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A Review On Application
A Review On Application
Review
a b s t r a c t
Flocculation is an essential phenomenon in industrial wastewater treatment. Inorganic coagulants (salts of multivalent metals) are being commonly used due to its low cost and ease of use. However, their application is constrained
with low occulating efciency and the presence of residue metal concentration in the treated water. Organic polymeric occulants are widely used nowadays due to its remarkable ability to occulate efciently with low dosage.
However, its application is associated with lack of biodegradability and dispersion of monomers residue in water
that may represent a health hazard. Therefore, biopolymers based occulants have been attracting wide interest of
researchers because they have the advantages of biodegradability and environmental friendly. But, natural occulants are needed in large dosage due to its moderate occulating efciency and shorter shelf life. Thus, in order to
combine the best properties of both, synthetic polymers are grafted onto the backbone of natural polymers to obtain
tailor-made grafted occulants. This paper gives an overview of the development of different types of occulants
that were being investigated for treatment of industrial wastewater. Furthermore, their occulation performance
will be reviewed and the occulation mechanism will be discussed.
2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Coagulationocculation; Direct occulation; Bio-occulants; Grafted occulants; Flocculation mechanism; Wastewater treatment
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Coagulationocculation and direct occulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Coagulationocculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Direct occulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Comparison between coagulationocculation and direct occulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chemical coagulants and occulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Inorganic coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Organic synthetic occulants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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493
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Abbreviations: BOD5 , 5 days biochemical oxygen demand; CD, charge density; C-F, coagulationocculation; COD, chemical oxygen
demand; C-PAM, cationic polyacrylamide; D-F, direct occulation; LDS, light diffraction scattering; MW, molecular weight; RP, reactive
phosphorus; SVI, sludge volume index; TDS, total dissolved solids; TOCsoluble , soluble total organic carbon; TP, total phosphorus; TS, total
solids; TSS, total suspended solids.
Corresponding author. Tel.: +60 3 8924 8347; fax: +60 3 8924 8017.
E-mail addresses: MeiFong.Chong@nottingham.edu.my, chong mei fong@yahoo.com (M.F. Chong).
Available online 2 May 2014
http://dx.doi.org/10.1016/j.psep.2014.04.010
0957-5820/ 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
490
4.
Natural bio-occulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Tannin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3. Gums and mucilage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4. Sodium alginate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5. Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6. Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Grafted occulants/graft copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Selection of occulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Flocculation mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.1. Mechanism for chemical occulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.1.1. Charge neutralisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.1.2. Polymer bridging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.1.3. Electrostatic patch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.2. Mechanism for natural bio-occulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.3. Mechanism for grafted occulants/graft copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.4. Summary of occulation mechanism for different types of occulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion and future perspectives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.
6.
7.
8.
1.
Introduction
496
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499
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501
501
503
503
503
504
504
504
505
505
506
developed or designed to improve the occulation process in wastewater treatment including synthetic or natural
organic occulants and grafted occulants.
Polymeric occulants, synthetic as well as natural have
become very popular in industrial efuent treatment due to
their natural inertness to pH changes, high efciency with
low dosage, and easy handling (Singh et al., 2000). However,
the synthetic polymeric occulants have the main problems
of non-biodegradability and unfriendly to the environment,
while the natural occulants are concerned with moderate
efciency and short shelf life. In order to combine the best
properties of synthetic and natural polymers, grafted occulants have been synthesised and studied extensively recently.
As occulants plays the major role in occulation process,
the search for high efcient and cost-effective occulants has
always become the challenge in many studies. The main process variables that are commonly measured to justify the
occulation efciency include settling rate of ocs, sediment
volume (sludge volume index, SVI), percent solids settled, turbidity or supernatant clarity, percentage of pollutants removal
or water recovery depending on the industrial application
(Bohuslav Dobias, 2005). All these output variables are actually
manifestations of the oc or aggregate size distribution and
the shape and structure of ocs produced during the occulation process. Bigger, stronger and denser ocs are preferable
for good sedimentation, easy ltration and high clarication.
The present review article classies the occulants that
have been studied and applied in wastewater treatment into
three categories including chemical coagulants/occulants,
natural bio-occulants and grafted occulants as shown
in Fig. 1. Chemical coagulants/occulants are conventionally applied in wastewater treatment and derived
from chemically/petroleum-based materials. Natural bioocculants are extensively explored on the past few years and
sourced from natural materials. Meanwhile, grafted occulants are investigated recently and synthesised by combining
the properties of chemical and natural occulants. This review
has compiled all the recent literature about occulants and is
expected to provide an overview of recent information regarding the development and application of various occulants
in treating wastewater. In addition, its occulating efciency
491
Categories of Flocculants
Natural Bio-flocculants
Chitosan
Synthetic polymers:
polyacrylamide, poly(2methacryloyloxyethyl) trimethyl
ammonium chloride
salts
Cellulose
Flocculants: Synthetic organic
polymers
Sodium alginate
Tannin
2.
Coagulationocculation and direct
occulation
There are two methods of wastewater treatment which are
coagulationocculation and direct occulation. The summary of their application in different types of wastewater is
presented in Tables 1 and 2.
2.1.
Coagulationocculation
2.2.
Direct occulation
492
Table 1 Application of coagulationocculation process with chemical coagulant(s) and occulant(s) in wastewater treatment.
Coagulant(s)
Flocculant(s)
Type of wastewater
Optimum results
Reference
Sanitary landll
leachates
COD
Colour
Anionic polyacrylamide
Copper
99.6% removal
Li et al. (2003)
Turbidity
Water
recovery
>98% removal
78%
TSS
3095% removal
TP
COD
3080% removal
1040% removal
Anionic polyacrylamide
Abattoir wastewater
COD
TSS
TP
94% removal
94% removal
97% removal
Coffee wastewater
COD
5560% removal
Ferric chloride
Non-ionic polyacrylamide
COD
TP
TSS
91% removal
99% removal
97% removal
Alum/ferric salt
Colour
Colour
62% removal
Turbidity
TSS
COD
SVI
Settling
time
99.7% removal
99.5% removal
95.6% removal
38 ml/g
12 s
Boron
TSS
153 mg/L
20005 mg/L
High-phosphorus hematite
otation wastewater
Turbidity
13,53012NTU
Aluminium polychloride
COD
82% removal
Turbidity
TOCsoluble
72% removal
13% removal
the author showed that the total treatment cost of conventional treatment was 3.6 times higher than direct occulation
due to larger volumes of phyto-toxic sludge produced from
coagulationocculation process.
As presented in Table 2, direct occulation was workable
in treatment of oily wastewater (Zhong et al., 2003), olive mill
efuent (Sarika et al., 2005), aquaculture wastewater (Ebeling
et al., 2005), coal waste slurry (Sabah and Erkan, 2006), pulp
and paper mill wastewater (Wong et al., 2006; Razali et al.,
2011), and textile wastewater (Kang et al., 2007; Yue et al.,
2008). The research ndings showed that high occulation
efciency could be achieved by using single polymer only as
occulant where more than 90% removal of turbidity, TSS, COD
and colour could be observed in specic wastewater.
2.3.
Comparison between coagulationocculation and
direct occulation
As presented above, direct occulation has been applied to
replace coagulationocculation in certain types of wastewater treatment. However, its application is mostly limited to
organic-based wastewater with high concentration of suspended and colloidal solids; such as food, paper and pulp, and
textile efuents. Thus, conventional coagulationocculation
process is still preferable and widely employed by most of the
industries because it can be applied for both inorganic and
organic-based wastewater with suspended and dissolved solid
constituents (Chong, 2012). As a summary, each treatment
process has its own pros and cons and the type of wastewater is the main factor that inuences the selection between
coagulationocculation and direct occulation. Regardless
of limited application of direct occulation, this process is
still worthwhile to be explored due to its advantages of less
chemical used in the treatment, simpler process, less sludge
is produced and lower treatment cost. An overview of the
differences between coagulationocculation and direct occulation and the general procedures for each process are
presented in Table 3 and Fig. 2, respectively.
Aluminium sulphate
Anionic polyacrylamide
(Magnaoc 155)
3.
Table 1
493
The conventional chemicals that are widely applied in industrial wastewater treatment can be classied into two major
groups: inorganic mineral additives/metal salts which are
used as coagulants and organic polymeric materials that are
employed as occulants.
3.1.
Inorganic coagulants
Inorganic salts of multivalent metals such as alum, polyaluminium chloride, ferric chloride, ferrous sulphate, calcium
chloride and magnesium chloride have been widely used for
decades as coagulant (Joo et al., 2007). It is mainly because
of its advantage of low cost, where their market price is very
much lower compared to the chemical occulants as shown
in Table 4.
However, the application of inorganic coagulants in
wastewater is quite limited nowadays and has been reduced
due to numerous disadvantages. As reported in many studies,
its usage would cause two important environmental consequences which are the production of large volumes of metal
hydroxide (toxic) sludge which will create disposal problem
and an increase in metal (e.g. aluminium) concentration in
the treated water which may have human health implications
494
Derivative of polyacrylamide
(Poly1 and 3530S), polyacrylamide
Optimum results
Reference
Oil
COD
TSS
COD
BOD5
Aquaculture wastewater,
6.977.78
TSS
99% removal
RP
9295% removal
TSS
TP
COD
9799% removal
5056% removal
1735% removal
Turbidity
256.8NTU
Turbidity
95% removal
TSS
COD
SVI
Water recovery
98% removal
93% removal
14 ml/g
91%
Cationic polydiallyldimethylammonium
chloride (PDADMAC)
Colour
>90% removal
Cationic polyamine
Colour
96% removal
Colour
90% removal
COD
89% removal
Turbidity
TSS
COD
91% removal
Nearly 100% removal
98% removal
Cationic
polydiallyldimethylammonium
chloride (polyDADMAC)
495
Coagulationocculation
Application
Treatment ability
Types of chemicals to be used
Direct occulation
Treatment process
Sludge generated
Overall treatment cost
Flocculating mechanism
Organic-based wastewater
Suspended and colloidal particles
Cationic or anionic polymeric occulants
(usually cationic)
Simpler, without pH adjustment
Less sludge is produced, may contain
monomers residue
Less expensive because only one chemical
is used and less sludge treatment cost
Charge neutralisation and bridging occur
concurrently
Wastewater collection
Characterization of wastewater
Coagulation-flocculation
Direct flocculation
Addition of flocculant
Addition of coagulant
Addition of coagulant
Addition of flocculant
Addition of flocculant
Sedimentation/settling of flocs
Sedimentation/settling of flocs
minimise the drawbacks of inorganic occulants, many factors have been taken into consideration to nd the alternative
and reduce the dosage of the harmful inorganic occulants.
3.2.
Table 4 Market prices for bulk sales of chemical coagulants and occulants (Sarika et al., 2005).
Chemical materials
Price, D /tonne
Coagulants
Cationic occulants
Anionic occulants
Lime
FeCl3
FO-4700
FO-4490
FLOCAN
AN 934
130
450
2980
2800
2500
2550
496
Categorisation
Nature of charges
Amphoteric/anionic/cationic/non-ionic
Molecular weight
Low
Medium
Standard
High
Very high
13 millions
36 millions
610 millions
1015 millions
Greater than 15 millions
Charge density
Low
Medium
High
Very high
110%
1040%
4080%
80100%
4.
Natural bio-occulants
Flocculant(s)
Type of wastewater
Iron(III) chloride
Chitosan
Chitosan
Aluminium sulphate
Chitosan
Chitosan
Anionic tannin
Anionic tannin
Dye-containing solutions
Drinking water
Ink-containing efuent from
cardboard box-making factory
Optimum results
Turbidity
COD
COD
Turbidity
Dye
Turbidity
Colour
101.1NTU
1303516 mg/L
80% removal
85% removal
99% removal
3002FTU
>99% removal
Municipal wastewater
COD
Cu2+ , Zn2+
and Ni2+
Turbidity
Sewage efuent
COD
BOD5
TSS
84% removal
90%, 75% and 70%
removal
Almost 100%
removal
Around 50% removal
Around 50% removal
95% removal
Tannery efuent
Tannery efuent
TSS
TSS
87% removal
85% removal
TDS
Dye
40% removal
60% and 25%
removal
67% removal
74% removal
Turbidity
COD
64% removal
90% removal
96% removal
93% removal
93.4% removal
80.1% removal
93% removal
Sodium alginate
Aluminium sulphate
Cellulose
Aluminium sulphate
Anionic sodium
carboxymethylcellulose (CMCNa)
Anionic dicarboxylic acid
nanocellulose (DCC)
Drinking water
Colour
TSS
Colour
Colour
COD
Turbidity
Municipal wastewater
Turbidity
4080% removal
COD
4060% removal
Ferric sulphate
Reference
Al-Hamadani et al.
(2011)
Tannin
Coagulant(s)
Wu et al. (2012)
497
498
4.1.
Chitosan
water treatment (zacar and Sengil, 2003), removal of suspended matters from synthetic raw water (zacar and Sengil,
2000), and removal of dyes, pigments and inks from inkcontaining wastewater (Roussy et al., 2005). In these studies,
coagulant such as aluminium sulphate was needed for destabilisation of the negatively charged colloidal particles, while
anionic tannin acted as occulant to bridge the destabilised
aggregates together to form ocs of such a size suitable for
sedimentation. A study showed that coupling of aluminium
sulphate as coagulant and tannin as occulant signicantly
reduced the required doses of the coagulant (zacar and
Sengil, 2003).
In order to eliminate the necessity of coagulant, modied
tannin (Tanoc occulant) has been investigated recently to
remove heavy metals from polluted surface water (Beltrn
Heredia and Snchez Martn, 2009) and in municipal wastewater treatment (Beltrn-Heredia and Snchez-Martn, 2009).
Tanoc is obtained from Acacia mearnsii bark and modied
by a physico-chemical process. Groups of hydrocolloid gums
and other soluble salts are included in the Tanoc structure with chemical modication which includes a quaternary
nitrogen to give Tanoc cationic character (Beltrn Heredia
and Snchez Martn, 2009). Due to its cationic property, it
can be used for direct occulation without coagulant and pH
adjustment.
4.3.
4.4.
4.2.
Sodium alginate
Tannin
Sodium alginate, the sodium salt of alginic acid, with an average molecular weight of 500,000, is a linear water-soluble
anionic polymer (Wu et al., 2012). A recent study investigated
its occulating efciency in treatment of industrial textile
wastewater and synthetic dye wastewater by using aluminium
sulphate as the coagulant (Wu et al., 2012). The experimental
Plant
Aqueous extraction
Drying
Fig. 3 General processing steps in preparation of
plant-based occulants.
results revealed that it exhibited high occulating property
where more than 90% colour removal and 80% of COD reduction were obtained after treatment.
4.5.
Cellulose
Cellulose is one of the most abundant natural polysaccharide. It has been the subject of research in recent years,
mainly with respect to modify its physical and chemical structure by improving its properties and broadening its industrial
applications (Das et al., 2012). Anionic sodium carboxymethylcellulose (CMCNa) that was prepared from an agricultural
waste date palm rachis was tested as eco-friendly occulants
coupled with aluminium sulphate as coagulant for removal
of turbidity in drinking water treatment (Khiari et al., 2010).
In another study, anionized dicarboxylic acid nanocellulose
(DCC) occulant was produced and examined its occulating property with ferric sulphate as coagulant in municipal
wastewater (Suopajrvi et al., 2013).
4.6.
Challenges
Even though bio-occulants displayed promising occulating efciency in treatment of different types of wastewater
but its future development is constrained by some disadvantages. Natural polymers have shorter shelf life because its
active components will biodegrade with time and thus needs
to be suitably controlled. Furthermore, the ocs tend to loose
stability and strength with time because of their biodegradability. Most biodegradable natural and biopolymers contain
hydrolysable groups along with the main chain which can
cause biodegradation to happen via hydrolysis (Singh et al.,
2000). In addition, some of the anionic bio-occulants (e.g. tannin, cellulose, alginate) are moderately effective and only can
be utilised as coagulant aid. In the coagulationocculation
process, cationic coagulant is required for charge neutralisation before bio-occulant could bridge the micro-ocs
together and high dosage is needed to achieve efcient occulation. Hence, in order to address all these concerns, new
generation of polymeric occulants has been developed by
499
5.
500
Aluminium chloride
Flocculant(s)
Chitosan grafted PDMC
(poly(2methacryloyloxyethyl)
trimethyl ammonium
chloride)
(2-methacryloyloxyethyl)
trimethyl ammonium
chloride (DMC) grafted
chitosan (cationic)
Type of wastewater
Turbidity
6878.7NTU
Turbidity
99.4% removal
Lignin
COD
Turbidity
81.3% removal
90.7% removal
204NTU
TS
Turbidity
602356 ppm
9754NTU
TS
COD
Turbidity
640309 ppm
586221 ppm
99.6% removal
Lignin
Water recovery
Turbidity
88.4% removal
74% removal
649NTU
TS
COD
Fe3+ , Mn2+ , Cr2+ ,
Ni2+
COD
COD
630230 ppm
540210 ppm
Almost 100%
removal
63.5% removal
540205 ppm
TSS
Fe3+ , Mn2+ , Cr2+ ,
Ni2+
Turbidity
33555 ppm
Nearly 100%
removal
386.525.3NTU
TS
COD
Anionic dye
(methyl orange)
928.7167.5 ppm
364.2112.6 ppm
93% removal
Cationic dye
(basic bright
yellow)
Al3+
COD
Turbidity
95% removal
TS
TSS
500100 ppm
22079.5 ppm
COD
418186 ppm
Polyacrylamide grafted
carboxymethylstarch
(CMS-g-PAM)
Municipal sewage
wastewater
Hydrolysed polyacrylamide
grafted
carboxymethylstarch (Hyd.
CMS-g-PAM)
Textile industry
wastewater
Starch-g-PAM-g-PDMC
[polyacrylamide and poly
(2-methacryloyloxyethyl)
trimethyl ammonium
chloride]
Polyacrylamide grafted
carboxymethyl guar gum
(CMG-g-PAM)
Carboxymethylstarch
grafted polyacrylamide,
tamarind kernel
polysaccharide grafted
polyacrylamide, sodium
alginate grafted
polyacrylamide (nonionic
or slightly anionic)
Hydroxypropyl methyl
cellulose grafted with
polyacrylamide
(HPMC-g-PAM)
Carboxymethyl chitosan
grafted polyacrylamide
(CMC-g-PAM)
Reference
Paper recycling
wastewater
Aluminium chloride
Optimum results
Municipal sewage
wastewater
Dye solution
Municipal sewage
wastewater
Raw mine
wastewater
Dye solution
Polyacrylamide grafted
oatmeal (OAT-g-PAM)
Municipal sewage
wastewater
Municipal
wastewater
85.8% removal
90.4% removal
6328NTU
Bharti et al.
(2013)
Rani et al. (2012)
501
photosensitizor can also be used, but low penetration of UVrays makes it suitable for surface grafting only.
Up to now, the best method of graft copolymer synthesis is
by use of microwave radiation to generate the free radical sites
on the backbone polymer (Mishra et al., 2011) but this method
is associated with high production cost. As a summary, more
researches are needed to discover an environmental friendly
and economic feasible method for synthesis of high quality
grafted occulants which exhibit excellent capability in pollutants removal and these modied products can be further
exploited for the treatment of many industrial efuents.
6.
Selection of occulants
7.
Flocculation mechanisms
502
Paper
Coffee wastewater
Beverage wastewater
Sauce wastewater
Pulp and paper mill wastewater
Treatment
process
C-F
C-F
C-F
C-F
D-F
Agricultural production
Dye/textile
Municipal
Others
Ink-containing efuent
Cardboard industry wastewater
Palm oil mill efuent
Aquaculture wastewater
Olive mill efuent
Abattoir wastewater
Dye-containing/textile wastewater
Sewage efuent
Municipal wastewater
C-F
D-F
C-F
D-F
C-F
D-F
C-F
C-F
D-F
Coagulant
(commonly
is cationic)
D-F
C-F
D-F
Tannery efuent
D-F
Ceramic wastewater
Polymer efuent
D-F
C-F
Cationic
occulant
Neutral
occulant
Anionic
occulant
Reference
Type of wastewater
Waals forces and the colloidal suspension becomes destabilised (Kleimann et al., 2005). If too much polymer is used,
however, a charge reversal can occur and the particles will
again become dispersed, but with a positive charge rather than
negatively charged. Sometimes, the ocs formed with charge
neutralisation are loosely packed and fragile and settle slowly.
Thus, addition of another high molecular weight polymer with
bridging effect is necessary to bond the microocs together
for fast sedimentation and high water recovery (Ahmad et al.,
2008).
7.1.2.
Renault et al., 2009a). The main mechanisms of coagulation/occulation involved in the removal of dissolved and
particulate contaminants which are often cited are charge
neutralisation, bridge formation and electrostatic patch.
These mechanisms are crucially dependent on the adsorption
of occulants on particle surfaces (Bolto and Gregory, 2007). If
there is some afnity between polymer segments and a particle surface, then adsorption of polymer chains may occur.
7.1.
7.1.1.
Charge neutralisation
For the case where the occulant and the adsorption site are of
opposite charge, generally charge neutralisation is postulated
as the major mechanism. In many practical cases, hydrophobic colloidal particles in wastewater are negatively charged
and thus inorganic occulants (metal salts) and cationic polyelectrolytes are preferable. The occulation could occur simply
as a result of the reduced surface charge of the particles
(reduction of zeta potential) and hence a decreased electrical
repulsion force between colloidal particles, which allows the
formation of van der Waals force of attraction to encourage
initial aggregation of colloidal and ne suspended materials
to form microoc (Fig. 4).
In many studies, it has been found that optimum occulation occurs at polyelectrolytes dosages around that needed
to just neutralise the particle charge, or to give a zeta potential close to zero (isoelectric point). At this point, the particles
would tend to agglomerate under the inuence of the Van der
503
Polymer bridging
Fig. 5 (a) Adsorption of polymer and formation of loops available for binding. (b) Polymer bridging between particles
(aggregation). (c) Restabilisation of colloid particles (oc breakup) (Sharma et al., 2006).
504
7.2.
7.1.3.
Electrostatic patch
When high charge density polyelectrolytes with low molecular weight adsorb on negative surfaces with a fairly low
density of charged sites, bridging capability is reduced and
another possibility arises, which is known as electrostatic
patch mechanism. The basic idea is that, when a highly
charged cationic polymer (Fig. 6b) adsorbs on a weakly charged
negative surface (Fig. 6a), to give overall neutrality, it is not
physically possible for each surface charged site to be neutralised by a cationic polymer segment (Blanco et al., 2002).
There is formation of cationic patches or islands between
regions of uncoated, negatively charged surfaces.
An important consequence of patchwise adsorption is
that, as particles approach closely, there is an electrostatic
attraction between positive patches and negative areas, which
7.3.
Mechanism for grafted occulants/graft
copolymers
The occulation mechanism for grafted occulants involved
in wastewater treatment is a combination of charge neutralisation and polymer bridging (Pal et al., 2011; Song et al., 2011;
Yang et al., 2012a, 2013). Charge neutralisation predominates
at the beginning of the occulation process and produces
numbers of insoluble complexes with a rapid speed. Then,
505
Type of occulant
Flocculation mechanism
Chemical coagulants
Charge neutralisation
Chemical occulants
Charge neutralisation
Bridging
Electrostatic patch
Electrostatic patch + bridging
Bio-occulants
Cationic chitosan
Anionic cellulose and tannin and sodium alginate
Anionic/neutral plant-based occulants
Grafted occulants
Characteristics of
occulant
Flocculation
medium
Flocculation
mechanism
Colloidal dispersion of
anionic polystyrene
latex particles
Suspension of calcium
carbonate
Bridging
Bridging
Polyethyleneimine (cationic)
PolyDADMAC (cationic)
Cationic copolymers of
acrylamide/
diallyldimethylammonium,
chloride
Medium MW (3 105 ),
low CD (10%)
Medium MW (1.1 105 ),
medium CD (40%)
Cationic homopolymer of
diallyldimethylammonium
chloride
Cationic polyacrylamide
(C-PAM)
Electrostatic patch
Charge neutralisation
Suspension of silica
particles
Bridging
Suspension of calcium
carbonate
Bridging
Suspension of calcium
carbonate
Electrostatic
patch + bridging
Bridging
Reference
Electrostatic patch
7.4.
Summary of occulation mechanism for different
types of occulants
The occulation mechanism for different types of occulants
could be summarised in Table 9. In addition, some case studies
have been conducted to investigate the underlying mechanism behind the occulation process induced by chemical
8.
The potential application of conventional occulants, bioocculants and grafted occulants in wastewater treatment
has been veried and well investigated. They have shown
remarkable results in reduction or removal of environmental concerned parameters such as TSS, turbidity, COD and
colour with more than 90% removal was achieved in some
of the studies. Although many occulating materials have
been developed and successfully used in removing pollutants
506
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