PROCESS ENGINEERING JOURNAL 1 (2017) 41–51

Process Engineering Journal

http://process-eng-j.webs.com/

Use of dispersed and beads chitosan in liquid effluents treatment

Dihia Aili a, Ibrahim Feraoun a, Lydia Adour a,b, Hakim Lounici b,c *
a Département de Chimie, Faculté des Sciences. Université Mouloud Mammeri, 15000 Tizi-Ouzou, Algeria
b Unité de Recherche en Ingénierie & Environnement (URIE), Ecole Nationale Polytechnique, 10 Avenue Hassen Badi, El-Harrach, BP 182, 16200 Alger, Algeria
c Université de Bouira, MDD, Campus Pole Technologique, 10000 Bouira, Algeria

ARTICLE INFO ABSTRACT

Article history: Chitosan, an amino-biopolymer, has received a great deal of attention in the last decades in the
Received 7 April 2017 treatment of various suspensions and solutions for the removal of particulate and dissolved
Received in revised form 21 contaminants. The advantage of chitosan over other polysaccharides is that its polymeric structure
Septembre 2017 allows specific modifications without too many difficulties. It is commonly prepared by
Accepted 24 September 2017 deacetylating chitin in alkali solution. Contrarily to bibliography, two low temperatures (25 ± 2
and 30 ± 2 °C) and several days (10-15) have been chosen for deacetylation of purified chitins
Keywords: (chemical and biological). The aim was to produce soluble chitosan in diluted acetic acid solution
Chitosan (1%) and applying the chitosan in dispersed and gel beads forms for liquid effluents treatment as
Bioflocculant adsorbent for the removal of dye (Direct blue 71) from synthetic effluent (first application) and as
Soft deacetylation bioflocculant for the capture of particulate suspension from drinking water plant effluent (second
Adsorbent application) and for the improved settling of biological colloids such as bacteria from activated
Dye sludge after biological treatment of wastewaters (third application). This study demonstrated that
chitosan prepared in soft deacetylation condition has conserved its high affinity for many classes
of contaminants such as humic substances, inorganic matters, suspended solids, dye molecules
and bacterial suspensions. Good results were obtained for the maximal reduction of turbidity and
suspension matter at very lower concentration of dispersed biopolymer (1 mg/L and 1.5 mg/L in
two effluents, respectively) and for the total removal of color in natural medium pH by adsorption
at a ratio: 1g of beads/50ml of dye solution. Chitosans prepared in this study are all efficient if
used dispersed and gels.
© 2017 Process Engineering Journal.

Inorganic and organic wastes produced by human activities

1. Introduction (domestic, industrial and agricultural) as well as the excessive use of
synthetic substances produced by chemistry [1] have resulted in
Water pollution results from all human activities: domestic, high volumes of contaminated water which threatens human health
industrial and agricultural, but it is also due to synthetic substances and other living organisms [8].
produced by chemistry [1]. When water is polluted, Discharge of colored substances into water bodies can, not only
decontamination becomes necessary. The best purification approach aesthetically cause issues, but also harmful to biological organisms
is sought to reach the decontamination objectives required by law. and ecology [9]. Textile industries and other dyeing industries such
The literature reports a multitude of processes for the treatment of as paper, printing, leather, food and plastic are major industrial
contaminated water and wastewater [2-7]. However, many of the wastewater sources. Generally, the volume of discharged
available processes proposed cannot be used at an industrial scale wastewater from each step of a textile operation is approximately at
for technological and especially economic reasons. a high rate of between 40 and 65 L/kg of the product [10]. The
presence of dyes in textile wastewater is an environmental problem

* Corresponding author. E-mail address: hakim_lounici@yahoo.ca

© 2017 Process Eng. J. Process Engineering Journal is licensed under a "Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0)".
42 PROCESS ENGINEERING JOURNAL 1 (2017) 41–51

due to their high visibility, resistance and toxic impact [11]. Even low abundant biopolymer in the world, after cellulose. The main sources
concentration of dye in water is easily visible and can reduce exploited are two marine crustaceans, shrimps and crabs. Chitosan
photosynthetic activities in aquatic environments by preventing the has unique properties among biopolymers especially due to the
penetration of light and oxygen [12]. Given their synthetic origin and presence of primary amino groups. Moreover, it is a commercially
complex aromatic structures, dyes are non-biodegradable interesting compound because of its high nitrogen content in
substances that remain stable under different conditions [13]. In this comparison to cellulose [71].
case, common methods for removing dyes are either economically This study tests chitosan obtained by soft deacetylation
unfavorable and/or technically complicated. condition, as bioflocculant (from dispersed chitosan), in effluent of
It is now recognized that adsorption using low-cost adsorbents Taksebt drinking water treatment plant, in mixed liquor of urban
is an effective and economic method for water decontamination. wastewater treatment plant and as biosorbent (from beads chitosan)
Much attention has recently been focused on various biosorbent in dye treatment of synthetic water.
materials such as fungal or bacterial biomass and biopolymers that
can be obtained in large quantities and that are harmless to nature. 2. Materials and methods
Special attention has been given to polysaccharides such as chitosan,
a natural aminopolymer. 2.1. Materials
It is clear from the literature that the biosorption of dyes using
chitosan is one of the more frequently reported emerging methods
2.1.1. Direct blue 71
for the removal of this pollutant.
The azo dye Direct blue 71 (DB 71), molecular formula:
Guibal’s group [14-21] published a series of papers on the ability
C40H28N7NaO13S4 (molecular weight: 1029.9 g/mol) C.I. 34140, was
of chitosan to act as an effective coagulant to treat not only
chosen as adsorbate. The dye was supplied by a textile industry. Fig.
particulate suspensions but also dissolved substances. In particular,
1 displays the structure of this dye. A stock solution of DB 71 at 1000
they showed that color can be removed either by adsorption onto
mg/L was prepared, which was diluted to required different initial
solid-state chitosan or by coagulation/flocculation using dissolved-
concentrations: 10, 50, 100, 200 and 300 mg/L. The concentration of
state chitosan.
DB 71 in textile wastewaters is 50 mg/L [73,74].
Vakili et al. [22] have concentrated on developing materials
based on natural polymers such as chitosan to serve as alternative
2.1.2. Commercial flocculants
adsorbents with improved adsorption capacity and not
Commercial chitosan, purchased from Fluka, was used in this
compromising the low cost [23]. Chitosan based adsorbents have
study and noted ChitosCom. It is commonly prepared by
received a lot of attention for adsorption of dyes [24]. Various
deacetylating chitin using 40–50% aqueous alkali at 110–115 °C for a
modifications of this polysaccharide have been investigated to
few hours [75]. It comes from a chitin shell crab and was
improve the adsorption properties as well as mechanical and
characterized by a low molecular weight.
physical characteristics of chitosan.
A synthetic anionic polymer AN 910 used by Taksebt drinking
Due to its biodegradability and no residual toxicity, its
water treatment plant was employed in the present work.
polyelectrolytic nature, its solublity in acidic solutions [25-27] and
its tendency to flocculation, chitosan is also able to overcome the
2.1.3. Biological material: chitin extracted from shrimp wastes
nuisances of traditional coagulants/flocculants. According to its
This polysaccharide used in the experiments is coming from
excellent intrinsic characteristics such as: high cationic charge
different purification modes: (1) commercial chitin, purchased from
density, its outstanding chelation behavior [28-30], long polymer
Fluka and noted ChitiCom; (2) chemical chitin extracted from
chains, bridging of aggregates and precipitation (in neutral or
shrimp shell by chemical treatment as described by Kadouche [76]
alkaline pH conditions), chitosan is very recommended in the
and noted ChitiChem; (3) biological chitin extracted from shrimp
removal of various contaminants including both particulate and
shell by biological treatment as described by Arbia et al. [77] and
dissolved substances. These properties have been exploited to the
noted ChitiBio.
treatment of various effluents using coagulation/flocculation such
as: food, seafood and fish processing wastes [31-36], wastewater
2.1.4. Backwashing water of Taksebt treatment plant
from milk processing plant [37], brewery wastewater [38], surimi
Washing water collected from Taksebt drinking water treatment
wash water [39], inorganic suspensions (bentonite, kaolinite) [40-42],
plant presents a turbidity situated between 300 and 400 NTU, a pH
bacterial suspensions [43-45], effluents containing humic substances
of 7−8, a conductivity of 400 µS/cm and a UV absorbance at 254nm
[46,47], effluents containing dyes [48,49], pulp and paper mill
of 0.15. All samples were analyzed at the same day of collection.
wastewater [50,54], olive oil wastewater [55-57], oil-in-water
emulsions [58], aquaculture wastewater [59], effluent containing
metal ions [60-62], effluent containing phenol derivatives [63], 2.1.5. Mixed liquor of wastewater treatment from Est Tizi-ouzou city
partially purified sewage [64], raw drinking water [65], solid plant
suspensions from various food processing wastes [66], brackish The samples are collected in the outlet of aeration tank. They
water [67], latex particles [68], microorganisms [69], and the represent the mixed liquor suspended solids (TSS) at the end of
treatment of dyes in liquid effluents [70]. biological treatment just before the passage through the clarifier. The
Chitosan is a linear copolymer of D-glucosamine and N-acetyl- characteristic properties are situated between 4800 and 5500 mg/L
D-glucosamine produced by the deacetylation of chitin, a natural of TSS, 7.6-8.2 of pH and 820-950 µS/cm of conductivity.
polymer of major importance [71,72]. Chitin is the second most
 PROCESS ENGINEERING JOURNAL 1 (2017) 41–51 43

In conventional well-settling activated sludge, the flocs often was diluted to 100 mL by middle stirring of 3 to 4 h, and then let it
have a core structure formed by the filaments of filamentous stay still for 1 to 2 h.
bacteria. However, these filaments may grow to project out of the (ii) In an ice bath, the above solution was poured into a burette
flocs. If this growth continues, they may form a bridge between equipped with a syringe 20G. 20 mL of the chitosan (commercial and
adjacent flocs and prevent their independent motion. The different deacetylated chitin) solution were dropped from the burette into a
forms that the flocs of activated sludge can take are related to 150 mL aqueous solution of NaOH (2N). The chitosan droplets
various settlement problems. formed a bead shape in the solution. It was left in the aqueous
The changes in process variables, including sludge loading, solution for more than 24 h. The filtered chitosan beads were washed
nutrient concentration and oxygen concentration are responsible of by distilled water and stored for later use. The diameter of the beads
various settlement problems such as deflocculation, pin-point floc, was measured with an electronic foot slides (Stailess Hardened
foaming and foam formation and filamentous bulking. Promotion of (mm/inch)).
sludge settling may also be attempted by the addition of lime, iron
salts or synthetic organic polymers. 2.2.4. Coagulation flocculation experiments (Jar Tests)
Coagulation-flocculation experiments were carried out through
2.2. Methods a conventional Jar Test (Janke and Hunkeler) having 5 agitators and
trains with variable speed. Each train is equipped with a 1 L beaker.
2.2.1. Deacetylation condition of chitin As soon as a fixed amount of the chitosan (commercial and
Chitosan was obtained by the deacetylation of chitin which was deacetylated chitin) solution was added to the suspension, the
made by alkaline hydrolysis: an amount of chitin, as presented mixture was strongly stirred at 200 rpm during 3 min for wash
above, is suspended in 40% NaOH at two temperatures (25 and waters and 250 rpm during 3 min for mixed liquor (coagulation
30°C) during various days (Table 1). The obtained chitosan was then phase). This step was followed by a slow mixing at 45 rpm during
filtered, washed with distilled water until pH stability and oven- 20 min for wash waters and 50 rpm during 20 min for mixed liquor
dried at 50 °C for 24h. The samples of chitin deacetylated are noted (flocculation phase) [78]. Thereafter, the solution was allowed to
Chiti DA. settle for 60 min. 25 mL of the supernatant were taken at different
settling times and measured by a Hach spectrophotometer for
Table 1 – Conditions of chitin deacetylation. turbidity level, TSS, pH and conductivity.
Mode T (°C) Time (day) Notation The experimental conditions should be chosen to simulate real
wastewater: ambient temperature (25±2°C) and natural pH (7-8).
Chemical 25 11 ChitiChemaDA 11dT25
Chemical 25 13 ChitiChemaDA 13dT25
Chemical 30 10 ChitiChemaDA 10dT30
Chemical 30 11 ChitiChemaDA 11dT30
Chemical 30 13 ChitiCombDA 13dT30
Chemical 30 15 ChitiCombDA 15dT30
Biological 25 11 ChitiBiocDA 11dT25
Biological 30 10 ChitiBiocDA 10dT30
Biological 30 13 ChitiBiocDA 13dT30
Fig. 1. Chemical structure of Direct Blue 71.
a: [76]; b: commercial chitin (Fluka); c: [77]
2.2.5. Batch decolorization studies
2.2.2. Preparation of chitosan solution for coagulation-flocculation tests In batch adsorption kinetic experiments, 1 g of wet chitosan
100 mg of chitosan (commercial and deacetylated chitin) were beads and 25 mL of dye solution were mixed in a 50 mL flask and
dissolved in 1 mL of acetic acid (85% (w/w)) under agitation and manually stirred at ambient temperature (25±3 °C). The DB 71 dye
subsequently hydrated overnight in 99 mL of demineralized water concentration was determined at a wavelength of 587 nm by a UV–
[78]. The final polymer solution was maintained at pH 4. One dose vis. spectrometer (Jasco V-530) at pH 6.5.
of polymer solution was tested: 1 mg of dispersed chitosan per liter The experimental conditions have been conducted at ambient
of Taksebt effluent optimized in previous study (results not temperature (25±2 °C) and natural pH (6.2), in accordance with
published) and 1.5 mg of dispersed chitosan per liter of mixed liquor Soleymani [80].
optimized in our study and presented by Belksir et al. [79]. Stirring is an important parameter in adsorption phenomena,
influencing the distribution of the solute in bulk solution and the
2.2.3. Preparation of chitosan beads for decolorization formation of the external boundary film. The Uzun’s work [81]
The preparation of chitosan beads involves two steps: (i) indicated that there is a small effect of shaking rate on the adsorption
chitosan dissolution and (ii) beads formation. of two model dyes by chitosan. Wu et al. [82] also noted that
(i) 1.5 g of chitosan (commercial and deacetylated chitin) were agitation had little effect on adsorption. Therefore, in this study,
dissolved in 25 mL of acetic acid solution (2N). The aqueous solution experiments were performed without stirring.
44 PROCESS ENGINEERING JOURNAL 1 (2017) 41–51

a)
100
Chiou and Li [83] reported that the adsorption rate on wet beads
90
is much faster than that on dry beads and the time lag to reach
80
-1 similar adsorption capacity is lower because it takes time for the dry
10mg.l
Removal yield of dye (%)

70
50mg.l
-1
beads to swell before adsorption can take place. The same result was
60 -1
100mg.l
50 200mg.l
-1 reported by Chang and Juang [84].
-1
300mg.l
40
ChitiBio DA13dT30
30 3. Results and discussion
20

10
3.1. Effect of chitosan beads on DB 71 removal
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
t (h) Chitosan beads are preferred since flake and powder forms of
100 b)
polymer are not suitable for use as adsorbents due to their low
90
10mg.l
-1
surface area and lack of porosity, as indicated by Varma et al. [85].
80 -1
50mg.l
-1
Chang and Juang [84] and Crini et al. [86] reported that bead-type
Removal yield of dye (%)

70 100mg.l
60
200mg.l
-1
chitosan gives a higher capacity for dye adsorption than the flake
-1
300mg.l
50
type by a factor of 2–4 depending on the source of fishery waste [82].
40 The authors explained this result by the fact that the beads possessed
30
ChitiChem DA10dT30 a greater surface area (i.e., more loose pore structure) than the flakes.
20 Guibal et al. [87] indicated that it would be interesting to use
10 chitosan gel beads instead of flakes since the production of gel beads
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
decreases the residual crystallinity of polymer, which enhances both
t (h) porosity and diffusion properties of the material, due to the
c)
100
expansion of the chitosan network and the increase in the specific
90
surface area.
Removal yield of dye (%) (%) (%)

80
The chitosan beads (commercial and all deacetylated chitins
70
prepared in this work) were spherical, except for ChitiCom DA
60
13dT30, rigid and presenting various diameters (Table 2).
50
ChitiChem DA13dT25 -1
40
10mg.l
-1

30
50mg.l
-1
Table 2 – Characteristics of formed beads (total weight, diameter)
100mg.l
20 200mg.l
-1 for commercial chitosan and different deacetylated chitins.
-1
300mg.l
10 Chitosans Total beads Average beads
0 weight (g) diameter (mm)
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
t (h) ChitosCom 11.64 1.76-2.29
100 d)
ChitiChem DA10dT30 11.51 2.07-2.79
90

80 ChitiChem DA13dT25 11.65 1.81-2.17

ChitiBio DA13dT30 11.6 1.85-2.27
Removal yield of dye (%)

70

60
10mg.l
-1 ChitiCom DA13dT30 10.15 Not spherical
50 ChitiCom DA13dT30 -1
50mg.l
40

30 Two parameters are studied: contact time and initial

20 concentration of DB 71. Contact time is an important parameter in
10
adsorption processes. Usually, the adsorption capacity and the
0
0 10 20 30 40 50 60 70 80 90 100 removal efficiency of dyes by chitosan become higher when
t (h) prolonging the contact time. However, in practice, it is necessary to
100 e)
optimize the contact time, considering the efficiency of desorption
90
and regeneration of the adsorbent.
80
The effect of contact time upon DB 71 removal by deacetylated
Removal yield of dye (%)

70

60
chitin (ChitiChim DA 10dT30, ChitiChim DA 13dT25, ChitiBio DA
50 13dT30 and ChitiCom DA 13dT30) and by commercial chitosan
40 10mg.l
-1
-1
(ChitosCom) is presented in Fig. 2. The removal rate increased with
Chitos Com 50mg.l
30
100mg.l
-1 the increase of time with all deacetylated chitins as well as with
ChitosCom. It reaches a maximum recovery above 98% within 150 h
-1
20 200mg.l
-1
300mg.l
10 (Fig. 2) with all initial dye concentrations varying from 10 to 300
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
mg/L. Thus, in these conditions, the contact time and adsorption
t(h) rate are not dependent on the initial DB 71 concentration. These
Fig. 2. Evolution of dye removal yield with contact time at different results contradict those of some researchers. Gibbs et al. [88]
initial dye concentrations (10−300 mg/L). observed that increasing the initial dye concentration increased the
 PROCESS ENGINEERING JOURNAL 1 (2017) 41–51 45

time required for complete recovery of the dye. This indicates that a 400
without floculant
350
large interval of initial dye concentration plays an important role in 300
with 1mg of synthetic flocculant
(polymer AN910)
the removal efficiency of DB 71 on the chitosan beads. 250
200

Residual turbidity (NTU)

10 (a) initial DB 71 concentration =10mg.l
-1
150
9 100
50
Residual dye concentration (mg.l )
-1

7
ChitosCom
10
6 ChitiChem DA10dT30
ChitiChem DA13dT25
5 ChitiBio DA13dT30 5
ChitiCom DA13dT30
4

3 0
0 10 20 30 40 50 60
2
t (min)
8,0
1

0
0 20 40 60 80 100 120 140 160 7,8
t (h)
50 -1
(b) initial DB 71 concentration= 50mg.l
45 7,6
Residual dye concentration (mg.l )
-1

40

pH
35
without floculant
7,4
with 1mg of synthetic flocculant
ChitosCom
30 (polymer AN910)
ChitiChem DA10dT30
25 ChitiChem DA13dT25
7,2
ChitiBio DA13dT30
20 ChitiCom DA13dT30
15
7,0
10 0 5 10 15 20 25 30 35 40 45 50 55 60
t (min)
5 400

0
0 20 40 60 80 100 120 140 160
380
t (h)
100 -1
(c) initial DB 71 concentration = 100mg.l
Conductivity (µS/cm)

90
360
Residual dye concentration (mg.l )
-1

80
ChitosCom
70 ChitiChem DA10dT30
ChitiChem DA13dT25 340
without floculant
60 ChitiBio DA13dT30
with 1mg of synthetic flocculant
50 (polymer AN910)
320
40

30
300
20
0 5 10 15 20 25 30 35 40 45 50 55 60
10 t (min)
0,14
0
0 20 40 60 80 100 120 140 160 180 200
t (h) 0,12
200 (d) initial DB 71 concentration= 200mg.l
-1
Absorbance u.a (254nm)

180 0,10
Residual dye concentration (mg.l )
-1

160
0,08
140 ChitosCom
120
ChitiChem DA10dT30 0,06 without floculant
ChitiChem DA13dT25 with 1mg of synthetic flocculant
100 ChitiBio DA13dT30
0,04 (polymer AN910)
80
0,02
60

40 0,00
0 5 10 15 20 25 30 35 40 45 50 55 60
20
t (min)
0
0 20 40 60 80 100 120 140 160
t (h)
300 Fig. 4. Evolution kinetics of turbidity, pH, conductivity and
-1
275 (e) initial DB 71 concentration = 300mg.l
absorbance at 254 nm without and with flocculant and anionic
250
Residual dye concentration (mg.l )
-1

225
polymer.
200
ChitosCom
175 ChitiChem DA10dT30 The kinetic curves show two phases: at the beginning, the dye
150 ChitiChem DA13dT25
125
ChitiBio DA 13dT30 ions were adsorbed by the exterior surface of chitosan beads, and
100 the adsorption rate was fast (almost 5 h). When the adsorption on
75
the exterior surface reached saturation, the DB 71 dye ions entered
50

25 into the pores of the beads and are adsorbed onto the interior surface
0 of the adsorbent. This phenomenon takes relatively long contact
0 20 40 60 80 100 120 140 160
t (h) time (almost few days). The time profile of dye uptake is single,
Fig. 3. Evolution of residual dye concentration with contact time at smooth and continuous, but not leading to saturation. The
different deacetylated chitins and commercial chitosan with all equilibrium was not attained under these operating conditions.
initials concentrations.
46 PROCESS ENGINEERING JOURNAL 1 (2017) 41–51

Thus, it is necessary to increase the DB 71 initial concentration or to mg/L, below 5 mg/L for C0 = 50 mg/L, below 10 mg/L for C0 = 100
decrease the amount of chitosan wet beads in solution. and 200 mg/L and below 20 mg/L for C0 = 300 mg/L.
At pH 6.2, the amine groups of chitosan molecules are
400 protonated to form −NH3+ [91], thereby increasing electrostatic
350 without flocculant
300 with 1.2mg of ChitosCom (Fluka) attractions between dye molecules and adsorption sites and causing
250 the observed removal of the dye.
200
Residual turbidity (NTU)

150 400
100 350
300
50
250 without flocculant
5
200 with 1mg of ChitiBioDA13dT30

Residual turbidity (NTU)

4 150

3 100
50
2
9
1 8
7
0 6
0 5 10 15 20 25 30 35 40 45 50 55 60 5
t (min) 4
10 3
2
9 1
0
8 0 5 10 15 20 25 30 35 40 45 50 55 60
t (min)
7

6 400
350
5
300
pH

without flocculant 250

without flocculant
4 with 1mg of ChitiChem DA10dT30
with 1.2mg of ChitosCom (Fluka) 200

Residual turbidity (NTU)

3 150
100
2
50
1
9
8
0
7
0 5 10 15 20 25 30 35 40 45 50 55 60 6
t (min) 5
500 4
3
450 2
1
400 0
0 5 10 15 20 25 30 35 40 45 50 55 60
350 t (min)
400
Conductivity (µS/cm)

300 350 without flocculant

300 with 1mg of ChitiChem DA11dT25
250
250
200 200
Residual turbidity (NTU)

without flocculant
150
150 with 1.2mg of ChitosCom(Fluka)
100
100 50
9
50 8
7
0 6
0 5 10 15 20 25 30 35 40 45 50 55 60 5
4
t (min) 3
0,50
2
1
0,45 0
0 5 10 15 20 25 30 35 40 45 50 55 60
0,40
t (min)
without flocculant 400
0,35 without flocculant
with 1.2mg of ChitosCom(Fluka) 350
Absorbance (254nm)

with 1mg of ChitiCom DA15dT30

0,30 300
250
0,25 200
Residual turbidity (NTU)

150
0,20
100
0,15 50

0,10 9
8
0,05 7
6
0,00 5
0 5 10 15 20 25 30 35 40 45 50 55 60 4
3
t (min) 2
1
0
0 5 10 15 20 25 30 35 40 45 50 55 60
t (min)
Fig. 5. Evolution kinetics of turbidity, pH, conductivity and
absorbance at 254nm without and with commercial chitosan.
Fig. 6. Evolution kinetics of turbidity with deacetylated chitins.
The presence of even small amounts of dyes (below 1 mg/L) is
clearly visible and influences considerably the water quality [89,90]. The above result is in agreement with the literature: at neutral
After 150 h of contact time, residual concentration of DB71 (Fig. 3) pH, about 50% of total amine groups remain protonated and
depends on initial dye concentration (C0): below 1 mg/L for C0 = 10 theoretically available for the adsorption of dyes. The existence of
free amine groups may cause direct complexation of dyes co-
 PROCESS ENGINEERING JOURNAL 1 (2017) 41–51 47

existing with anionic species, depending on the charge of the dye. 3.2. Effect of dispersed chitosan on washing water treatment of
Guibal et al. [92] showed that not all the amino groups are really Taksebt plant
available or at least accessible. The weakly porous structure of the
polymer and its residual crystallinity are critical parameters for the Without flocculant, turbidity decreases rapidly from 376 to 102
hydratation and the accessibility to adsorption sites. NTU within 5 min and then, slowly decreases to reach 60 NTU at the
Additionally, it was important to note that no variation of pH end of treatment (1 h) (Fig. 4). The wash water contained settling
solution was observed during adsorption process. matters such as silica. Natural settling is not efficient because
residual turbidity is higher than the norm (5 NTU for treated water).
5500
When 1 mg of anionic polymer (AN 910) is added in 1 L of
5000
effluent, turbidity rapidly decreases from 376 to 8 NTU within 5 min
4500
without flocculant
1.5mg of ChitiBio DA 10dT30 and then, slowly decreases to reach 6 NTU at the end of treatment (1
4000
h) (Fig. 4). After 24 h, no return to stabilization was observed.
TSS (mg.l )
-1

3500

3000
Residual turbidity is near the norm (5NTU) using the synthetic
Residual MES

34
32
30 polymer AN 910.
28
26
24
22 In the presence of anionic polymer, pH and conductivity (Fig. 4)
20
18
16
14
values do not change over time. They are situated in the same
12
10
8
6
interval obtained without flocculant: 7.5-8 and 375-400 µS/cm,
4
2
0 respectively. The UV absorbance value at 254 nm do not vary with
0 5 10 15 20 25 30 35 40 45 50 55 60
time (0.11 with flocculant and 0.14 without flocculant). Polymer
t (mn)
reduces humic substances from water.
5500

5000
without flocculant With 1 mg of commercial chitosan (Fluka) added to 1 L of
1.5mg of ChitiBio DA 11dT25
4500
effluent, turbidity decreases rapidly from 376 to 1 NTU within 5 min
4000
and then, decreases very slowly for reaching 0.98 NTU at the end of
TSS (mg.l )

treatment (1 h) (Fig. 5). After 24 h, return to stabilization was not

-1

3500

3000 observed. Residual turbidity (0.98 NTU) obtained with ChitosCom

Residual MES

34
32
30
28
is below the norm (5 NTU) contrarily to plant polymer (6 NTU) and
26
24
22
20
to natural settling (60 NTU). The amino polysaccharide is very
18
16
14 efficient if compared to synthetic polymer in treatment of filters
12
10
8
6 washing waters. The pH is situated at lower values (7-7.5) than its
4
2
0 value for anionic polymer and without flocculant (7.5-8). For
0 5 10 15 20 25 30 35 40 45 50 55 60
t (mn) conductivity and UV absorbance at 254 nm (Fig. 5), the values are
5500
the same as with synthetic polymer. These parameters remain
5000 constant with time.
4500 without flocculant Coagulation-flocculation of washing water with addition of 1
1.5mg of ChitiChem DA11dT30
4000 mg of deacetylated chitin (ChitiBio DA13dT30, ChitiChem
TSS (mg.l )
-1

3500 DA10dT30, ChitiChem DA11dT25 and ChitiCom DA15dT30) in 1 L

3000 of effluent produced a very low residual turbidity (1 NTU) within 5
Residual MES

34
32
30
28
26
min, this value remains constant until the end of treatment (1 h) (Fig.
24
22
20 6) and also during 24 h. In our experiments, all chitosans cited
18
16
14
12 previously and ChitosCom (Fluka) conducted in 5 min to a similar
10
8
6
4
yield removal of turbidity (up to 99.7%). Consequently,
2
0
0 5 10 15 20 25 30 35 40 45 50 55 60
deacetylation conditions (temperature and duration) have no effect
t (mn) on flocculant properties. The results of pH, conductivity and
5500 absorbance at 254 nm with all chitosans are identical to commercial
without flocculant
5000 1.5mg of ChitiChem DA11dT25 chitosan (data not presented).
4500 It was important to notice that 1 mg of dispersed chitosan added
4000 to 1 L of liquid effluent (in acidic condition) does not modify the pH
TSS (mg.l )
-1

3500
and does not increase the organic matters concentration.
3000
Residual MES

34
32
30
28
26 3.3. Effect of dispersed chitosan on mixed liquor of wastewater
24
22
20
18
treatment from Est Tizi-ouzou city plant
16
14
12
10
8
6
4 Without flocculant addition, settling test was established for
2
0
0 5 10 15 20 25 30 35 40 45 50 55 60 each coagulation-flocculation experiment. The average residual TSS
t (mn) demonstrated a rapidly decrease in the first minutes: 67 mg/L after
1 min, 29 mg/L after 2 min, 25 mg/L after 3 min, 16 mg/L after 4
Fig. 7. Evolution kinetics of TSS with deacetylated chitins. min and 13 mg/L after 5 min (Fig. 7). After this time, a slowly
48 PROCESS ENGINEERING JOURNAL 1 (2017) 41–51

decrease was obtained reaching 9 mg/L after 20 min and 5 mg/L effluent—an overview. Environ. Eng. Sci. 25 (2008) 383–
after 60 min. 396.
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The addition of 1.5 mg of all deacetylated chitins (ChitiBio
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concentration.
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In natural settling, treated water approaches the norm of TSS (30 Adsorption of phenolic compounds by activated
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with amino polysaccharide, the residual TSS was lower and 1070.
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Please cite this article as: D. Aili, I. Feraoun, L. Adour, H. Lounici, Use of dispersed and beads chitosan in liquid effluents
treatment, Process Eng. J. 2 (2017) 41−51.