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A Review On Applicatio PDF
A Review On Applicatio PDF
Review
a b s t r a c t
Flocculation is an essential phenomenon in industrial wastewater treatment. Inorganic coagulants (salts of multiva-
lent 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 poly-
meric 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 occu-
lants 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.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
2. Coagulationocculation and direct occulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 491
2.1. Coagulationocculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 491
2.2. Direct occulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 491
2.3. Comparison between coagulationocculation and direct occulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
3. Chemical coagulants and occulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
3.1. Inorganic coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
3.2. Organic synthetic occulants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495
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 Process Safety and Environmental Protection 9 2 ( 2 0 1 4 ) 489508
Categories of Flocculants
Tannin
and the relevant occulating mechanisms for treatment of (non-ionic polyacrylamide) resulted in the production of
wastewater are presented and discussed. It is an essential area sludge volume with reduction of 60% of the amount produced
to be reviewed here considering there is no systematic compi- when coagulant was solely used for the treatment of beverage
lation available up to date and this information is expected to industrial wastewater (Amuda and Amoo, 2007).
be signicant for future development and scaling purposes. As shown in Table 1, many studies have proved that the
addition of a polymeric occulant to an inorganic coagulant
2. Coagulationocculation and direct showed better removal where it was effective in the reduction
occulation of environmental concerned parameters (>90% generally) such
as chemical oxygen demand (COD), total suspended solids
There are two methods of wastewater treatment which are (TSS), turbidity and colour, reduce the amount of coagulant
coagulationocculation and direct occulation. The sum- used and thus reduced the cost of the coagulation/occulation
mary of their application in different types of wastewater is process (Ahmad et al., 2005, 2008; Amuda and Alade, 2006;
presented in Tables 1 and 2. Irfan et al., 2013; Martn et al., 2011; Sher et al., 2013; Yang
et al., 2010; Zayas Perez et al., 2007).
2.1. Coagulationocculation
Ferric chloride, aluminium Neutral (N200), two cationic (K1370 Sanitary landll COD About 80% removal Tatsi et al. (2003)
sulphate and lime and K506) and an anionic (A321) leachates Colour About 100% removal
polyelectrolytes
Sodium diethyldithiocarbamate (DDTC) Anionic polyacrylamide Copper electroplating wastewater Copper 99.6% removal Li et al. (2003)
trapping agent
Modied alum (Envioc-40L) Industrial grade occulant (Prooc Palm oil mill efuent Turbidity >98% removal Ahmad et al. (2005)
4190) Water 78%
recovery
Alum, ferric chloride and ferric Anionic polyacrylamide Abattoir wastewater COD 94% removal Amuda and Alade (2006)
sulfate TSS 94% removal
TP 97% removal
Commercial coagulant: T-1 Commercial occulants: Ecooc 6260, Coffee wastewater COD 5560% removal Zayas Perez et al. (2007)
Ecooc 6700, Ecooc 6705, Ecooc 5400,
Ecooc 6708
Ferric chloride Non-ionic polyacrylamide Beverage industrial wastewater COD 91% removal Amuda and Amoo (2007)
TP 99% removal
TSS 97% removal
Alum/ferric salt Synthetic cyanoguanidine- Synthetic reactive dyes wastewater Colour Almost 100% removal Joo et al. (2007)
formaldehyde based
polymer
Real reactive dye wastewater Colour 62% removal
Alum and polyaluminium chloride Cationic (Organopol 5415) and Pulp and paper mill wastewater Turbidity 99.7% removal Ahmad et al. (2008)
(PACl) anionic (Chemoc 430A) TSS 99.5% removal
polyacrylamides COD 95.6% removal
SVI 38 ml/g
Settling 12 s
time
Palm oil mill boiler (POMB) Cationic polymer (KP 1200B) and Ceramic industry wastewater Boron 153 mg/L Chong et al. (2009)
adsorbent anionic polymer (AP 120C) TSS 20005 mg/L
Mixture of ferric chloride and Cationic, anionic and non-ionic High-phosphorus hematite Turbidity 13,53012NTU Yang et al. (2010)
polyaluminium chloride polyacrylamides otation wastewater
Aluminium polychloride Anionic polyacrylamide (Actipol Wastewater from sauce COD 82% removal Martn et al. (2011)
A-401) manufacturing plant
Process Safety and Environmental Protection 9 2 ( 2 0 1 4 ) 489508 493
98% removal
91% removal
99% removal
76% removal
95% removal
95% removal
Turbidity
COD
TSS
pended 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
Industrial polymer efuent
chloride
Derivative of polyacrylamide Oily wastewater from Oil 6 g/L to 220 mg/L Zhong et al. (2003)
(Poly1 and 3530S), polyacrylamide renery plant
COD 3 g/L to 668 mg/L
Four cationic (FO-4700-SH, FO-4490-SH, Olive mill efuent, 5.56.7 TSS Nearly 100% removal Sarika et al. (2005)
FO-4350-SHU and FO-4190-SH) and two COD 55% removal
anionic (FLOCAN 23 and AN 934-SH) BOD5 23% removal
polyelectrolytes
Cationic (FO-4700-SH and FO-4490-SH) Olive mill efuent, 5.15.3 TSS 9799% removal Ginos et al. (2006)
polyelectrolytes TP 5056% removal
COD 1735% removal
Polyacrylamide-based polymers (anionic: Coal waste slurry, 8.3 Turbidity 256.8NTU Sabah and Erkan (2006)
Praestol 2515, Praestol 2540, non-ionic:
Magnooc 351, cationic: Praestol 857 BS)
Cationic (Organopol 5415, Organopol Pulp and paper mill Turbidity 95% removal Wong et al. (2006)
5020, Organopol 5470, Organopol 5450, wastewater, 7.38.3
Chemoc 1515C) and anionic (Organopol TSS 98% removal
5540, Chemoc 430A, AN 913, AN 913SH) COD 93% removal
polyacrylamides SVI 14 ml/g
Water recovery 91%
Cationic polydiallyldimethylammonium Simulated reactive dye Colour >90% removal Kang et al. (2007)
chloride (PDADMAC) wastewater, 7
Cationic polyamine Simulated dye liquor Colour 96% removal Yue et al. (2008)
wastewater, 6.637.89
Actual printing and dyeing Colour 90% removal
wastewater, 11.2
COD 89% removal
Cationic Pulp and paper mill Turbidity 91% removal Razali et al. (2011)
polydiallyldimethylammonium wastewater, 7 TSS Nearly 100% removal
chloride (polyDADMAC) COD 98% removal
Process Safety and Environmental Protection 9 2 ( 2 0 1 4 ) 489508 495
Wastewater collection
Characterization of wastewater
Addition of flocculant
Addition of coagulant pH adjustment (if necessary)
Sedimentation/settling of flocs
Rapid stirring and mixing Addition of flocculant
Sedimentation/settling of flocs
Fig. 2 General procedures for coagulationocculation and direct occulation process (Joo et al., 2007; Martn et al., 2011;
Razali et al., 2011; Sher et al., 2013; Yue et al., 2008).
(Flaten, 2001; Ward et al., 2006). Recent epidemiological, neu- minimise the drawbacks of inorganic occulants, many fac-
ropathological and biochemical studies suggest a possible link tors have been taken into consideration to nd the alternative
between the neurotoxicity of aluminium and the pathogenesis and reduce the dosage of the harmful inorganic occulants.
of Alzheimers disease (Banks et al., 2006; Polizzi et al., 2002).
Other drawbacks include large amount is required for 3.2. Organic synthetic occulants
efcient occulation, highly sensitive to pH, inefcient
towards very ne particles, inefcient in cold water (e.g. In recent years, many synthetic polymers have been used as
polyaluminium chloride) and applicable only to a few dis- the main occulants (coagulant aids) which could enhance
perse systems (Bratby, 2006; Sharma et al., 2006). In order to the coagulation and occulation efciency with promising
Table 4 Market prices for bulk sales of chemical coagulants and occulants (Sarika et al., 2005).
Chemical materials Coagulants Cationic occulants Anionic occulants
Chitosan Iron(III) chloride Chitosan Pulp and paper mill wastewater Turbidity 101.1NTU Rodrigues et al. (2008)
COD 1303516 mg/L
Chitosan Cardboard industry wastewater COD 80% removal Renault et al. (2009a,b)
Turbidity 85% removal
Chitosan Dye-containing solutions Dye 99% removal Szygua et al. (2009)
497
498 Process Safety and Environmental Protection 9 2 ( 2 0 1 4 ) 489508
they have particular macromolecular structures with a variety water treatment (zacar and Sengil, 2003), removal of sus-
of functional groups (e.g. carboxyl and hydroxyl groups) which pended matters from synthetic raw water (zacar and Sengil,
can interact with contaminants (zacar and Sengil, 2003). For 2000), and removal of dyes, pigments and inks from ink-
many years, biopolymers based occulants such as chitosan, containing wastewater (Roussy et al., 2005). In these studies,
tannins, cellulose, alginate, gums and mucilage have been coagulant such as aluminium sulphate was needed for desta-
attracting wide interest of researchers. The research work con- bilisation of the negatively charged colloidal particles, while
cerning the application of these bio-occulants in wastewater anionic tannin acted as occulant to bridge the destabilised
treatment has been compiled and presented in Table 6. aggregates together to form ocs of such a size suitable for
sedimentation. A study showed that coupling of aluminium
4.1. Chitosan sulphate as coagulant and tannin as occulant signicantly
reduced the required doses of the coagulant (zacar and
Since most natural colloids are negatively charged, cationic Sengil, 2003).
polymers or polyelectrolytes are of particular interest as In order to eliminate the necessity of coagulant, modied
potential occulants. Chitosan is one of the most promis- tannin (Tanoc occulant) has been investigated recently to
ing biopolymer for extensive application due to its cationic remove heavy metals from polluted surface water (Beltrn
behaviour. Chitosan is a partially deacetylated polymer Heredia and Snchez Martn, 2009) and in municipal wastew-
obtained from the alkaline deacetylation of chitin, a biopoly- ater treatment (Beltrn-Heredia and Snchez-Martn, 2009).
mer extracted from shellsh sources. It is a linear hydrophilic Tanoc is obtained from Acacia mearnsii bark and modied
amino-polysaccharide with a rigid structure containing both by a physico-chemical process. Groups of hydrocolloid gums
glucosamine and acetylglucosamine units. It is insoluble in and other soluble salts are included in the Tanoc struc-
either water or organic solvents but soluble in dilute organic ture with chemical modication which includes a quaternary
acids such as acetic acid and formic acid and inorganic nitrogen to give Tanoc cationic character (Beltrn Heredia
acids (with the remarkable exception of sulphuric acid) where and Snchez Martn, 2009). Due to its cationic property, it
the free amino groups are protonated and the biopolymer can be used for direct occulation without coagulant and pH
becomes fully soluble (Renault et al., 2009a; Szygua et al., adjustment.
2009). At acidic pH (below pH 5), chitosan becomes a sol-
uble cationic polymer with high charge density (Rinaudo, 4.3. Gums and mucilage
2006). Thus, treatment of wastewater with chitosan dissolved
in acids produces protonated amine groups along the chain Gums and mucilage have been proposed as a safer alternative
and this facilitates electrostatic interactions between poly- to conventional polymers in wastewater treatment because its
mer chains and the negatively charged contaminants (metal production process and applications which are environmental
anions, dyes, organic compounds, etc.) (Renault et al., 2009a). friendly and benecial to human and ecology. Up to date, nat-
This amino-biopolymer possesses several intrinsic char- ural occulants based on gums and mucilage that are derived
acteristics such as high cationic charge density (due to the from plant species include Hibiscus/Abelmoschus esculentus
presence of primary amino groups) (Guibal and Roussy, 2007) (Okra), Malva sylvestris (Mallow), Plantago psyllium (Psyllium),
and long polymer chains with high molecular weight, thus Plantago ovata (Isabgol), Tamarindus indica (Tamarind) and
make it an effective coagulant and/or occulant for the Trigonella foenum-graecum (Fenugreek) have been developed.
removal of contaminants in the suspended and dissolved state These plant-based occulants are generally obtained through
(Guibal et al., 2006; No and Meyers, 2000; Renault et al., 2009a). aqueous extraction, precipitation with alcohol and drying
As the active amino groups ( NH2 ) in the chitosan molecule (Fig. 3).
can be protonated with H+ in water into a cationic polyelec- They have shown promising results with respect to
trolyte (Jaafari et al., 2004) the molecule has characteristics treatment of landll leachate (Al-Hamadani et al., 2011), bio-
of static attraction and adsorption. Besides, chitosan can also logically treated efuent (Anastasakis et al., 2009), textile
occulate particles into bigger ocs which become deposited. wastewater (Mishra and Bajpai, 2005), tannery efuent (Mishra
Therefore, the development of chitosan-based materials as et al., 2004) and sewage efuent (Mishra et al., 2003). At least
useful coagulants and occulants is an expanding eld in 85% of TSS removal, 70% of turbidity removal, 60% of COD
the area of water and wastewater treatment due to its high reduction and 90% of colour removal have been reported in
afnity for many classes of contaminants. Numerous works these studies. Some of them were effective in low concen-
have demonstrated its outstanding coagulation and occula- trations and comparable to synthetic occulants in terms of
tion properties for dye molecules in dye-containing solutions treatment efciency. More than 85% removal of suspended
(Guibal and Roussy, 2007) or textile wastewater (Szygua et al., solids from sewage wastewater and tannery efuent was
2009), organic matter (e.g. lignin and chlorinated compounds) achieved by using 0.12 mg/L of okra gum and 0.08 mg/L Fenu-
in pulp and paper mill wastewater (Rodrigues et al., 2008), greek mucilage respectively, and the occulation efciency of
heavy metals and phenolic compounds in cardboard-mill these bio-occulants was found at par with synthetic poly-
wastewater (Renault et al., 2009b), and inorganic suspensions acrylamide (Agarwal et al., 2001; Mishra et al., 2004).
in kaolinite suspension (Li et al., 2013).
4.4. Sodium alginate
4.2. Tannin
Sodium alginate, the sodium salt of alginic acid, with an aver-
Tannin is a biodegradable anionic polymer (zacar and Sengil, age molecular weight of 500,000, is a linear water-soluble
2000) which comes from vegetal secondary metabolytes such anionic polymer (Wu et al., 2012). A recent study investigated
as bark, fruits, leaves and others (Beltrn Heredia and Snchez its occulating efciency in treatment of industrial textile
Martn, 2009). Its occulating property has been tested in wastewater and synthetic dye wastewater by using aluminium
removal of suspended and colloidal materials in drinking sulphate as the coagulant (Wu et al., 2012). The experimental
Process Safety and Environmental Protection 9 2 ( 2 0 1 4 ) 489508 499
Aluminium chloride Chitosan grafted PDMC Paper recycling Turbidity 6878.7NTU Wang et al. (2007)
(poly(2- wastewater
methacryloyloxyethyl)
trimethyl ammonium
chloride)
Aluminium chloride (2-methacryloyloxyethyl) Pulp mill wastewater Turbidity 99.4% removal Wang et al. (2009)
trimethyl ammonium
chloride (DMC) grafted
chitosan (cationic)
Lignin 81.3% removal
COD 90.7% removal
Polyacrylamide grafted Municipal sewage Turbidity 204NTU Sen et al. (2009)
carboxymethylstarch wastewater
(CMS-g-PAM)
TS 602356 ppm
Hydrolysed polyacrylamide Textile industry Turbidity 9754NTU Sen et al. (2011)
grafted wastewater
carboxymethylstarch (Hyd.
CMS-g-PAM)
TS 640309 ppm
COD 586221 ppm
Aluminium chloride Starch-g-PAM-g-PDMC Pulp mill wastewater Turbidity 99.6% removal Wang et al. (2011)
[polyacrylamide and poly
(2-methacryloyloxyethyl)
trimethyl ammonium
chloride]
Lignin 88.4% removal
Water recovery 74% removal
Polyacrylamide grafted Municipal sewage Turbidity 649NTU Pal et al. (2011)
carboxymethyl guar gum wastewater
(CMG-g-PAM)
TS 630230 ppm
COD 540210 ppm
Fe3+ , Mn2+ , Cr2+ , Almost 100%
Ni2+ removal
Dye solution COD 63.5% removal
Carboxymethylstarch Municipal sewage COD 540205 ppm Pal et al. (2012)
grafted polyacrylamide, wastewater
tamarind kernel
polysaccharide grafted
polyacrylamide, sodium
alginate grafted
polyacrylamide (nonionic
or slightly anionic)
TSS 33555 ppm
Fe3+ , Mn2+ , Cr2+ , Nearly 100%
Ni2+ removal
Hydroxypropyl methyl Raw mine Turbidity 386.525.3NTU Das et al. (2013)
cellulose grafted with wastewater
polyacrylamide
(HPMC-g-PAM)
TS 928.7167.5 ppm
COD 364.2112.6 ppm
Carboxymethyl chitosan Dye solution Anionic dye 93% removal Yang et al. (2013)
grafted polyacrylamide (methyl orange)
(CMC-g-PAM)
Cationic dye 95% removal
(basic bright
yellow)
Al3+ 85.8% removal
COD 90.4% removal
Polyacrylamide grafted Municipal sewage Turbidity 6328NTU Bharti et al.
oatmeal (OAT-g-PAM) wastewater (2013)
TS 500100 ppm
Polyacrylamide grafted agar Municipal TSS 22079.5 ppm Rani et al. (2012)
wastewater
COD 418186 ppm
Process Safety and Environmental Protection 9 2 ( 2 0 1 4 ) 489508 501
copolymers showed superior occulation characteristics in photosensitizor can also be used, but low penetration of UV-
turbidity removal when compared with commercially avail- rays makes it suitable for surface grafting only.
able occulants (Pal et al., 2005; Singh et al., 2006; Wang et al., Up to now, the best method of graft copolymer synthesis is
2008a). by use of microwave radiation to generate the free radical sites
Another great advantage of grafted occulant is the conse- on the backbone polymer (Mishra et al., 2011) but this method
quent reduced biodegradability because of the drastic change is associated with high production cost. As a summary, more
in the original regular structure of the natural polymer as well researches are needed to discover an environmental friendly
as the increased synthetic polymer content in the product. and economic feasible method for synthesis of high quality
The graft copolymers are found less susceptible to biodegra- grafted occulants which exhibit excellent capability in pol-
dation because grafting promotes alteration of structure of lutants removal and these modied products can be further
polysaccharide molecules and thus will make it less suitable exploited for the treatment of many industrial efuents.
as a substrate for enzymatic degradation. Moreover, the inert
polyacrylamide content also increases with grafting polysac- 6. Selection of occulants
charides, making it less prone to biological attack and more
biodegradable resistant (Singh et al., 2000). It is also observed After understanding the treatment processes including
that grafting of shear degradable polymers onto the rigid coagulationocculation and direct occulation and different
polysaccharide backbone provides fairly shear stable systems types of occulants, the task to achieve the desired clarica-
(Singh et al., 2000). tion or purication will be much easier. Based on literature
In principle, cationic organic occulants should be more work, the occulants that have been used for treatment of
effective in dealing with negatively charged contaminants or different types of wastewaters are compiled and presented
particle suspensions, such as clay and dye. Therefore, cationic in Table 8. For any wastewater treatment, the rst step is to
occulants have been synthesised by incorporating a cationic examine the characteristics of the wastewater where it will
moiety N-(3-Chloro-2-hydroxypropyl) trimethyl ammonium determine the selection of treatment process. As presented
chloride (CHPTAC) onto the backbone of guar gum (Singh et al., in Table 3, coagulationocculation is normally suitable for
2006) or starch (Pal et al., 2005; Pal et al., 2008) in presence any kind of wastewaters that contain suspended and dis-
of sodium hydroxide. These studies showed that the cationic solved constituents while direct occulation is only applicable
occulants with longer CHPTAC chains showed better oc- to treat organic-based efuents that contain suspended solids.
culation performance compared with commercially available The next move is to choose the type of occulant(s) to
occulants in suspension containing negatively charged par- be used. As the surface charge of the colloidal suspensions
ticles. is generally negative, thus cationic coagulant or occulant is
However, some wastewater such as textile efuent is com- always elected. For coagulationocculation process, cationic
plicated and may contain undesirable cationic and anionic coagulant is commonly coupled with non-ionic or anionic oc-
colloidal particles. Therefore, it was proposed that ampho- culants. On the other hand, cationic or anionic occulants are
teric occulants containing both cationic and anionic ions usually selected for direct occulation process. There is a wide
could eliminate both cationic and anionic contaminants. In variety of occulants available in the market with different
recent years, amphoteric chitosan-based occulants have molecular weight and charge density. Normally, high molec-
been synthesised and their occulating characteristics have ular weight occulants are preferable because it is associated
been evaluated using kaolin suspension as synthetic wastew- with bridging mechanism which is stronger compared to other
ater (Yang et al., 2012a,b), raw water from river (Yang et al., occulation mechanisms.
2012a), and dye-containing solution (Yang et al., 2013). It
was noticed that amphoteric chitosan copolymer showed
7. Flocculation mechanisms
higher removal efciency compared to chitosan and produced
notably more compacted ocs.
Generally, development of ocs formation involves several
In short, grafting is the most effective way of regulating
steps occurring sequentially:
the properties of polysaccharides which can be tailor-made
according to the needs and produce high efcient graft
copolymers. However, the main problem in the case of graft (a) Dispersion of the occulant in the solution.
copolymers is the lack of commercial methods of synthesis (b) Diffusion of the occulant towards the solid-liquid inter-
(Mishra et al., 2011). The chief methods of synthesis of grafted face.
polysaccharides involve the use of chemical free radical ini- (c) Adsorption of the occulant onto the surface of the parti-
tiator (conventional method), high energy radiations (gamma cles.
and X-ray), UV-radiation based method and microwave based (d) Collision of particles carrying an adsorbed occulant with
methods. other particles.
The conventional method of synthesis uses a chemical free (e) Adsorption of the occulant onto other particles in order
radical initiator (e.g. ceric ammonium nitrate or CAN) to gen- to form microocs.
erate free radical sites on the backbone polymer, where the (f) Growth of the microocs to larger and stronger ocs by
monomer of the graft gets added up to form the graft chain successive collision and adsorption.
(da Silva et al., 2007; Sen et al., 2009). This method of synthe-
sis has low reproducibility and is not suitable for commercial Several occulation mechanisms such as polymer bridg-
scale synthesis. A better method of graft copolymer synthe- ing, polymer adsorption and charge neutralisation (including
sis is by using high energy radiation (gamma rays or electron electrostatic patch effects), depletion occulation, displace-
beam) as the free radical generator (Vahdat et al., 2007; Wang ment occulation, etc. have been proposed to explain the
et al., 2008a) but this method can cause damage to the polysac- destabilisation of colloids and suspensions by polymers and
charide backbone (radiolysis). UV rays in presence of suitable the mechanism of ocs formation (Bolto and Gregory, 2007;
502
Table 8 Selection of occulants based on different wastewaters.
Industry area Type of wastewater Treatment Coagulant Cationic Neutral Anionic Reference
process (commonly occulant occulant occulant
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 Process Safety and Environmental Protection 9 2 ( 2 0 1 4 ) 489508
Quaternary ammonium based High MW (16 106 ), Colloidal dispersion of Bridging Biggs et al. (2000)
derivative of polyacrylamide high CD (100%) anionic polystyrene
(cationic) latex particles
Cationic polyacrylamide (C-PAM) High MW, low CD Suspension of calcium Bridging Blanco et al. (2002)
carbonate
Polyethyleneimine (cationic) Low MW, high CD Electrostatic patch
PolyDADMAC (cationic) Medium MW, medium Charge neutralisation
CD
Cationic copolymers of Medium MW (3 105 ), Suspension of silica Bridging Zhou and Franks (2006)
acrylamide/ low CD (10%) particles
diallyldimethylammonium, Medium MW (1.1 105 ), Charge neutralisa-
chloride medium CD (40%) tion + bridging/bridging
Cationic polyacrylamide High MW, low CD Suspension of calcium Bridging Rasteiro et al. (2007)
(C-PAM) carbonate
High MW, high CD Electrostatic patch
Cationic polyacrylamide High MW (7.2 106 ), Suspension of calcium Electrostatic Rasteiro et al. (2008)
(C-PAM) high CD (80%) carbonate patch + bridging
High MW (13 106 ), Bridging
medium CD (50%)
through bridging effect due to the exible polymeric graft polymeric occulants by using Light Diffraction Scattering
chains, the insoluble complexes aggregate and form larger (LDS) technique. As shown in Table 10, it is clear that molec-
net-like ocs. Finally, the compacted ocs are formed and set- ular weight and the charge density play the important role to
tled down rapidly (Yang et al., 2013). inuence and decide the acting mechanism.
Other research works revealed that bridging is the lead- In order to control and optimise the occulation process,
ing occulation mechanism (Das et al., 2013; Pal et al., 2011). it is highly important to know and understand the occu-
The reason for better occulation characteristics of graft lation mechanism during the whole process. However, the
copolymers over linear polymer is essentially due to polymer investigation and discovery of the underlying mechanism for
bridging mechanism. Segments of the polymer chain adsorbed removal of impurities or contaminants from wastewater with
onto different particles surface, forming bridges between adja- bio-occulants and grafted occulants is still lacking and
cent particles and nally linked all the particles together. The immature.
length of the polymer chains of grafted occulants are longer
and the radius of gyration is higher, thus the adsorbed poly-
mer molecules tend to adopt more extended conguration for 8. Conclusion and future perspectives
interacting with more than one particle.
The potential application of conventional occulants, bio-
7.4. Summary of occulation mechanism for different occulants and grafted occulants in wastewater treatment
types of occulants has been veried and well investigated. They have shown
remarkable results in reduction or removal of environmen-
The occulation mechanism for different types of occulants tal concerned parameters such as TSS, turbidity, COD and
could be summarised in Table 9. In addition, some case studies colour with more than 90% removal was achieved in some
have been conducted to investigate the underlying mecha- of the studies. Although many occulating materials have
nism behind the occulation process induced by chemical been developed and successfully used in removing pollutants
506 Process Safety and Environmental Protection 9 2 ( 2 0 1 4 ) 489508
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