alternative due to their major advantages
appreciated in terms of efficiency and cost. Also, adsorption is one of the methods very useful in the treatment of
coloured wastewaters because of their design simplicity, inexpensiveness, specific physic-chemical interactions
between dyes and the solid adsorbent, and low matrix effects [3-6]. Dye removal by adsorption in batch or dynamic
conditions is a relatively simple method which can be carried out without sophisticated equipments.
Among other advantages of this method we can mention: increase of process sensibility; increase of selectivity;
reduction of matrix effects; possibility of simultaneous achievement of pre-concentration and the proper estimation. But
the main advantage of adsorption is the possibility to use to use as adsorbents many types of materials: synthetic to
natural low-cost materials (natural as well as wasted materials from different industries and agriculture) as suitable
adsorbents for decolourization of industrial effluents.
The intention of this chapter is to make a review of our works developed over time about the use of polymeric
materials (ion-exchange resins, cellulose ion exchange cellulose functionalized or physical /chemical modified) for
retaining dyes textile diverse aqueous media. The results are presented in the context of development in this area and
presented in the literature.

62
 Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.)
_______________________________________________________________________________________________

2. Adsorbents based on polymeric materials

The choice of an adsorbent was based on requirements concerning high selectivity, large capacity of adsorption,
favorable kinetic features, physical-chemical stability, mechanical strength, easy regeneration and availability at low
cost [6].
Because of compatibleness between these criteria and their adsorptive features, the synthetic materials, such as ion
exchange resins (Amberlite IRA-401S, Vionit AT-1, Purolite, A-400, Purolite, A-500, Purolite C-100), polyamide, ion
exchange celluloses, chitosan, functionalized polymers (with chelating group), and activated charcoal constitute, in
many instances, a solution of election [1,6-9] .
In order to avoid some disadvantages of conventional adsorbents based on synthetic polymers (high prices,
difficulties in obtaining, pollution produced during their synthesis), and in accordance with the tendency of replacing
chemically synthesized compounds, unconventional materials are increasingly used for wastewaters analyzes and
treatment [6]. These materials can be:
 synthetic (e.g., ashes, different charcoals in the presence or not of biodegradable polymers such as
polyelectrolytes);
 natural, such as: peat, algae, seashell;
 different types of wastes:
 industrial waste [10,11]: coal ash from thermo-electric power plant, for retaining metal ions and textile dyes;
cellolignin - residual product obtained after treating the wood with dilute mineral acid; sawdust, from wood
industries; textile fibers (hemp, polyacryl-amidoxime chelating fiber, PAN, etc.); microbial biomass resulted
from industrial fermentative technology (food and pharmaceutical industry) [10,11].
 agro-industry waste - cellulosic and/or lignocellulosic materials which present different chelatic groups in their
structure, (e.g., pumpkin core peels, seed pods, straws, jute fibers, hemp, cotton [10-12].

3. Ion exchange resins

3.1 Structure

Synthetic resins are largely used as adsorptive supports in various fields, including ecology and biotechnology. They are
used in their active form, or can be physical or chemical modified, therefore the adsorptive properties are dictate by the
macromolecular structure or by the adopted physical/chemical routes to obtain the resin. The most used ones contains
cross-linked divinylbenzene (for instance with styrene or metacrylic esters, see Tables 1, 2.). These resins are
characterized by high stability over the whole range of pH, thus being possible to use eluents which have extreme pH-s.
Another advantage of these resins is their physical-chemical stability, which allows several utilizations (large number of
cycles).

Table 1 Properties of Purolite anionic resins [13]

Type of Purolite resins
Parameter A – 400 A – 500
Matrix polystyrene-divinylbenbeze polystyrene-divinylbenzene
Structure gel macroporous
Functional group R – (CH3)3N+ R – (CH3)3N+
Ionic form Cl- Cl-
Mean particle diameter/ mm 0.64 (  0.03) 0.64 (  0.03)
Capacity*/ meqg-1 3.72 3.93
*
- determined by pH-metric titration of resins dried at room temperature for 72 hours

63
 Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.)
_______________________________________________________________________________________________

Table 2 Physico-chemical characteristics of used cationic Purolite resins [1]

Characteristics Type of Purolite resins
C 107E C 145
specific gravity g/mL 1.15 1.22
bead size range/ µm 630-1300 300 - 1200
physical form transparent white beads
operating temperature 100 oC (max.) 120 0C (max.)
polymer matrix structure polymethacrylic crosslinked with polystyrene crosslinked
divinylbenzene with divinylbenzene
structure macroporous macroporous
functional group R – COO- R – SO3-
ionic form as shipped H+ Na+
type of resins weak acid strong acid
pH range, operating 5 - 14
pH limits (stability) 0 - 14
total exchange capacity *eq/L 3.7 1.5
*
- determined by pH-metric titration of resins dried at room temperature for 72 hours

Unlike rigid structures, as for example silica gel, whose properties depends by the porosity and pore size distribution,
the physical characteristic of the styrene-divinylbenzene resins are related by the polymerization conditions (initiator
type, temperature, etc) and the cross-linked degree. These parameters are manipulated during fabrication, and strongly
influenced the resins performances: specific surface, size and shape pores, and also pore size distribution [14, 15]. As
lower as the cross-linking, the higher the adsorption capacity is. For example, in the case of microporous
divinylbenzene-styrene resins, or those “gel” type, the optimum cross-linking degree is between 2 and 8%, which
ensures both good mechanical properties and adsorption efficiency [14, 15]. Macroporous resins could be obtained in
polar solvents by suspension polymerization. To achieve the macroporous structure, often are introduced in the
polymerization system an inert solvent or inorganic fine salts, for example CaCO3. In this way, spherical particles are
obtained, having a high specific surface (25-800 m2/g) and an average pore size between 20–500 Å. The high cross-
linking degree of these resins gives them a good mechanical strength. [14, 16].
Internal structure of the resins depends on the presence of micro/macro pores. Macropores facilitates the migration of
the solute through adsorbant during adsorption/desorption processes. Micropores role is very similar with capillars,
providing small centers on the surface for adsorption process. [14, 17]. A wide variety of conditioning resins exist: from
rigid or soft granules, nonporous or porous materials, with pore sizes of 600 nm, with specific surfaces ranging from 2
to 1000 m2/g, anionic or cationic charged 14, 18.
The adsorption selectivity of the macro cross-linked resins is influenced by the pores shape, size and distribution, but
also by the polarity of the surface, being affected by polymerization process: monomer type, cross-linking agent,
initiator, filler material, etc.
The three-dimensional structure ensures a good stability in harmful media (acid, alkaline, organic solvents), so these
adsorbents are easily regenerated, being used in dynamic systems.
Adsorptive properties of the macro cross-linked porous polymers are influenced by formation of the cavities in
solvated adsorbent and also by the hydrogen bond, which can modify the selectivity [16].
In order to be used in chromatographic columns for separation in dynamic conditions, the degree of impregnating
resin in solvent is an important factor in their design because swelling can block resin beads or glass columns break due
to pressure. Also, solvent impregnation modifies pore size by more than 20-30% as compared to a hydrated form.

3.2 Applications of ion exchange resins

The resins, styrene-divinylbenzene type copolymers may be adsorbents for various organic compounds. These resins
are effective extraction systems from different fermentation in lightening and removing organic compounds from waste
streams and recovery, separation and purification of reaction mixtures produced [19]. This class of resin includes
polymers derivatives of styrene crosslinked with divinylbenzene (XAD-2, XAD-4, XAD-1180 XAD-16, HP-20, HP-21)
and polymers based on acrylic esters type: XAD-7, XAD-8.
The scientific literature contains some valuable information about the applicability of ion exchange resins in removal
of dyes from aqueous solutions, probably due to their advantages related to ease of use in dynamic systems with
increased adsorption efficiency, the possibility of employ in several consecutive cycles of adsorption - desorption and
high performance in terms of degree of discoloration and treatment of aqueous effluents [1, 20-25]. The major
advantages outweighed high cost of the synthetic resins involved. Various ion exchange resins investigated recently for
the removal of dyes from aqueous solutions are summarized in Table 3.

64
 Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.)
_______________________________________________________________________________________________

Table 3 Application of ion exchange resins as adsorbents for removal of different dyes
Ion exchange resin used/ main characteristics Removed dye Ref.
Gel anion exchangers (weakly basic Amberlite IRA-67 and strongly basic Amberlite Acid Orange 7 [23]
IRA-458)
Strongly basic polystyrene anion exchangers: Amberlite IRA-900 and Amberlite Tartrazine [26]
IRA-910
Acrylic resins: Amberlite IRA-458 with gel structure and Amberlite IRA-958 with Reactive Black 5 [27]
macroporous structure
Gel anion exchanger Purolite A-850 of N+(CH3)3 functional groups Acid Blue 29 [28]
Strongly basic anion exchanger of macroporous structure – Purolite A-520E Acid Blue 29 [29]
Purolite ion exchange resins of macroporous (A – 500) and gel (A – 400) structure Blue M-EB [13]
Purolite ion exchange resins C-100 Methyl Violet [30]
Purolite macroporous ion exchange C-107E (polymethacrylic crosslinked with Basic Blue 9 [1]
divinylbenzene) and C-145 (polystyrene crosslinked with divinylbenzene)
Strong cation - exchange resin obtained by poly(glycidylmethacrylate) grafted via Crystal Violet [31]
surface-initiated-atom transfer radical polymerization on a cross-linked acrylate and
based resin Basic Fuchsine
Acrylic weak base anion exchange resin with ethylenediamine-functional groups Acid Green 9 [32]

Polystyrene anion exchangers Amberlite IRA-900 and Amberlite IRA-910 with Allura Red and [33]
macroporous structure Sunset Yellow

4. Cellulosic materials

4.1 Structure
Cellulose [(C6H10O5)n], represent the most abundant regenerable polymer on Earth, with applications almost on every
field of the human needs. Cellulose possesses a fibrous structure, high internal surface (caused by the size and
distribution of pores), higher higroscopicity (correlated with porous structure and the presence of hydroxyl groups) and
offers the possibility of functionalization with organic reagents, under certain conditions. The most important
functionalization processes on cellulose are the esterification and etherification reactions which were firstly developed
since the nineteen century, with a great impact on the humanity. Adsorptive properties of cellulose can be improved by
changing the physical and / or chemical functional groups of constituents. For the synthesis of ion exchange pulps often
are used the cellulose from cotton or wood. The main cellulose cation exchange (Table 4) are those cellulose sorts
containing carboxyl groups, introduced by selective oxidation using appropriate oxidizing agent (nitrogen dioxide,
perchloric acid, periodic acid, nitroxyl radical, i.e. TEMPO, N-hydroxyphthalimide). These selective reagents are able
to oxidize only the primary hydroxyl groups on the cellulose unit, converting them to carboxylic acids, via an aldehyde
structure intermediate, Figure 1[34-39].

Fig. 1 Possible oxidation routes for the cellulose selective oxidation, in presence of nitroxyl radicals or periodates.

Cation exchange cellulosic materials with radicals of citric acid, phthalic acid, maleic acid, succinic acid, glutaric or
salicylic acid are of great interest.

65
 Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.)
_______________________________________________________________________________________________

Celluloses anion exchange (Table 5) containing anionic groups, which gives them basic character. They are more
hydrophilic materials than synthetic resins anionites, but shows smaller exchange capacity.
Instead there is the possibility of increasing the adsorption capacity, maintaining fibrous structure by chemical
treatments based on bifunctional crosslinking reagents and introducing ionogene groups, operations that can be
performed sequentially or simultaneously. Some crosslinking agents are: formaldehyde, epichlorohydrin, divinyl
sulfone, 1,3-dichloro-2-propanol, diepoxide derivatives [14].

Table 4. Characterization of some cation exchange celluloses

Cation exchange cellulose / Acid Functionalization method Nominal exchange
Ionogen strength capacity, meq/g
CM a-cellulose / - weak Alkali cellulose treated with 0 7  0,1
OCH2COOH monochloroacetic acid
medium 0,7
CEb-cellulose / -OC2H4COOH
Alkali cellulose treated with
Pc-cellulose / -O-PO3H2 medium POCl3/NH3 or esters-phosporic acid 0,85  0,1

SEd-cellulose / -O-C2H4SO3H strong Alkali cellulose treated with 2-

sodium chloroethyl sulfate 0,2  0,06
SMe-cellulose / -O-CH2-SO3H strong Alkali cellulose treated with 2- -
sodium chloromethyl sulfate

Notes: a-carboxymethyl cellulose; b- carboxyethyl cellulose; c-cellulose phosphate; d-sulfoethyl cellulose; e-sulfomethyl celuloza

Table 5. Characterization of some anion exchange celluloses

Anion exchange cellulose / Base strength Functionalization method Nominal
Ionogen exchange
capacity, meq/g
AEa/-OCH2CH2NH2 medium Cellulose reaction with 2-aminoethyl
sulfonic acid, in the presence of NaOH,
or ethyl amine in the presence of acids 0,8  0,1
catalysts.
DEAEb/-O(CH2)2N(C2H5)2 medium Cellulose treated with 2-chlorotriethyl
amine, in the presence of NaOH. 0,7  0,1
TEAEc/-O(CH2)2N+(C2H5)3]X- strong Diethylaminoethyl cellulose reaction
with alkil halides 0,5  0,08
ECTEOLA/-OCH2CHOHCH2O- medium Alkali cellulose treated with
CH2CH2N((CH2)2OH)2 epichlorohydrin and triethanol amine. 0,3  0,05
GEd/ -O(CH2)2NHC(NH)NH2 strong Aminoethyl cellulose treated with
thiourea in tampon solution carbonate- 0,4  0,1
bicarbonate.
PABe/-O-CH2-C6H4-NH2 weak Reaction of cellulose with para
nitrobenzil, in the presence of NaOH, 0,2  0,1
followed by reduction with sodium
hydrosulphite.
Notes: a-aminoethyl cellulose; b-diethylaminoethyl cellulose; c-triethylaminoethyl cellulose; d-guanidoethyl cellulose; e-p-amino
benzyl cellulose.

Special ion exchange cellulosic materials (DEAE Sephacel) based on microcrystalline cellulose were prepared, from
cotton linters by partial hydrolysis, yielding products with low molecular weight and satisfactory mechanical strength.
A new type of cellulose materials type is Cellets 200 and 350, a versatile product which combines different
properties such as perfect sphericity, narrow particle size distribution, low friability, low solubility and inertness [40].
Cellets are microcrystalline cellulose beads, produced exclusively by microcrystalline cellulose and purified water,
without any additive. They possess high spherical starter cores with extreme stability and low friability (Table 6) [40].
Recently, an extensive work has been dedicated to produce pellets of Cellets 200 by a continuous mode of operation,
using a Wurster fluidized bed, in contrast with batch-wise technique, to reduce the production costs and improve the
process control [41]. The authors found that the particle size distribution (PSD) of the obtained Cellets 200 pellets is
narrow, ranging from 200 to 400 m [41]. The coordination number for Cellets 200, which is a basic attribute that
influences many properties of products made of particulate materials, has been determined as 8.1±1.5 by using

66
 Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.)
_______________________________________________________________________________________________

DBSCAN (Density-Based Spatial Clustering of Applications with Noise) for segmentation of X-ray micro-tomographic
images [42].

Table 6 Physical and chemical characteristics of microcrystalline cellulose Cellets

Cellets 200 Cellets 350
Particle size distribution 200 – 355 m (≥ 85 %) 350 – 500 m (≥ 85 %)
Loss on drying ≤ 7.0 %
Bulk density (g/cm) 0.80 ± 5 %
Sphericity degree (average) 0.90 ± 0.05
Degree of polymerization ≤ 350
pH value 5.0 – 7.0
Conductivity/(µS/cm) ≤ 75

Made for biomedical applications, this material has been studied also as a potential adsorbent for retaining dyes from
aqueous medium due to outstanding mechanical properties that confer them resistance to repeated manipulations (such
as repeated cycles of adsorption - desorption) [40].
Granular cellulose and its derivatives are characterized by availability at a low price, spherical particle, availability
with selectable particle size, strength, having already applications as industrial filters, high porosity, hydrophilicity,
compatibility with biological structures, and are readily for various functionalization reactions. These properties are
considered performance factors as compared with other materials such as agarose (Sepharose) and cross-linked dextran
(Sephadex) [14].
Depending on the technological process used to manufacture them, celluloses may be create in many forms and types
ranging from fibers, linters, microcrystalline powders, softwood pulp, bacterial cellulose and many others [40, 43-53].

4.2 Applications of cellulosic materials

Cellulose-based materials have successfully been used as adsorbents for retaining various types of dyes from aqueous
media (Table 7). Their adsorption capacity depends primarily on the adopted synthesis protocol, existing functional
groups and the presentation form, and secondly by the structure and properties of the studied dyes (molecular weight,
functional groups).

Table 7 Application of cellulosic materials as adsorbents for removal of different dyes

Adsorbents based on cellulose Dye Adsorption capacity, q Ref.
(mg/g)
Acrylic acid grafted cellulosic Luffa Methylen Blue 65.15 [54]
cylindrical fiber
Bead cellulose Methylene Blue / 0.6 105/2.3 105/4.4 105 [55]
Alizarin Red / Congo Red
Carboxymethyl cellulose – g- Methyl Orange 1825 [56]
poly(2-(dimethylamino) ethyl
methacrylate) hidrogel B
Carboxymethyl cellulose Methylene Blue 369-652 [57]
Ion exchanger cellulosic materials Acid Clue 25 / Acid Yellow 9 / 294/333/175/127 [58]
Reactive Yellow 23/Acid Blue
79
Cellulose multicarboxyl Malachite Green / Basic 458.72/1155.76 [47]
fuchsine
Carboxylate – functionalized Methylene Blue / Rhodamine 185.63 / 118.21 [44]
cellulose from waste cotton fabrics 6G
Cellulose nanocrystal – alginate Methylene Blue 256.41 [43]
hydrogel beads
Cellulose nanocrystal Methylene Blue 118 [59]
Microcrystalline cellulose Cellets Methylene Blue [40]
Brilliant Red HE-3B 4.45

5. Conclusions
Synthesizing information from literature allows the assertion that polymer remain a valuable category of adsorbents for
retaining the dyes, in dynamic or static, continuous or discontinuous systems, present in aqueous media due to more

67
 Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.)
_______________________________________________________________________________________________

than a few advantages such as: (1) use easily in dynamic systems, (2) Their excellent mechanical properties facilitates
the use in consecutive repeated cycles of adsorption – desorption, (3) a good report between efficiency and price and (4)
high performance in terms of degree of discoloration and treatment of aqueous effluents [1, 23, 25, 40].
Also, the morphological properties and the physicochemical characteristics of these classes of adsorbents allow their
use to treat large volumes of wastewater which is an advantage for situations where the pollutant is found dispersed in
large volumes of influent or in the case of the effluent of sewage treatment plants, that it allows both removal and
concentrating the pollutant.
Due to outstanding mechanical properties that give it resistance to repeated manipulations (such as repeated cycles of
adsorption – desorption), it was tried testing them, as the adsorbent material for retention of different persistent
pollutants such as organic dyes or for persistent organic micropollutants such as drug residues and for heavy metal ions
present in various aqueous environments.

References
[1] Suteu D, Bilba D, Coseri S. Macroporous polymeric ion exchangers as adsorbents for the removal of cationic dye basic blue 9
from aqueous solutions. Journal of Applied Polymer Science. 2014a; 131 (1): DOI: 10.1002/app.39620.
[2] Zaharia C, Suteu D. Textile organic dyes – characteristics, polluting effects, and separation/elimination procedures from industrial
effluents. A critical overview. In: Puzyn T, Mostrag-Szlichtyng A, editors. Organic Pollutants Ten Years After the Stockholm
Convention - Environmental and Analytical Update. Rijeka, Croatia: INTECH Publisher; 2012. p. 57-86.
[3] Allen SJ, Koumanova B Decolourisation of water⁄wastewater using adsorption (review). J. of the University of Chemical
Technology and Metallurgy. 2005; 40(3): 175- 192.
[4] Babu RB, Parande AK, Raghu S, Kumar PT. Textile Technology - Cotton Textile Processing: Waste Generation and Effluent
Treatment. The Journal of Cotton Science. 2007; 11: 141-153.
[5] Crini G. Non-conventional low-cost adsorbents for dyes removal: A review. Bioresource Technology. 2006; 97: 1061-1085.
[6] Suteu D, Zaharia C, Bilba D, Surpateanu M. Conventional and unconventional materials for wastewater treatment. Bulletin of the
Transilvania University of Brasov (Romania). 2007a; IV: 692 –696.
[7] Neagu V, Bunia I, Plesca I, Popa M. Synthesis of new chelating ion exchange resin with hydroxamic and
amidoxime groups and study of its metal binding property. J. Appl. Polym. Sci. 2003; 88: 2956-2962.
[8] Perju M M., Dragan E S. Removal of azo dyes from aqueous solutions using chitosan based
composite hydrogels. Ion exchange letters. 2010; 3: 7-11.
[9]. Dragan E S., Cazacu M. Ionic hybrid hydrogels. In: Dragan E S., editor. New Trends in Ionic (Co)Polymers and Hybrids. Nova
Science Publishers; 2007. p.145-164.
[10] Suteu D, Blaga AC, Zaharia C. Biosorption-Current bioprocess for wastewater treatment. In: Zaharia C., editor. Current topics,
concepts and research priorities in environmental chemistry. Vol. 1. Iasi, Romania. “A I Cuza” University Publishing; 2012.
p.398-422.
[11] Suteu D, Zaharia C, Muresan A, Muresan R, Popescu A. Using of industrial waste materials for textile wastewater treatment.
Environ. Eng. Manage. J. 2009b; 8(5): 1097-1102.
[12] Suteu D, Zaharia C, Malutan T. Biosorbents based on lignin used in biosorption processes from wastewater treatment. In Ryan J.
Paterson., editor. Lignin. Properties and Applications in Biotechnology and Bioenergy. New York, U.S.A. Nova Science
Publishers; 2011: p. 279-305.
[13] Suteu D, Bilba D, Zaharia C. Kinetics of Blue M-EB dye sorption on ion exchange resins. Hung. J. Chem. 2002; 30: 7-11.
[14] Gorduza VM, Tofan L, Suteu D, Gorduza EV. Biomaterials – Biotehnologies - Biocontrol, Iasi, Romania. Cermi Publishing.
2002.
[15] Tarabasanu-Mihaila C, Gorduza VM, Radu F, Mazgareanu M. Organic dyes with interest in food, cosmetic and pharmaceutical
products (in Romanian). Bucuresti, Romania. UNI-PRESS Publishing House. 1997.
[16] Namasivayam C, Kanchana N. Waste banana pith as adsorbent for color removal from wastewaters. Chemosphere. 1992;
25(11): 1691-1705.
[17] Porta V, Sarzanini C, Mentasti E, Abollino O. On-line preconcentration system for inductively coupled plasma atomic emission
spectrometry with quinolin-8-ol and Amberlite XAD-2 resin. Anal. Chim. Acta. 1992; 258: 237 - 244 .
[18] Gorduza VM, Tarabasanu-Mihaila C, Athanasiu A, Pop C, Gorduza EV. Organic dyes - Unconventional applications (in
Romanian). Bucuresti, Romania. UNI-PRESS Publishing House. 2000.
[19] Hou M, Baughman G L. Predicting the precipitation of acid and direct dyes in natural waters. Dyes and Pigments. 1992; 18: 35
– 46.
[20] Macoveanu M , Bilba D, Bilba N, Gavrilescu M, Soreanu G. Ion Exchange Process in environmental Protection (in Romanian),
Publisher MatrixRom. Bucuresti,. Romania. 2002.
[21] Karcher S, Kornmuller A, Jekel M. Anion exchange resins for removal of reactive dyes from textile wastewaters. Water Res.
2002; 36: 4717-4724.
[22] Yu Y, Zhuang Y-Y, Wang Z-H, Qiu M-Q. Adsorption of water-soluble dyes onto modified resin.Chemosphere. 2004; 54: 425–
430.
[23] Greluk M, Hubicki Z. Evaluation of polystyrene anion exchange resin for removal of reactive dyes from aqueous solutions.
Chem. Eng. J. 2011; 170: 184-193.
[24] Wawrzkiewicz M, Hubicki Z. Equilibrium and kinetic studies on the sorption of acidic dye by macroporous anion exchanger.
Chem. Eng. J. 2010; 157: 29-34.

68
 Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.)
_______________________________________________________________________________________________

[25] Wawrzkiewicz M, Hubicki Z. Anion Exchange Resins as Effective Sorbents for Removal of Acid, Reactive, and Direct Dyes
from Textile Wastewaters. In: Ion Exchange - Studies and Applications. Kilislioglu A editor. Croatia: INTECH Publisher;
2015. p. 37-72.
[26] Wawrzkiewicz M, Hubicki Z. Removal of tartrazine from aqueous solutions by strongly basic polystyrene anion exchange
resins. J.Hazard. Mater. 2009; 164: 502-509.
[27] Greluk M, Hubicki Z. Kinetics, isotherm and thermodynamic studies of Reactive Black 5 removal by acid acrylic resins. Chem.
Eng. J. 2010; 162: 919-926.
[28] Wawrzkiewicz M, Hubicki Z. Equilibrium and kinetic studies on the adsorption of acidic dye by the gel anion exchanger. J.
Haz. Mater. 2009 ; 172: 868-874.
[29] Wawrzkiewicz M, Hubicki Z. Weak base anion exchanger amberlite fpa51 as effective adsorbent for acid blue 74 removal from
aqueous medium - kinetic and equilibrium studies. Sep. Sci. Technol. 2010; 45: 1076-1083.
[30] Suteu D, Zaharia C, Bilba D,Surpateanu M. Conventional and unconventional materials for wastewater treatment, Bulletin of the
Transilvania University of Brasov (Romania). 2007; IV: 692 –696
[31] Bayramoglu G, Altintas B, Yakup Arica M. Adsorption kinetics and thermodynamic parameters of cationic dyes from aqueous
solutions by using a new strong cation-exchange resin. Chem. Eng. J. 2009; 152: 339–346.
[32] Dulman V, Simion C, Barsanescu A, Bunia I, Neagu V. Adsorption of anionic textile dye Acid Green 9 from aqueous solution
onto weak or strong base anion exchangers. J.of Appl.Polym. Sci. 2009; 113: 615–627.
[33] Wawrzkiewicz M, Hubicki Z. Kinetics of adsorption of sulphonated azo dyes on strong basic anion exchangers. Environmental
Technology. 2009; 30: 1059-1071.
[34] Coseri S, Nistor G, Fras L, Strnad S, Harabagiu V, Simionescu BC. Mild and Selective Oxidation of Cellulose Fibers in the
Presence of N-Hydroxyphthalimide. Biomacromolecules. 2009; 10 (8): 2294-2299.
[35] Biliuta G, Fras L, Strnad S, Harabagiu V, Coseri S. Oxidation of Cellulose Fibers Mediated by Nonpersistent Nitroxyl Radicals.
Journal of Polymer Science, Part A: Polymer Chemistry. 2010; 48 (21): 4790-4799.
[36] Coseri S, Biliuta G. Bromide-free oxidizing system for carboxylic moiety formation in cellulose chain. Carbohydrate Polymers.
2012; 90: 1415-1419.
[37] Biliuta G, Fras L, Drobota M, Persin Z, Kreze T, Stana-Kleinschek K, Ribitsch V, Harabagiu V, Coseri S. Comparison study of
TEMPO and phthalimide-N-oxyl (PINO) radicals on oxidation efficiency toward cellulose. Carbohydrate Polymer. 2013; 91(2):
502-507.
[38] Coseri S, Biliuta G, Simionescu B C, Stana-Kleinschek K, Ribitsch V, Harabagiu V. Oxidized cellulose—Survey of the most
recent achievements. Carbohydrate Polymers.2013; 93(1): 207-215.
[39] Coseri S, Biliuta G, Fras-Zemljic L, Stevanic Srndovic J, Larsson T, Strnad S, Kreze T, Naderi A, Lindstrom T. One-shot
carboxylation of microcrystalline cellulose in the presence of nitroxyl radicals and sodium periodate. RSC Advances. 2015; 5 :
85889-85897.
[40] Suteu D, Biliuta G, Rusu L, Coseri S, Nacu G. Cellulose CELLETS as new type of adsorbent for the removal of dyes from
aqueous media. Environmental Engineering and Management Journal. 2015; 14: 525-532
[41] Hampel N, Buck A, Peglow M, Tsotsas E. Continuous pellet coating in a Wurster fluidized bed process. Chem Eng Sci. 2013;
86: 87-98.
[42] Nguyen TT, Tran TN, Willemsz TA, Frijlink HW, Ervasti T, Ketolainen J, van der Voort Maarschalk K. A density based
segmentation method to determine the coordination number of a particulate system. Chem Eng Sci. 2011; 66: 6385-6392.
[43] Mohammed N, Grishkewich N, Berry RM, Tam KC. Cellulose nanocrystal-alginate hydrogel beads as novel adsorbents for
organic dyes in aqueous solution. Cellulose. 2015; 22:3725-3738
[44] Tiam D, Zhang X, Lu C, Yan G, Zhang W, Zhou Z. Solvent-free synthesis of carboxylate-functionalized cellulose from waste
cotton fabrics for the removal of cationic dyes from aqueous solutions. Cellulose. 2014; 21: 473-484.
[45] Melone L, Rossi B, Pastori N, Panzeri W, Mele A, Punta C. TEMPO-oxidized cellulose cross-linked with branched
polythyleneimine: nanostructured adsorbent sponges for water remediation. ChemPlusChem. 2015; 80:1408-1415
[46] Hubbe MA, Beck KR, O`Neal WG, Sharma YCh. Cellulosic substrates for removal of pollutants from aqueous systems: A
review. 2. Dyes. BioResource. 2012; 7: 2592-2687
[47] Zhou Y, Zhang M, Hu X, Wang X, Niu J, Ma T. Adsorption of cationic dyes on a cellulose based multicarboxyl adsorbent. J
Chem Eng Data. 2013; 58: 413-421
[48] Palit D, Monlik SP. Adsorption of Methylene Blue on cellulose from its own solution and its mixture with methyl orange.
Indian J Chem. 2000; 39A:611-617
[49] Hwang MC, Chen KM. The removal of color from effluents using polyamide – epichlorohydrin-cellulose polymer. I.
Preparation and use in direct dye removal. J Appl Polym Sci. 1993a; 48:299-311.
[50] Hwang MC, Chen KM. The removal of color from effluents using polyamide – epichlorohydrin-cellulose polymer. II. Use in
acidic dye removal. J Appl Polym Sci. 1993b; 48: 975-989.
[51] Hwang MC, Chen KM. The removal of color from effluents using polyamide – epichlorohydrin-cellulose polymer. III. Use in
anionic dye removal from batch process. J Appl Polym Sci. 1993c; 50: 735-744.
[52] Zhang G, Yi L, Deng H, Sun P. Dyes adsorption using a synthetic carboxymethyl cellulose – acrylic acid adsorbent. J Environ
Sci. 2014 ; 26:1203-1211
[53] Silva JA, Lima LCB, Bezerra RDS, Osajima JA Filho ECS. Use of cellulosic materials as dye adsorbent – A prospective study.
In: Poletto M and Ornaghi HL Jr, editors. Cellulose – Fundamental aspects and current trends. Croatia: Intech Publishing;
2015. p 115-132.
[54] Gupta VK, Agarwal S, Singh P, Pathania D. Acrylic acid grafted cellulosic Luffa cylindrical fiber for the removal of dye and
metal ions. Carbohydr Polym. 2013; 98:1214-1221.
[55] Morales A, Bordallo E, Leon V. Adsorption and releasing properties of bead cellulose. Chin J Polym Sci. 2004; 22:417-423
[56] Salama A, Shukry N, El-Sakhawy M. Carboxymethyl cellulose –g-poly(2-(dimethylamino) ethyl methacrylate) hidrogel as
adsorbent for dye removal. Int J Biol Macromol. 2015; 73:72-75.

69
 Polymer science: research advances, practical applications and educational aspects (A. Méndez-Vilas; A. Solano, Eds.)
_______________________________________________________________________________________________

[57] Begum HA, Mahbub MKB. Effectiveness of carboxymethyl cellulose for the removal of methylene blue from aqueous solution.
Dhaka Univ J Sci. 2013; 61:193-198
[58] Baouab MHV, Gauthier R, Gauthier H, Chabert B, El Baker Rammah M. Immobilization of residual dyes onto ion-exchanger
cellulosic materials. J Appl Polym Sci. 2000; 77: 171-183.
[59] Batmaz R, Mohammed N, Zaman M, Minhas G, Berry RN, Tam KC. Cellulose nanocrystals as promising adsorbents for the
removal of cationic dyes. Cellulose. 2014; 21:1655-1665.

70