Water Research 143 (2018) 608e631

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Water Research
journal homepage: www.elsevier.com/locate/watres

Review

Coagulation/flocculation in dewatering of sludge: A review*

Hua Wei, Boqiang Gao, Jie Ren, Aimin Li, Hu Yang*
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, 210023, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Sludge disposal is an integral part of wastewater treatment systems, and its cost usually accounts for
Received 8 February 2018 more than half of the total operation cost. Sludge disposal technology is facing challenges and oppor-
Received in revised form tunities simultaneously and can still be improved. Sludge dewatering is an essential process in sludge
9 July 2018
disposal, and it is important for the effective reduction of the final processing cost. Coagulation/floc-
Accepted 10 July 2018
Available online 11 July 2018
culation is a relatively mature, cost-effective, user-friendly sludge dewatering technology. In this work,
coagulation/flocculation and their combinations with other pretreatments, including dewatering
mechanisms, are reviewed. Various coagulants/flocculants used in sludge dewatering, including inor-
Keywords:
Dewatering of sludge
ganic coagulants, organic synthetic and natural polymeric flocculants, and bioflocculants, are introduced
Characteristics of sludge in detail because coagulants/flocculants are the key in coagulation/flocculation. The different factors that
Coagulation/flocculation influence the dewatering performance of these coagulants/flocculants are also presented briefly.
Coagulants/flocculants Moreover, aiming at the complicated composition of sludge and its treatment difficulty, the prospects
Coagulation/flocculation mechanisms and technical developments of coagulation/flocculation in sludge dewatering are discussed.
© 2018 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
2. Characteristics of sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
2.1. Characteristics of water in sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
2.2. Characteristics of solids in sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
2.3. Characteristics of sludge cake . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
2.3.1. Analysis of the properties of flocs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
2.3.2. Sludge cake properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
3. Coagulation/flocculation in sludge dewatering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
3.1. Factors that influence sludge dewatering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
3.1.1. Conditioner dose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
3.1.2. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
3.1.3. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
3.2. Chemical coagulants/flocculants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
3.2.1. Inorganic salt coagulants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
3.2.2. Organic synthetic polymeric flocculants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
3.2.3. Natural polymeric flocculants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
3.2.4. Bioflocculants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
3.2.5. Evaluation of various coagulants/flocculants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
3.3. Techniques combined with other pretreatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
3.3.1. Physical conditioning treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
3.3.2. Chemical conditioning treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626

*
Supported by the Natural Science Foundation of China (grant nos. 51778279 and 51438008), the Natural Science Foundation of Jiangsu Province of China (grant no.
BK20161405), and Six Talent Peaks Project in Jiangsu Province of China (grant no. 2015-JNHB-003).
* Corresponding author.
E-mail address: yanghu@nju.edu.cn (H. Yang).

https://doi.org/10.1016/j.watres.2018.07.029
0043-1354/© 2018 Elsevier Ltd. All rights reserved.
 H. Wei et al. / Water Research 143 (2018) 608e631 609

4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628

Abbreviations LAP leucyl aminopeptidase

LB-EPS Loosely bound extracellular polymeric substances
AA Acrylic acid MBFs Microbial flocculants
AF Acidithiobacillus ferrooxidans MC Moisture content
Al13 Medium polymeric Al species MW Molecular weight
Ala Mainly made up of monomer and oligomeric forms of NMR Nuclear magnetic resonance
aluminum PAA Poly(acrylic acid)
Alb Mainly made up of middle polymer forms of PAC Poly-aluminum chloride
aluminum PAM Polyacrylamide
Alc Mainly made up of high polymer forms of aluminum P(AM-AA-AMPS) Poly(acrylamide-co-acrylic acid-co-2-
Almon Monomeric Al species acylamido-2-methyl propane sulfonic acid)
Alun Undetectable Al species P(AM-DAC) Poly(acrylamide-co-acryloyloxyethyl trimethyl
AM acrylamide ammonium chloride)
AMPS 2-acylamido-2-methyl propane sulfonic acid P(AM-DAC-BA) Poly(acrylamide-co-acryloyloxyethyl trimethyl
APAM Anionic polyacrylamide ammonium chloride-co-butylacrylate)
ATP Adenosine 50 -triphosphate P(AM-DMC-DAC) Poly(acrylamide-co-methacryloxyethyl
BA Butylacrylate trimethyl ammonium chloride-co-
BCA Bicinchoninic acid acryloyloxyethyl trimethyl ammonium
CER Cationic exchange resin chloride)
Chitosan-g-PDMDAAC Chitosan-graft-poly(diallyl dimethyl PDMDAAC poly(diallyl dimethyl ammonium chloride)
ammonium chloride) PFS Polyferric sulfate
CPAM Cationic polyacrylamide PN Protein
CST Capillary suction time PS Polysaccharide
CTA 3-chloro-2-hydroxypropyl trimethyl ammonium s The coefficient of compressibility
chloride SABR Superabsorbent resin
DAC 2-(acryloyloxy)ethyl trimethyl ammonium chloride SEM Scanning electron microscopic
DMC [2-(methacryloyloxy)ethyl] trimethyl ammonium SRF Specific resistance to filtration
chloride STC-g-PDMC Starch-graft-poly[(2-methacryloyloxyethyl)
DMDAAC Diallyl dimethyl ammonium chloride trimethyl ammonium chloride]
DLVO Derjguin-Landau-Verwey-Overbeek STC-g-PDMDAAC Starch-graft-poly(diallyl dimethyl ammonium
DOC Dissolved organic carbon chloride)
DS Dry solids TB-EPS Tightly bound extracellular polymeric substances
DSC Differential scanning calorimetry TSC Titanium salt coagulant
DTA Differential thermal analysis TSS Total suspended solid
EPS Extracellular polymeric substances TTF Time to filter
FCC Filtration-compression cell WAS Waste activated sludge
IPCs Inorganic polymeric coagulants

1. Introduction parameters in evaluating sludge dewaterability (Pan et al., 2003;

Sawalha and Scholz, 2010; Scholz, 2005; Yukseler et al., 2007). The
Sludge is the product of sewage treatment, and the total solid CST test is simple and inexpensive because it does not require an
content in it is generally below 8% before treatment (Anjum et al., external source of pressure or suction (Scholz, 2005). The SRF test,
2016; Nellenschulte and Kayser, 1997). Sludge disposal is an as defined in Eq. (1.1), is time consuming, complex, and expensive
important part of sewage treatment systems, and its cost accounts because it requires the application to be in a vacuum (Sawalha and
for more than half of the total cost (Mowla et al., 2013; Ӧrmeci, Scholz, 2010; Yukseler et al., 2007). However, the SRF test is
2016). Sludge disposal and management are thus major chal- regarded as more scientific than the CST test because of its hy-
lenges in the global water industry. In the latest reports issued by drodynamic characteristic (Fitria et al., 2013). Sawalha and Scholz
the 10th Water Conference of the International Water Association (2010) established an empirical model to obtain SRF from CST
on October 10, 2016, sludge disposal and management are highly data due to the empirical relativity of SRF and CST.
popular topics (Ӧrmeci, 2016). Efficient separation of liquid and
solid in sludge is one of the key steps in reducing the costs of sludge
2PA2 b
treatment, transportation, and final disposal (Mowla et al., 2013). SRF ¼ ; (1.1)
Moisture content (MC) in sludge directly corresponds to the mu
dewatering extent (Lu et al., 2017; Novak, 2006). Capillary suction
where P (kg/m2) is the pressure applied; A (m2) is the filter area; b
time (CST) and specific resistance in filtration (SRF) are two popular
(s/m6) is the time-to-filtration ratio, which is the slope of the curve
610 H. Wei et al. / Water Research 143 (2018) 608e631
that is obtained by plotting the ratio of the time of filtration to the
volume of the filtrate (t/V) versus the filtrate volume (V); m (kg$s/
m2) is kinetic viscosity (KV); and u (kg/m3) denotes the mass of dry
solids (DS) per volume of sludge in the filtrate medium and should
be assumed constant.
CST and SRF are empirical and lacking in accuracy. The SRF test
is based on classical filtration theory (Yukseler et al., 2007). In this
test, mean porosity, mean cake size, and pore-water pressure are
assumed constant, but this assumption does not conform to actual
practice (Sawalha and Scholz, 2010). The CST test is also unable to
predict variable physical properties and processes in reality
because of its theoretical limitation (Pan et al., 2003; Scholz,
2005). Meanwhile, the process of dissolving extracellular poly-
meric substances (EPS) and releasing bound water might break
large flocs into fine particles and could result in poor filtration
performance. Therefore, whether SRF reduction is consistent with
a decrease in MC is unknown (Guan et al., 2017). Dehydration rate
was recently used as the main index to evaluate the dewater-
ability of sludge with high pressure in a study on the second
dewatering of urban sewage dewatered sludge (Zhang et al.,
2017b). The filtrationecompression cell (FCC) test is another
powerful tool that can assess filtration and compression stages in
sludge compression dewatering at the laboratory scale (Lu et al.,
2017; Raynaud et al., 2012; Vaxelaire and Olivier, 2006). In the
filtration stage, a compressive piston pushes the sludge toward
the filtering media, and a filter cake builds up. The compression
(expression) phase corresponds to the removal of liquid by
squeezing of the filter cake (Raynaud et al., 2012). However, the
actual dewatering process is complex due to the large amount of
particles with different sizes, shapes, and components. Sludge
properties should be considered comprehensively to estimate
sludge dewaterability accurately.
Sludge desiccation is an indispensable process in sludge man-
agement after mechanical dewatering, which includes filtration
and centrifugation (Bennamoun, 2012). Mechanical dewatering is
important in reducing sludge volume before further drying disposal
because of the considerable influence of the site and climate on
natural drying and the high energy consumption during artificial
desiccation (Bennamoun, 2012). However, direct mechanical dew-
atering of sludge without any pretreatment cannot achieve the
ideal dewatering effect, and the MC of sludge after mechanical
dewatering could only reach 80%e98% (Wang et al., 2010a) because
sludge is a highly complex system composed of numerous small
and surface-charged solids, which could be relatively dynamically
stable in water not only because of their low gravity and electro-
static repulsion effects, but also because part of the water is tightly
Fig. 1. Various conditioning methods for sludge dewatering.
combined to the surface or captured inside the colloidal network
(Vaxelaire and Ce
zac, 2004). Especially, highly charged EPS can
readily form a stable gel-like suspended structure that binds with
water molecules due to its steric force (Keiding et al., 2001; Mowla
et al., 2013; Neyens et al., 2004; Qi et al., 2011a). Thus, efficient
sludge separation is difficult to achieve, and the mechanisms of
dewatering remain unclear (Anjum et al., 2016; Christensen et al.,
2015; Liu and Fang, 2003; Mowla et al., 2013).
Various pretreatments are applied to enhance sludge filtration
and final dewatering efficiency (Dhar et al., 2012; Liu et al., 2016b;
Ruiz-Hernando et al., 2014; Zhang et al., 2015c; Zhen et al., 2013).
Existing methods of sludge conditioning can be mainly categorized
as physical, chemical, and biological, as shown in Fig. 1. Physical
conditioning refers to changing the physicochemical properties of
sludge through physical methods, including the addition of skel-
eton builders (Wu et al., 2016c), the thermal approach (Neyens and
Baeyens, 2003), the freezeethaw approach (Hu et al., 2011), use of
microwave (Cai et al., 2017), ultrasonic conditioning (Feng et al.,
2009), and their combinations (Dhar et al., 2012; Ruiz-Hernando
et al., 2014). Chemical conditioning refers to the addition of acids,
alkalis (Li et al., 2005), surfactants (Chen et al., 2001; Guan et al.,
2017), oxidants (Zhang et al., 2015c), coagulants/flocculants
(Mowla et al., 2013), and other bio-chemical agents (Guo et al.,
2015), or use of electrochemical methods (Mahmoud et al., 2018;
Zhen et al., 2013), to the sludge to change the nature of the sludge
and improve dewatering performance. Coagulation/flocculation is
one of the most commonly used sludge conditioning approaches
when cost and efficiency are considered; small colloidal particles in
the sludge form large flocs and compacted cakes for the improve-
ment of sedimentation and dewatering performance by increasing
the sludge dewatering rates and solid content (Chen et al., 2015,
2016a; Novak and O'Brien, 1975). In this paper, the characteristics of
sludge, which intrinsically result in dewatering difficulties, are first
introduced. Second, coagulation/flocculation applied in sludge
dewatering is reviewed based on various employed coagulants/
flocculants, including inorganic coagulants, organic synthetic and
natural polymeric flocculants, and bioflocculants. Combined pre-
treatment technologies associated with coagulation/flocculation
are also introduced. Third, different influencing factors are dis-
cussed briefly. The main framework of this review is described in
Fig. 2. Lastly, the prospects and technical developments in coagu-
lation/flocculation in sludge dewatering are further presented,
aiming at the characteristics of sludge and the difficulty of its
treatment.
Fig. 2. Schematic description on sludge dewatering using coagulation/flocculation.
 H. Wei et al. / Water Research 143 (2018) 608e631 611

2. Characteristics of sludge
2.1. Characteristics of water in sludge
The components of sludge are highly complicated, and they
mainly include water and various types of solids (Anjum et al.,
2016; Mowla et al., 2013). With regard to the existing water,
different forms with different properties, such as vapor pressure,
enthalpy, entropy, viscosity, and density, usually exist in sludge due
to the presence of various solids (Erdincler and Vesilind, 2003;
Katsiris and Kouzeli-Katsiri, 1987; Vaxelaire and Ce
zac, 2004;
Vesilind, 1994). A clear classification of the moisture in sludge is
essential for the study of dewatering. Generally, sludge water can
be classified according to the degree of removal difficulty (Vaxelaire
and Ce
zac, 2004). The first classification is free water that is unaf-
fected by solid particles. It includes water in void but unaffected by
capillary force and accounts for approximately 70% of the total
water (Chen et al., 2015; Vaxelaire and Ce
zac, 2004). The second
classification is interstitial water that is trapped inside the crevices
and interstitial spaces of flocs and organisms (Mikkelsen and
Keiding, 2002). The third classification is surface water that is
adsorbed or adheres onto the surface of particles. The last classifi-
cation is hydration (or internal) water, which is tightly bound to the
solids (Vaxelaire and Ce
zac, 2004). The sum of the three latter
forms of water is usually collectively referred to as bound water
(Lee and Hsu, 1995; Lee and Lee, 1995). The content of bound water
is one of the major influencing factors that limit sludge dewater-
ability (Erdincler and Vesilind, 2003; Mowla et al., 2013; Vaxelaire
and Ce
zac, 2004). However, Jin et al. (2004) believed that free water
might reflect sludge dewaterability better than bound water can
due to the strong binding characteristics and small portion of
bound water.
Vaxelaire and Ce
zac (2004) summarized various methods of
determining the moisture distribution in sludge, including thermal
analysis technologies and mechanical strain tests, to examine
sludge conditioning and dewatering. The four forms of water,
namely, free, interstitial, surface, and internal water, can be roughly
determined via the transition points in various tests (Lee and Hsu,
1995; Vaxelaire and Ce
zac, 2004). For example, interstitial, surface,
and internal water can be estimated through the centrifugal
settling test (the cake is incompressible or slightly compressible),
from the sum of surface and internal water obtained from drying
and DSC tests, and from the internal water content from an
expression test, respectively (Lee and Hsu, 1995; Lee and Lee, 1995;
Vaxelaire and Ce
zac, 2004). The criteria of these approaches are not
unified yet, and the parameters of each test should not be ignored.
Table 1 lists several commonly used thermal analysis approaches
for measuring the content of bound water in sludge together with
their mechanisms or hypotheses.
Conventional dewatering processes can remove only free water
and a part of bound water (Erdincler and Vesilind, 2003). Further
release of bound water inside the cell structure can be achieved by
the disruption of sludge cells via sonication and alkali, NaCl, and
heat treatments (Erdincler and Vesilind, 2003; Ruiz-Hernando
et al., 2014). Sludge cell disruption changes the water distribution
in sludge, and a considerable amount of interstitial water trapped
inside the cells including many organic matters is released. How-
ever, cell disruption creates additional surfaces for water binding
and increases the “unfreezable” water content (mostly vicinal wa-
ter, water of hydration, and a fraction of interstitial water)
(Erdincler and Vesilind, 2003). Ruiz-Hernando et al. (2014)
discovered that the content of bound water in sludge increases
when the intensity of three treatments (ultrasound, thermal, and
alkali) increases, but sludge dewatering can still be improved by
these treatments. Katsiris and Kouzeli-Katsiri (1987) reported that
the bound water in activated and digested sludge is reduced by 30%
and 70% by heat and freezeethaw treatments, respectively.
Although organic matter and bound water are released because of
the disruption of flocs and cells during pretreatments, extra sur-
faces for water binding are created, as mentioned above; thus,
further treatments, such as flocculation/coagulation, for decreasing
the binding sites are required (Vaxelaire and Ce
zac, 2004). The ef-
fect of coagulation/flocculation on bound water (to be discussed in
detail later) is largely acknowledged (Vaxelaire and Ce
zac, 2004).
2.2. Characteristics of solids in sludge
The main solid components of different sludge types are usually

Table 1
Commonly used thermal analysis technologies applied in measuring the content of bound water in sludge.

Technique Mechanism or main hypothesis Operating conditions Sludge type Refs

Differential The bound water would persist in the liquid T ¼ 20 to 20  C, cooling rate ¼ 1  C/min, and T ¼ 20 to 150  C Digested sludge (He et al., 2016)
scanning phase at some low temperature instead of heating rate ¼ 5  C/min
calorimetry freezing T ¼ 25 to 40  C, cooling rate ¼ 2  C/min, and T ¼ 40 to40  C WAS (Ruiz-
(DSC) heating rate ¼ 2  C/min Hernando et al.,
2014)
T ¼ 150 to 725  C, cooling rate ¼ 2  C/min WAS (Erdincler and
Vesilind, 2003)
T ¼ room temperature to 60  C, cooling rate ¼ 1e10  C/min and WAS and (Lee and Lee,
T ¼ 60  C to room temperature, heating rate ¼ cooling rate synthesized sludge 1995)
Differential T ¼ 150 to 500  C, cooling rate ¼ 2  C/min, sample weight ¼ 18 Surplus activated (Katsiris and
thermal e25 mg and waste digested Kouzeli-Katsiri,
analysis (DTA) sludge 1987)
Combined DSC T ¼ 20 to 20  C, cooling rate ¼ 1  C/min, and T ¼ 20 to 20  C Digested sludge (He et al., 2015)
and DTA heating rate ¼ 1  C/min tested by DSC; followed by T ¼ 20e150  C
tested by TGA
Dilatometric test Hydraulic oil, Aerobically digested (Smith and
T ¼ 35 to 3  C sludge Vesilind, 1995)

Drying test The bound water would evaporates slower Tc ¼ 35 C Chemical and (Robinson and
than other kind of water Hc ¼ 50e60% biological sludges Knocke, 1992)
Tc ¼ 30  C Sludge obtained (Jin et al., 2016)
Hc was controlled by sparging compressed dry air with 400mL/min from pilot tank in
lab
Tc ¼ 80  C Excess sludge (Wang et al.,
Hc ¼ 60% 2017)

Hc: controlled humidity; T: temperature; Tc: constant temperature; WAS: waste activated sludge.
612 H. Wei et al. / Water Research 143 (2018) 608e631

content exhibits a negative correlation with sludge settlement

Fig. 3. Schematic configuration of WAS (Yu et al., 2016).
dissimilar because of the different pollutants in various wastewa-
ters and because sludge produced in different water treatment
units present different characteristics. The biological method can
effectively reduce organic pollutants in wastewater and has been
widely used in sewage treatment for decades. A large amount of
waste activated sludge (WAS), which usually contains over 95% of
water, is generated in this process (Colin and Gazbar, 1995; Zhu
et al., 2013); thus, WAS is highly popular, and its main in-
gredients include microorganisms, EPS, organic debris, and inor-
ganic colloidal particles (Christensen et al., 2015). A schematic of
the configuration of WAS is presented in Fig. 3 (Yu et al., 2016). The
existence of EPS (Liu and Fang, 2002, 2003), one of the main factors
that influence the rheological properties of sludge (Dong et al.,
2011), is the main cause of the difficulty of efficient sludge
dewatering.
Yu et al. (2010) divided sludge flocs into five fractions: super-
natant, slime, loosely bound EPS (LB-EPS), tightly bound EPS (TB-
EPS), and pellet. LB-EPS is diffused from TB-EPS, which surrounds
cells (Cao et al., 2016; Li and Yang, 2007). The dewaterability of
sludge as influenced by EPS fraction, which is negatively charged
and highly hydrated and captures a large amount of water, is
currently a popular topic in sludge management studies (He et al.,
2016). The impact of EPS fraction on the properties of the dew-
atering effect remains debatable. Research has shown that the
addition of EPS extracted from sludge does not influence sludge
cake porosity but deteriorates SRF (Kang et al., 1989), and LB-EPS
and dewatering performance (Li and Yang, 2007). Moreover, high
EPS concentrations worsen floc settlement and compressibility (Jin
et al., 2003). Nevertheless, a certain EPS content is conducive for
optimal dewatering performance (Houghton et al., 2001; Houghton
and Stephenson, 2002), and a study has shown that the total
extracted EPS content is positively correlated with dewaterability
(Jin et al., 2004). These conflicting results based on extracted EPS
might be due to the low extraction efficiency and inaccurate char-
acterization of EPS (Wile
n et al., 2003). Therefore, extraction
methods exert a significant impact on EPS quantification
(Wingender et al., 1999).
Various individual methods of EPS extraction (mainly divided
into physical and chemical methods) and their mechanisms were
summarized and categorized by Sheng et al. (2010). Most studies
combined two or more methods to extract EPS. Table 2 lists the
most recent, commonly used EPS extraction techniques formed by
various individual extraction methods. D'Abzac et al. (2010)
pointed out that higher EPS yields can be achieved by chemical
extraction procedures (except for ethanol) compared with physical
procedures, and the yield order of the four investigated sludge was
as follows: raw sludge z sonication z ethanol  heating < cationic
exchange resin
(CER) < CER þ sonication < formaldehyde þ heating << EDTA <<<
formaldehyde þ NaOH. Notably, knowledge on EPS is insufficient,
and no standard approach of EPS extraction exists (Anjum et al.,
2016; Sheng et al., 2010). The difficulty of accurately analyzing
EPS in sludge might also be due to the high sensitivity of EPS to
various environmental factors, resulting in uncertain trans-
formation between different EPS forms and even in the release of
extra organic matter because of sludge cell disruption caused by
several pretreatments.
Previous research has also attempted to determine the detailed
chemical compositions of EPS, which mainly includes “protein-like”
compounds (PN, <60%), carbohydrates (PS, 40%e95%), lipids
(<40%), DNA (<10%), aquatic humic substances, and small mole-
cules (Flemming and Wingender, 2001; Sheng et al., 2010), to

Table 2
Various combined processes for EPS extraction.

Process Physical processes Chemical processes

References Centrifugation Heat Sonication Vibration Grind NaOH H2SO4 Formaldehyde EDTA Cation Aceton/
and exchange ethanol
shearing resin

(Cao et al., 2016; Chen et al., 2015, 2016b; Niu et al., 2013; ✓ ✓ ✓ ✓
Wei et al., 2018; Zhen et al., 2012a)
(Wang et al., 2010b; Zhen et al., 2012b) ✓ ✓ ✓
(D'Abzac et al., 2010; Guo et al., 2014; Yu et al., 2007, ✓ ✓
2010; Yuan et al., 2014; Zhang et al., 2015a, 2015b)
(Li and Yang, 2007; Liu et al., 2016a; Mo et al., 2015; Zhen ✓ ✓ ✓
et al., 2013)
(Morgan et al., 1990; Houghton et al., 2001; Houghton and ✓ ✓ ✓
Stephenson, 2002)
(Zhen et al., 2012c) ✓ ✓ ✓ ✓
(D'Abzac et al., 2010; Guo et al., 2014; Mikkelsen and ✓ ✓ ✓
Keiding, 2002; Wile
n et al., 2003; Yu et al., 2007)
(D'Abzac et al., 2010; Guo et al., 2014; Yu et al., 2007) ✓
(Guo et al., 2014) ✓ ✓ ✓
(Huang et al., 2016a; Wu et al., 2016a) ✓ ✓ ✓
(D'Abzac et al., 2010; Guo et al., 2014; Yu et al., 2007) ✓ ✓
(Guo et al., 2014; Yu et al., 2007) ✓ ✓
(D'Abzac et al., 2010; Guo et al., 2014; Yu et al., 2007) ✓ ✓ ✓
(Guo et al., 2014; Yu et al., 2007) ✓ ✓ ✓
(Guo et al., 2014) ✓ ✓ ✓
(D'Abzac et al., 2010) ✓ ✓ ✓ ✓
(D'Abzac et al., 2010; Guo et al., 2014) ✓ ✓
(D'Abzac et al., 2010) ✓ ✓ ✓
(D'Abzac et al., 2010) ✓ ✓
 H. Wei et al. / Water Research 143 (2018) 608e631
Fig. 4. The process of sludge dewatering companied with the formation of sludge cake.
obtain insights into the effects of various EPS fractions on sludge
dewaterability (Li and Yang, 2007). PN and PS are the two main
components. Several colorimetric methods, including Kjedahl,
Biuret, Lowry, bicinchoninic acid (BCA), and Bradford, have been
utilized to analyze PN content; the latter three methods have been
used extensively for biologically treated effluents in the past 20
years due to their simplicity and precision (Le et al., 2016). Other
colorimetric methods, such as anthrone and phenol-sulfuric acid,
have also been utilized to analyze PS content (Le and Stuckey, 2016).
With regard to the effects of various EPS components on sludge
dewaterability, many studies have demonstrated the negative
correlation between sludge filterability and PN content in soluble
EPS (Cao et al., 2016; Zhang et al., 2014b, 2015a, 2015c), and the
positive correlation between normalized CST and PN/PS in outer
layers; meanwhile, no apparent correlation has been observed
between normalized CST and PS (Yu et al., 2008). These results
may be due in part to the molecular size of PN being larger than
that of PS (Murthy et al., 2000; Yu et al., 2008). You et al. (2017)
considered the impact of PN on sludge dewatering and studied
the distribution of PN through the activity of leucyl aminopepti-
dase (LAP, a hydrolytic enzyme related to the degradation of PN)
and the concentration of adenosine 50 -triphosphate (ATP, a sup-
plier of energy in many enzymatic reactions) in the presence of
CeO2 nanoparticles. They found that inhibited LAP activity and
reduced ATP concentrations enhance the production of PN, which
results in increased sludge SRF and reduced dewatering perfor-
mance (You et al., 2017). However, Le et al. (2016) discovered that
the “protein” measured in wastewater samples using these
colorimetric assays often produces false positive results and has
little correlation to the real value. The methods used for analyzing
PS content encounter the same issue (Le and Stuckey, 2016).
Colorimetric methods, including anthrone and phenol-sulfuric
acid, were compared with three commercial assay kits in a pre-
vious study, and the results showed that existing colorimetric
methods can seriously under- or over-estimate the PS present in
wastewater (Le and Stuckey, 2016). Moreover, various pre-
treatments, such as coagulation/flocculation, have been proven to
exert strong effects on the transformation and change in EPS
fractions; thus, they significantly change the contents of various
EPS compositions in sludge and influence the moisture distribu-
tion and final dewatering performance (Cao et al., 2016; Chen
et al., 2015). This condition adds complication, and as a result,
the effects of various EPS fractions and their components become
difficult to explain accurately (Cao et al., 2016; Chen et al., 2015).
In addition, most studies on the effects of EPS on sludge dew-
aterability made deductions based on experimental results. The
mechanisms involved, especially those associated with various
pretreatments, remain unclear to date. To explore effective mech-
anisms in detail (Sheng et al., 2010), increased attention should be
given to the development of novel EPS extraction methods, in-situ
dynamic and quantitative analytical techniques (including the main
chemical compositions of PN and PS), elucidation of various influ-
encing factors, and microscopic investigation of the surface
613
structures of EPS and their interactions with various conditioners,
especially at the molecular level. This topic is discussed in detail in
the following sections.
2.3. Characteristics of sludge cake
2.3.1. Analysis of the properties of flocs
The process of sludge dewatering, shown in Fig. 4, is closely
related to the formation of sludge cake in water. Sludge cake is
formed by the aggregation of flocs in raw water, which consists of
various colloidal solids, including EPS. Floc properties affect the
characteristics of sludge cake and dewatering performance. Floc
properties mainly include floc size and compactness, and various
pretreatment processes that follow different dewatering mecha-
nisms result in distinct floc properties and sludge cake, which
significantly affect the final dewatering performance (Cao et al.,
2016; Fitria et al., 2013). Floc properties can be investigated using
the image or light scattering technique in combination with fractal
theory (Mandelbrot, 1983; Serra, 1982; Wei et al., 2009). Conflicting
results have been obtained regarding the effects of floc structure on
sludge dewatering. Fitria et al. (2013) found that large floc size
equates to high water removal. Cao et al. (2016) indicated that small
flocs with high compactness serve as skeleton builders to aid
dewatering in the pressure process. Floc compactness might play a
greater role in sludge dewatering than floc size. Floc compactness
by sweep flocculation is reported to be the highest due to the
particles enmeshed in the precipitation of flocs, and comparisons
show that the floc structure resulting from bridging flocculation is
the loosest because of the polymer molecules connecting the par-
ticles (Li et al., 2006). Thus, large but loose flocs form due to the
bridging effect only, and sludge conditioned with PAM alone cannot
achieve ideal dewatering performance (Chen et al., 2016b).
In addition to floc size and compactness, floc surface charac-
teristics, including surface charges and hydrophilicity/hydro-
phobicity, also affect floc aggregation and dewatering
performance. The changes in the surface characteristics and ag-
gregation of sludge can be determined with extended Derja-
guineVerweyeLandaueOverbeek (DLVO) theory and via
aggregation tests (Liu et al., 2010). The low energy barrier of
sludge flocs and high hydrophobicity promote flocculation,
which is conducive for good solideliquid separation (He et al.,
2015). Liao et al. (2001) showed that a strong inverse correla-
tion exists between the surface charge and hydrophobicity
(contact angles) of sludge, and Pere et al. (1993) revealed an
inverse correlation between the zeta potential and water contact
angle of sludge from pulp and paper mill effluents. Floc charac-
teristics can be also tested by contact angle to determine dew-
aterability to a certain extent (Pere et al., 1993). Thus, geometric
floc structures and surface characteristics should be considered
to obtain a comprehensive understanding of floc properties and
their effects on dewatering performance.
2.3.2. Sludge cake properties
Another main reason for inconsistent reports on the effects of
floc structure on sludge dewatering is that the determined factor is
the structure of the sludge cake itself and not that of the flocs on the
basis of the principle of the structureeactivity relationship. The
structure and formation process of sludge cake are important.
Sludge dewatering by draining and repelling water includes two
procedures: formation of sludge cake and subsequent compression
of the sludge cake (Fig. 4) (Thapa et al., 2009a). During the former
procedure, the solid in sludge is concentrated and aggregated,
resulting in the formation of a cake with the structural character-
istics of an interconnected network, which could be a sediment or a
filter cake at a certain concentration (Stickland, 2015). A portion of
614 H. Wei et al. / Water Research 143 (2018) 608e631
free water remains trapped in the cake. The sludge water and solids
in the cake present a complicated coexistence relationship; the
interaction between them results in unique characteristics through
various dewatering treatments. In the latter procedure, if the
applied pressure exceeds a certain load, the sludge network would
collapse, such that the water in the sludge is seriously trapped
because of cake void closure and subsequent deterioration in
sludge filterability, i.e., the permeability of the cake decreases with
the excess pressure (Liu et al., 2013; Novak et al., 1999; Qi et al.,
2011b; Smollen and Kafaar, 1997; Stickland, 2015). Thus, exces-
sively high pressure is useless for improving the dewatering rate.
Sveegaard et al. (2012) pointed out that within a low pressure range
(0e50 kPa), a linear relation is obtained between SRF and pressure
drop across the cake.
Therefore, the permeability and compressibility exhibited in
different types of sludge are important for dewatering perfor-
mance, including the removal of sludge water and the increase in
solid content (Qi et al., 2011a). Many studies have characterized the
compressibility of sludge by using the coefficient of compressibility
(s), which is obtained by two values of SRF under different applied
pressures, P1 and P2 (kg/m2), using Eq. (2.1) (Cao et al., 2016; Qi
et al., 2011a).

S
SRF1 P1
¼ (2.1)
SRF2 P2
Accordingly, a small value of s indicates low sludge compress-
ibility, which is beneficial for sludge dewaterability (Cao et al.,
2016; Zhang et al., 2017c).
Many researchers have also analyzed sludge expression char-
acteristics via experimental evaluations. For example, Shirato et al.
(1974) adopted the combined TerzaghieVoigt rheological model
with three parameters (B, h, and Ce) to study the time dependence
of the consolidation ratio during the dewatering process, as shown
in Eq. (2.2).
L1  L
Uc ¼
L1  Lf
" !#
p2 i2 Ce
¼ ð1  BÞ 1  exp  ,tc þ B½1  expðh,tc Þ;
4u20
(2.2)
where Uc represents the consolidation ratio; B represents the
fraction occupied by the second stage; Ce represents the modified
consolidation coefficient; h is a creep factor; u denotes the specific
volume of wet cake; i is the number of drainage surfaces; L is the
cake thickness at a certain consolidation time (tc); and L1 and Lf are
the cake thicknesses at the starting and ending times, respectively.
Under infinite consolidation time and assuming that the rate of
the second consolidation stage is much slower than that of the first
consolidation, Eq. (2.2) can be written as
Uc ¼ 1  B expðh,tc Þ; (2.3)
where B and h can be determined through the results of ln(1-Uc)
versus tc (Shirato et al., 1974). The TerzaghieVoigt rheological
model is a phenomenological model that lacks a theoretical basis
(Chang and Lee, 1998). This model can be applied to describe the
consolidation process of sludge without a large amount of bound
water, such as clay (Chu and Lee, 1999) and kaolin slurry (Chang and
Lee, 1998).
However, an unexpected consolidation stage is speculated to
arise from the erosion of strongly bound moisture (Chang and Lee,
1998). A modified three-stage consolidation model, shown in Eq.
(2.4), is proposed for sewage sludge to further reflect the consoli-
dation degree of sludge in the round (Chang and Lee, 1998; Chu and
Lee, 1999).
L1  L
Uc ¼
L1  Lf
" !#
p2 i2 Ce
¼ ð1  B  FÞ 1  exp  ,tc þ B½1  expðh,tc Þ
4u20
" #
tc
þF * ;
tC
(2.4)
where tC* is the duration of the entire stage and (1 e BeF), B, and F
represent the fractions occupied by the first, second, and third
stages, respectively. The first consolidation stage was proposed to
be a process of pore water leakage and cake structure collapse, the
second stage was interpreted as the reconfiguration of sludge
particles into a stable structure, and the third one was speculated to
be the erosion of bound water (Chang and Lee, 1998). The drawback
of this modified three-stage consolidation model is its weak sen-
sibility toward B and the fraction of moisture removed in the sec-
ond stage, which makes model outputs with very different B values
appear similar. Meanwhile, the model outputs have high sensibility
to h, which causes a large error (Vaxelaire and Olivier, 2006).
A visual and qualitative observation for the comparison of the
difference between the first and second stages could be obtained by
(1 e Uc) or ln(1 e Uc) versus the consolidation time plots (Lu et al.,
2017; Raynaud et al., 2012; Vaxelaire and Olivier, 2006). As pre-
sented in Fig. 5 (Raynaud et al., 2012), the steep slope of the first
stage indicates the high elasticity of the sludge cake. The slope of
the second stage characterizes viscous behavior, and a steep slope
indicates high mobility of aggregates. The two steep slopes are
desired for dewatering by expression (Chu and Lee, 1999; Lu et al.,
2017; Raynaud et al., 2012).
The structure of sludge cake intrinsically accounts for the final
dewatering performance. However, direct study of the condensed
structures of sludge cake is limited to qualitative observation by
microscopes (Cao et al., 2016; You et al., 2017; Yu et al., 2016). Few
study has performed quantitative or semi-quantitative investiga-
tion of the structural information of sludge cakes and the rela-
tionship between cake structure and dewatering performance,
0.0
0.1
1-Uc
0.01
Second consolidation stage
First consolidation stage Third consolidation stage
0.001
0 5000 10000 15000 20000 25000
tc (s)
Fig. 5. Analysis of compression dewatering curves (Raynaud et al., 2012).
 H. Wei et al. / Water Research 143 (2018) 608e631
which are important in the construction and regulation of a suit-
able sludge cake structure with porous and incompressible char-
acteristics by various pretreatments, such as coagulation/
flocculation, skeleton building, thermal method, microwave
method, ultrasonic conditioning, acidification/alkalinity, oxidation,
etc. The major difficulties in investigating this topic might be due to
insufficient advanced technologies and sophisticated analytical
instruments for highly complicated cake structures.
3. Coagulation/flocculation in sludge dewatering
Coagulation/flocculation is one of the most commonly applied
techniques to achieve efficient solideliquid separation in water
treatment (Bolto and Gregory, 2007; Bratby, 2016; Chang, 2011;
Ghernaout and Ghernaout, 2012; Gregory, 2006; Ives, 1977; Jiang,
2015; Khachan et al., 2014; Lee et al., 2014; Lyklema, 1985;
Overbeek, 1977; Sillanpa €€
a et al., 2018; Thomas et al., 1999; Verwey
and Overbeek, 1948; Yang et al., 2016b). In the coagulation process,
small suspended colloids in water are destabilized after diminish-
ing their surface charges by the addition of coagulants with an
opposite charge; then, the destabilized particles aggregate and
settle down (Bratby, 2016; Chang, 2011; Lee et al., 2014; Yang et al.,
2016b). To accelerate particle aggregation further and improve
settlement efficiency, polymeric flocculants with flexible long-
chain conformation are sometimes fed after coagulation as coag-
ulant aids. These polymeric flocculants act as bridges that adsorb
and connect various colloidal particles in water to form large flocs
that can be effectively removed by sedimentation (Bratby, 2016;
Chang, 2011; Lee et al., 2014; Yang et al., 2016b). The latter process
is called flocculation. Coagulation/flocculation technology is widely
employed in many industrial fields, including mining (Roussy et al.,
2004), oil extraction (Ahmad et al., 2005), and paper production
(Ahmad et al., 2008), aside from water treatment.
Coagulation/flocculation efficiency depends largely on the
selected coagulants/flocculants. Different coagulants/flocculants
exhibit different coagulation/flocculation performance due to their
different structural characteristics, namely, charge characteristics,
ionic properties, special functional groups, and molecular weight
(MW) (Bratby, 2016; Chang, 2011; Lee et al., 2014; Yang et al.,
2016b). Owing to the different characteristics of various types of
targeted pollutants, a suitable coagulant/flocculant should be
selected according to the coagulation/flocculation mechanisms. On
the basis of coagulation/flocculation effects, charge neutralization
and bridging are two widely accepted mechanisms (Bratby, 2016;
Chang, 2011; Yang et al., 2016b; Zhang et al., 2010a, 2014b). Given
that most of the insoluble suspended solids in water contain
negative surface charge, traditional coagulants are mainly trivalent-
metal inorganic salts, such as aluminum sulfate, ferric chloride,
poly-aluminum chloride (PAC), etc., to obtain high charge
neutralization effects on the basis of DLVO theory and the diffuse
electric double layer model (Hubbard, 2002; Overbeek, 1977;
Verwey and Overbeek, 1948). Meanwhile, the commonly used
flocculants are organic polymeric materials, including synthetic
and natural polymeric flocculants and bioflocculants. The MW of
polymeric flocculants is important in bridging flocculation (Anbu
Clemensis et al., 2012; Meyn et al., 2012; Zheng et al., 2014). The
MW of polyacrylamide (PAM), one of the most popular flocculants,
is usually more than 10,000,000 g/mol. In addition, cationic poly-
meric flocculants usually possess dual functions of coagulation and
flocculation (Lee et al., 2014; Yang et al., 2016b).
Certain coagulant/flocculant is commonly of single function-
ality, which always results in a single mechanism and high dose.
Low-MW inorganic coagulants and organic polymeric flocculants
exhibit different coagulation/flocculation behaviors and removal
superiorities because they possess substantially different molecular
615
structures and various affinities to different contaminants in water
(Bratby, 2016; Chang, 2011; Lee et al., 2014; Yang et al., 2016b).
Moreover, real wastewater and sludge are both usually complex
mixtures and contain various contaminants with different charac-
teristics. Thus, in addition to the sole use of various coagulants/
flocculants, the combined usages of various inorganic coagulants
and organic polymeric flocculants by making full use of their
different advantages are crucial. For example, the dewatering effi-
ciency of adding PAC in sludge followed by cationic polymers is
better than that conditioned by cationic polymeric flocculants
alone because PAC can efficiently neutralize the surface charge of
sludge and enhance the permeability of conditioned sludge
(Pambou et al., 2016).
The main mechanisms of sewage coagulation/flocculation,
namely, charge neutralization and bridging effect, are also suitable
for sludge dewatering (Bo € hm and Kulicke, 1997; Thapa et al.,
2009b). Coagulants can effectively destroy the relative stability of
charged particles and make them agglomerate into large flocs prior
to sedimentation and mechanical dewatering (Qi et al., 2011a;
Zheng et al., 2013, 2014; Zhu et al., 2013). In the dewatering process,
the charge neutralization effect can still reduce the thickness of the
hydrated shell of sludge particles and enhance the free water
content by compressing the electric double layer and weakening
the surface tension of sludge water (Wang et al., 2016a). Moreover,
coagulants can destroy the sludge network structure and weaken
its water-trapping capability in deep dewatering (Zhang et al.,
2017b). The bridging effect is also essential in sludge dewatering
and floc stability (Lee and Liu, 2000). The packed sludge flocs
formed by high-MW polyelectrolytes demonstrate good filtration
performance (Thapa et al., 2009b). Therefore, increasing the MW of
flocculants is a major modification method for improving dew-
atering efficiency.
Although the coagulation/flocculation mechanisms in sludge
dewatering are similar to those in contaminant removal, such as
suspended colloids and natural organic matter, in normal water and
wastewater treatment (Jiang, 2015; Lee et al., 2014; Sillanp€ € et al.,
aa
2018; Yang et al., 2016b), the treatment conditions and objectives of
the two processes are fundamentally different. Generally, the pur-
pose of coagulation/flocculation applied in normal water and
wastewater treatment is to remove various contaminants and
finally purify the water while that in sludge dewatering process is
mainly to thoroughly separate water from solids as far as possible.
Thus the former focuses on the aggregation and separation of
contaminants promoted by coagulants/flocculants; in addition to
this effect, the latter one still emphasizes the construction of suit-
able structure of sludge cake with good filtration performance
(Raynaud et al., 2012; Thapa et al., 2009a; Wei et al., 2018).
With regard to the treatment process, the solid content in sludge
dewatering is higher and more complicated than that in the normal
wastewater coagulation/flocculation process, which results in a
heterogeneous coverage of dewatering conditioner on the oppo-
sitely charged sludge particles (Sun et al., 2016). In normal waste-
water coagulation/flocculation, this similar phenomenon is called
charge patching, in which the zeta potential of the supernatant
deviates from zero at the optimal dose (Yang et al., 2016b). The
presence of many sludge particles and the non-uniform distribu-
tion of negative charge on the particles’ surfaces deteriorate the
ideal charge neutralization effect in the sludge dewatering process.
Moreover, some particles are trapped in the net-like structure
before being fully neutralized; thus, the zero zeta potential ach-
ieved by the dose might not the optimal one for sludge dewatering
(Sun et al., 2016). This fact might be interpreted as another phe-
nomenon, that is, the sludge with the large but loose flocs has not
ideal dewateriblity (Chen et al., 2016b). Numerous studies have
confirmed that cationic sludge conditioners can improve
616 H. Wei et al. / Water Research 143 (2018) 608e631
dewaterability effectively and have used the zeta potential as a
controlling parameter in interpreting the coagulation/flocculation
mechanisms in sludge dewatering (Jin et al., 2016; Lee and Liu,
2000, 2001; Lu et al., 2017; Sun et al., 2016; Zheng et al., 2014;
Zhu et al., 2013). However, the results showed that the zeta po-
tential is not significantly correlated with other controlling pa-
rameters, such as solid content and floc size (Sun et al., 2016; Zheng
et al., 2014). Moreover, charge neutralization and bridging simul-
taneously affect the coagulation/flocculation process, and the
combined action of charge neutralization and bridging has been
obtained based on experimental results (Sun et al., 2016; Zheng
et al., 2014). Thus, the explicit coagulation/flocculation mecha-
nisms in sludge dewatering are still unknown.
3.1. Factors that influence sludge dewatering
Coagulants/flocculants make contact with suspended colloids to
form large flocs that down easily (Bolto and Gregory, 2007; Gregory
and Barany, 2011), and are affected by various environmental fac-
tors. Therefore, the various factors that influence sludge dewatering
should be understood and considered. Conditioner dose, pH, and
temperature are three popular environmental factors and are
briefly discussed below.
3.1.1. Conditioner dose
Dose is one of the most important factors that affect the coag-
ulation/flocculation process in sludge dewatering. An optimum
dose exists for any conditioner in consideration of dewatering ef-
ficiency and economic issues. Insufficient or low doses of co-
agulants/flocculants result in weak charge neutralization and
bridging effects. Meanwhile, excessive doses might cause sludge
particles to be covered with coagulatants/flocculants, resulting in
the regeneration of the suspension stability of flocs, that is, the
“restabilization effect” (Lin et al., 2015; Yang et al., 2016b). Conse-
quently, the turbidity induced by bio-matters, such as PN and PS
with a relatively high MW, decreases initially and then increases
under coagulant overdose, which results in the fluctuation of sol-
uble EPS properties and affects dewaterability (Zhang et al., 2014b).
The “restabilization effect” is usually evident in coagulation sys-
tems that mainly follow simple charge neutralization and is not
evident in those that follow the charge patching mechanism
(Guibal et al., 2006; Ives, 1977). Sludge flocs exhibit reduced
compactness at high coagulant doses (Verrelli et al., 2009).
For organic polymeric flocculants and microbial flocculants
(MBFs), overdosing deteriorates the dewatering performance (Guo
et al., 2015; Guo and Ma, 2015; Jin et al., 2016; Pambou et al., 2016).
The CST curve that corresponds to sludge conditioned with poly-
mers drops initially and then rises as the dose increases, which
means that an optimal conditioning dose exists (Pambou et al.,
2016). Besides, system re-stability caused by superabundant posi-
tive charge and overdose of polymeric conditioners increase the
viscosity of the sludge water system and thus result in the reduc-
tion of filtrate and deterioration of dewaterability (Christensen
et al., 1993; Pambou et al., 2016). In a previous work, the SRF of
conditioned sludge increased and the filter paper broke due to the
very high viscosity of conditioned sludge at a polymeric flocculant
overdose of approximately 40 mg/g DS (Dong et al., 2011). In
addition, optimal conditioner doses change in different environ-
mental conditions, such as pH and temperature (Novak and
Bandak, 1989). Therefore, optimal doses under different situations
should be determined.
3.1.2. pH
The effect of pH on sludge dewatering is also crucial in the
wastewater treatment process (Zheng et al., 2013). Generally, the
surface charges of colloidal particles in wastewater and coagulants/
flocculants, especially in ionic coagulants/flocculants, vary under
different pH levels, which affect the charge neutralization effect
seriously. As reported by Neyens and Baeyens (2003), Besra et al.
(2004), and Raynaud et al. (2012), the negative charges of
colloidal particles are usually enhanced by the increasing pH value
of the system.
Various coagulants/flocculants usually exhibit different pH de-
pendencies in terms of sludge dewatering performance. The system
pH in inorganic coagulants can influence solubility, speed of the
hydrolysis reaction, and precipitation forms (Verrelli et al., 2009),
as shown in Fig. 6. Cao et al. (2016) reported that the hydrolysis
degree of inorganic salt coagulants exerts a significant impact on
dewatering performance, and monomer aluminum and oligomeric
state aluminum exhibit poor performance. Meanwhile, compared
with slow, reaction-limited cluster aggregation that forms denser
aggregates, rapid, diffusion-limited cluster aggregation that results
from a high metal hydrolysis ratio in a high-pH system deteriorates
the dewatering performance (Verrelli et al., 2009). Li et al. (2005)
pointed out that only acidification can decrease CST and SRF
when Al salts are used to treat sludge.
Water-soluble organic polymeric flocculants exhibit compli-
cated pH dependencies because of their distinct molecular struc-
tures and charge properties. Neutral and strongly ionic polymeric
flocculants are usually suitable for a relatively wide pH range in
sludge dewatering (Zheng et al., 2014). For example, three organic
polymeric flocculants, namely, PAM, cationic PAM (CPAM), and
chitosan-graft-poly(dimethy ldiallyl ammonium chloride) (chito-
san-g-PDMDAAC), can reduce MC to below 80% at a dose of 20 mg/L
in the range of pH 2e9, and they exert an excellent effect in the pH
range of 4e7 (Wang et al., 2016a). Amphoteric ones also show
improved water solubility, salt resistance, and flocculation perfor-
mance in a wide pH range (Dao et al., 2016; Lee et al., 2014; Rabiee
et al., 2014). However, weak ionic polymeric flocculants usually
exhibit strong pH effects. For example, chitosan, a weak cationic
natural polymer, usually shows good flocculation performance in
acidic conditions (Wang et al., 2016a).
For MBFs, the effect of system pH on dewatering is evident and
important because most microorganisms contain weak acidic and/
or alkaline ions, such as carboxyl groups, which are highly sensitive
to pH. The MBFs reported by Guo et al. (2015) exhibit better dew-
atering performance in the pH range of 6.5e8.5 than in other pH
ranges. Similarly, Zhang et al. (2010b) found that pH 7.5 is optimal
for the hydration of sludge conditioned by MBFs.
Fig. 6. Al3þ and Fe3þ coagulation diagrams (M3þ ¼ Al3þ or Fe3þ) (Johnson and
Amirtharajah, 1983).
 H. Wei et al. / Water Research 143 (2018) 608e631
In addition to the pH effects of coagulants/flocculants, the
impact of pH on EPS in sludge has also been considered. Extreme
pH causes a disruption on the cell wall, which results in intracel-
lular material leakage (Neyens et al., 2004). For example, EPS is
released and dissolved in the sludge bulk after acidification due to
instability at extreme pH values (Zhang et al., 2015c). In practice,
the mechanisms of EPS extraction are mainly based on the
improvement of repulsive force and disruption of the interaction
between EPS and cells after acidic or alkaline treatments (Sheng
et al., 2010). Chen et al. (2001) reported that sludge demonstrates
good dewaterability and settleability in acidic conditions due to the
destruction and reduction of EPS. Raynaud et al. (2012), who pro-
posed that pH variation releases trapped water and fine particles,
also confirmed the effect of pH on the floc structure.
3.1.3. Temperature
Practical experience in the coagulation/flocculation of waste-
waters shows that ambient temperature also affects coagulation/
flocculation processes. The optimal doses of coagulants/flocculants
usually increase as temperature decreases in a suitable range (Chen
et al., 2007; Zhang et al., 2010a). Zhang et al. (2010a) reported that
the difference between the optimal doses for a chitosan-based
flocculant in summer (~0.5 mg/L) and in winter (~1.0 mg/L) in
treating portable water can be double. This finding can be ascribed
to two factors (Yang et al., 2016b). One is that the viscosity of liquid
increases with decreasing temperature, which impedes the Brow-
nian movements of colloid particles and decreases agglomeration
as a consequence (Zhang et al., 2010a). The other is that high
temperature can usually improve the solubility and activity of
polymeric flocculants and therefore results in a high extended
conformation of macromolecules, which benefits bridging floccu-
lation (Sperling, 2006). However, a higher temperature is not
benefical for the flocculation effects also (Lu et al., 2005). Lu et al.
(2005) compared the temperature effect on trona suspension us-
ing a MBF at 35  C, 45  C, 55  C, and 65  C. The status of the coag-
ulation system, the suspension viscosity, and the activity of MBFs
were affected by temperature, and a maximum sedimentation rate
was obtained at 45  C (Lu et al., 2005). Because the flocs formed at
relatively high temperature was unstable, and the sedimentation
solid volume was easy to be expanded. Meanwhile, the bio-
flocculant might be partly denaturation in high temperature situ-
ation (Lu et al., 2005).
The effect of temperature on sludge dewatering can also be
explained by the abovementioned principles. In a previous study,
the limiting viscosity (the value of viscosity at the infinite shear
rate) decreased from 8.42 to 1.70 mPa for raw sludge and from
12.52 to 1.83 mPa for conditioned sludge and network strength
weakened for those sludge as temperature increased from 10  C to
70  C (Dong et al., 2011). From another aspect, temperature in-
fluences dewaterability by changing sludge properties. When the
temperature is lower than 15  C, the concentration of EPS, including
PN and PS, increases significantly; moreover, suspended solids have
a high concentration due to the weak floc structure in winter
(Wile
n et al., 2008). When the temperature drops further to the
freezing stage, limited quantities of organic matters are released
(Hu et al., 2011).
Freezeethaw and thermal treatments in sludge dewatering have
also been studied under further temperature regulation (Hu et al.,
2011; Wang et al., 2017). WAS dewatered by freezeethaw treat-
ment is accomplished through the separation of solid and liquid
fractions during the formation of the ice matrix. When bulk sludge
is completely frozen, tiny unfrozen regimes exist in the ice matrix,
and extended freezing or curing of sludge can improve sludge
dewaterability (Hu et al., 2011). Freezeethaw treatment not only
enhances sludge dewaterability but also solubilizes organic matters
617
from the sludge matrix (Hu et al., 2011). The improvement in sludge
dewaterability after thermal treatment can be attributed to the
changes in the original structures and properties of sludge (Wang
et al., 2017). Wang et al. (2017) pointed out that a significant
disintegration in EPS occurs, and the binding energy of water in
sludge decreases after hydrothermal treatment, in which most of
the energy input is consumed in breaking down the binding
strength between the adjacent water and solid particles; free water
becomes the main form of moisture existence in hydrothermal
sludge when the temperature exceeds 180  C. The melioration of
surface properties, including surface charge and relative hydro-
phobicity, reportedly promotes the decrease in negative electro-
static repulsion and destroys the binding effect between particles
and water (Wang et al., 2014). Thermal treatment in the tempera-
ture range of 60  Ce180  C destroys the cell wall and makes the
protein susceptible to biological degradation (Neyens and Baeyens,
2003). Organic solubilization increases logarithmically with treat-
ment duration in thermal pre-treatment (60  Ce180  C), and high
temperatures (>180  C) lead to high organic solubilization rates
(Zhang et al., 2017a).
3.2. Chemical coagulants/flocculants
Common dewatering reagents include inorganic salt coagulants,
such as ferric and aluminum salts, and synthetic organic polymeric
flocculants mainly include PAM and PAM derivatives. The addition
of these chemicals is conducive to the agglomeration of fine sludge
colloids through charge neutralization and bridging effects (Dentel
et al., 2000; Niu et al., 2013), thereby decreasing the SRF and con-
tent of bound water in sludge (Katsiris and Kouzeli-Katsiri, 1987).
Several novel bioflocculants and many combinations of techniques
with other pretreatments were reported and utilized to enhance
the final sludge dewatering of coagulation/flocculation.
3.2.1. Inorganic salt coagulants
Inorganic salt coagulants facilitate the conglomeration of sludge
particles into flocs through charge neutralization (Niu et al., 2013).
Besides, inorganic coagulants have been reported to serve as skel-
eton builders and improve the porosity of sludge cake (Qi et al.,
2011a). Sludge containing alum flocs or ferric flocs usually
demonstrate low compressibility, small but compact structures,
and high solid contents (Chen et al., 2015; Lai and Liu, 2004). The
most commonly used inorganic salt coagulants in wastewater
treatment are ferric and aluminum salts, which can be divided into
small-molecule inorganic coagulants, such as AlCl3, Al2(SO4)3,
FeCl3, Fe2(SO4)3, etc., and inorganic polymeric coagulants (IPCs),
such as PAC, polyferric sulfate (PFS), etc. IPCs generally have higher
charge density and larger molecular weight than small-molecule
inorganic coagulants. The various inorganic coagulants applied in
different sludge dewatering processes are summarized in Table 3.
3.2.1.1. Aluminum salt coagulants. Aluminum salts are the most
commonly used inorganic coagulants. Turchiuli and Fargues (2004)
investigated the dewatering performance and sludge flocs of two
small-molecule inorganic coagulants, Al2(SO4)3 and FeCl3, in clay
suspensions. They pointed out that the floc structure is linked to
sludge dewaterability (Turchiuli and Fargues, 2004). Alum flocs are
larger and more compact than ferric ones, resulting in the faster
settling of alum flocs; ferric flocs contain approximately 20% less
bound water than alum flocs but exhibit higher CST values and
therefore higher resistance to water removal than alum ones
(Turchiuli and Fargues, 2004). However, Verrelli et al. (2009) re-
ported that alum sludge exhibits poorer dewatering performance
than ferric sludge at high pH and doses due to the high hydrolysis
ratio of PAC. The same group also concluded that ferric and alum
618 H. Wei et al. / Water Research 143 (2018) 608e631

Table 3
Summary of various coagulants applied in sludge dewatering processes.a

Coagulants/ Sludge type pH of Solid Zeta potential MC (%) SRF(  1012 m/ CST (s) Optimal condition Refs
flocculants sludge contents (%) (mV) kg) (mg/g DS) b

initial final initial final initial final

FeCl3 þ an anionic Synthetic sludge ~7.2 0.05e0.5 176 75.7 (Turchiuli and
copolymer Fargues, 2004)
FeCl3 Sewage sludge 6.48 1.21 1.72 ~0.07 100 (Niu et al., 2013)
e7.12
Enzyme þ FeCl3 WAS 7.5 2.05 15.2 97.95 81.5 320 150 enzyme þ150 (Chen et al., 2015)
FeCl3
FeCl3 þ Na2SiO3 Urban dewatered- ~7.85 18.8 40.53 81.2 ~50.3 33 FeCl3 þ13 Na2SiO3 (Zhang et al.,
sewage sludge 2017a,b,c)
Al2(SO4)3 þ an Synthetic sludge ~7.2 0.05e0.5 176 55.5 (Turchiuli and
anionic Fargues, 2004)
copolymer
PAC Sewage sludge 6.48 1.21 1.72 <0.55 <100 (Niu et al., 2013)
e7.12
Enzyme þ PAC WAS 7.5 2.05 15.2 97.95 82.6 320 150 enzyme þ150 (Chen et al., 2015)
PAC
PAC þ cationic WAS ~0.8e0.9 ~80 ~5.9 (Pambou et al., 2016)
polymers
High performance Sewage sludge 6.48 1.21 1.72 ~0.16 100 (Niu et al., 2013)
PAC e7.12
AlCl3 Urban dewatered- 7.95 18.8 41.52 81.2 54.03 ~142 (Xia et al., 2016)
sewage sludge
Fe2(SO4)3 Anaerobic digested 7.45 ~2.03 1878.5 35.3 7
and Bien
(Bien
, 2014)
sludge
Titanium salt Surplus sludge 7.5 1.82 14.2 98.18 ~18.2 ~5.0 86.2 ~5 (Zhang et al., 2017c)
a
0e2 digits kept after the decimal point of all data based on the original reports.
b
DS means dry solid.

sludge yielded similar performance in dewatering kinetics after
comparing and assessing the dewaterability of a range of drinking
water treatment plant sludges through computation of dewatering
performance indicators for a diaphragm filter press (Verrelli et al.,
2010). Those inconsistent results might result from their different
characteristics of treated sludge and experimental conditions
(Turchiuli and Fargues, 2004; Verrelli et al., 2009, 2010). In addition
to using conventional inorganic coagulants in primary sludge
conditions, Xia et al. (2016) studied the influence of AlCl3 on deep
dewatering of dewatered-sewage sludge and found that the MC of
filter sludge cake decreases from 73.41% to 54.03% when the dose is
8 g AlCl3/300 g of dewatered-sewage sludge.
In addition to small-molecule aluminum salts, Zhang et al.
(2014b) investigated the conditioning effects of IPCs, PAC, and a
composite coagulant (HPAC) on the characteristics of soluble EPS.
They found that SRF is correlated with zeta potential, soluble EPS,
and dissolved organic carbon (DOC), and HPAC with high charge
density and good bridging capability is more efficient than PAC in
sludge dewaterability. Flocs conditioned by PAC and HPAC are
larger but looser than those using FeCl3 (Niu et al., 2013). Chen et al.
(2015) also reported that the floc formed using PAC in coagulation is
larger than that formed by FeCl3 at a low dose due to the abundant
binding sites with particles. Moreover, Zhao et al. (2009) used
silane coupling agents and AlCl3 to synthesize covalently bound
organic silicate aluminum hybrid coagulants, which possess prime
advantages of large MW and superior coagulation efficiency
compared with traditional coagulants, and their net positive
modification in comparison with using negatively charged acti-
vated silicic acid or polysilicic acid.
Several studies have investigated the roles of metal species in
sludge conditioning. Different speciation of aluminum, which is
generally separated into Ala or Almon (monomer and oligomeric
forms of aluminum), Alb or Al13 (mainly made up of middle
polymer forms of aluminum), and Alc or Alun (primarily
composed of high polymer forms of aluminum), can be catego-
rized by Ferron assay according to the polymerization degree,
and Alb and Alc are more positively charged and more stable than
Ala (Cao et al., 2016). Moreover, sludge flocs conditioned by Alb
and Alc are less compressible and smaller but more compact and
stable than those conditioned by Ala, and Alb and Alc also
perform better in protein-like substance removal and EPS
compression; thus, they exhibit better dewaterability than olig-
omeric forms of Al (Cao et al., 2016). PAX-14 (commercial PAC
coagulant), an IPC with a highly charged tridecameric polymer
aluminum polycation [AlO4Al12(OH)24(H2O)12]7þ (included in
Alb) relative to AlCl3 and Al2(SO4)3, is effective in terms of sludge
drying rate (Pambou et al., 2016). Salt inorganic flocculants with
suitable polymerization could improve their dewaterability (Cao
et al., 2016; Zhao et al., 2009).
Peeters et al. (2013) presented a new application of PAC as a
conditioner for WAS prior dewatering and drying to avoid world-
wide fouling problems in direct sludge dryers and to reduce torque
issues in indirect sludge dryers and sludge decanter centrifuges.
This beneficial effect is proposed to be the result of the bound water
associated with Al polymers in PAC solutions, which act as a type of
lubrication for intrinsically sticky sludge solids during drying
(Peeters et al., 2013).
3.2.1.2. Ferric salt coagulants. Ferric salts are another important
class of inorganic coagulants. Given their low cost, fast settling
velocity of ferric flocs, and lower toxicity, wider pH range of ap-
plications, better effect in low temperatures compared to PAC
(Bratby, 2016; Lee et al., 2014), ferric salts are also favored in many
wastewater treatment plants (Bien
and Bien
, 2014; Niu et al., 2013).
Ferric ions reportedly exhibit high affinity to protein-like sub-
stances (Chen et al., 2015; Wei et al., 2018; Yu et al., 2008), which is
the deciding factor of sludge filterability (Zhang et al., 2015b). Chen
et al. (2016b) compared the sludge floc structure and dewatering
performance of three coagulants, namely, FeCl3, PAC, and PAM. The
sludge flocs conditioned by FeCl3 had the smallest size but the
lowest MC of sludge cake without CaO2 pretreatment because of
their high charge density that enabled the efficient compression of
 H. Wei et al. / Water Research 143 (2018) 608e631
the double electric layer and skeleton builders of the hydrolysis
products (Chen et al., 2016b). Similarly, the sludge flocs conditioned
by FeCl3 were smaller but denser than those conditioned by PAC,
and the former showed better dewatering performance (Niu et al.,
2013). Moreover, sludge with a high Fe3þ concentration has a small
volume of small pores (1e10 nm) but a large volume of large pores
(>10 nm). The minimal small pores contribute to the affinity of
water in sludge, and the numerous large pores result in a rigid,
porous lattice structure (Yu et al., 2016). In addition, although Fe2þ
is usually employed as Fenton's reagent, the Fe3þ translated from
Fe2þ after oxidation can also be used as a good coagulant (Yu et al.,
2016; Zhang et al., 2015c). Yu et al. (2016) found that higher Fe3þ
content in comparison with Fe2þ content sharply reduces the
specific surface area of sludge and has lower SRF and CST and lower
MC of the cake.
In addition to small-molecule ferric salts, the suspended solid
colloid equivalence charge neutralization rate can increase to
nearly 100% with PFS conditioning but only to approximately 50%
with FeCl3 conditioning due to the characteristics of IPCs with high
charge density and large molecular weight; moreover, these two
conditioners can both decrease CST to a low value (Watanabe et al.,
1999).
3.2.1.3. Others. Apart from these traditional inorganic salt co-
agulants, other inorganic coagulants have been proposed. Na2SiO3
can be used as a common coagulant aid due to its high bridging
function. The synergistic effect between Na2SiO3 and FeCl3 on
dewatering urban dewatered-sewage sludge was investigated in a
previous work (Zhang et al., 2017b), and the results showed that
Na2SiO3 alone exerts an adverse effect on sludge dewaterability,
whereas the dehydration rate of sludge improved significantly after
conditioning with FeCl3 followed by Na2SiO3. In the combination of
FeCl3 and Na2SiO3, Na2SiO3 was proven to restructure sludge net-
works with high strength and low compression and therefore im-
proves sludge dewaterability (Zhang et al., 2017b).
Moreover, novel environmentally friendly inorganic materials,
CH2 CH
n
C O
NH2
CH2 CH CH2 CH
n m
C O C O
NH2 O-
CH2 CH CH2 CH
n m
C O COO(CH2)2N+(CH3)3 Cl-
NH2
CH2 CH CH2 CH
n m
C O COO-Na+
NH2
Fig. 7. Typical structures of various polymeric conditioners including nonionic, anionic, cationic, and ampholytic ones (Sun et al., 2016; Watanabe et al., 1999).
619
such as titanium (Ti) and magnesium (Mg) salt coagulants, which
exhibit good performance in wastewater treatment (Wang et al.,
2016b; Wu et al., 2001; Zhang et al., 2017c), have elicited much
attention in sludge dewatering (Huang et al., 2016a; Zhang et al.,
2017c). Sludge dewaterability is enhanced by the combination of
Mg(OH)2 and NaOH due to the bridging effect between Mg2þ and
EPS (Huang et al., 2016a). Zhang et al. (2017c) reported that using a
titanium salt coagulant (TSC) prepared with different basicity can
enhance WAS dewaterability, and the MC of sludge cake can
decrease to below 80% through the effective compression of EPS,
which is considered the most important mechanism of sludge
dewatering for TSCs. The floc size in sludge conditioned with pre-
hydrolyzed polytitanium chloride and Ti xerogel coagulant is larger
than that conditioned with PFS, and this condition may benefit
dewaterability (Wang et al., 2016b). Thus, conditioners synthesized
with novel inorganic materials present advantages over conven-
tional conditioners. However, these novel inorganic materials also
have drawbacks. For example, TSCs are usually expensive, easy to
hydrolyze, and affect the system pH (Zhang et al., 2017c). The
practical applications of these new inorganic coagulants are yet to
be investigated.
3.2.2. Organic synthetic polymeric flocculants
The application of inorganic coagulants is limited because these
coagulants are sensitive to pH. In comprehensive consideration of
dewatering rates, MC of sludge cake, and equipment costs, poly-
meric flocculants exhibit good dewatering performance due to
their larger floc size and more void spaces for water drainage (Lo
et al., 2001; Novak and O'Brien, 1975). PAM and its derivatives are
the most commonly used organic polymeric conditioners in sludge
dewatering. On the basis of different monomeric units that contain
various types of charges, polymeric conditioners can be categorized
as nonionic, cationic, anionic, and ampholytic (Novak and O'Brien,
1975; Sun et al., 2016; Watanabe et al., 1999), as described in
Fig. 7. The various organic polymeric flocculants applied in different
sludge dewatering processes are summarized in Table 4.
nonionic conditioner
anionic conditioner
cationic conditioner
R
R: H, CH3
CH2 C
o
COO(CH2)2N+(CH3)3Cl-
ampholytic conditioner
620 H. Wei et al. / Water Research 143 (2018) 608e631

Table 4
Organic polymeric flocculants applied in sludge dewatering process.a

Coagulants/ Sludge type pH of Initial solid Zeta potential MC (%) SRF(  1012 m/ CST (s) Optimal Refs
flocculants sludge content (%) (mV) kg) condition
b
(mg/g DS)
initial final initial final initial final

CPAM Sewage sludge 7.53 3.54 24.7 ~48 11.5 ~11.3 20 (Lu et al.,
2017)
CPAM Thickened ~2.20 79.59 205 44.3 2 (Yang et al.,
sludge 2016a)
CPAM Excess sludge ~7.4 ~0.58 ~98.5 84.9 17.6 1.4 3 (Jin et al.,
(thickened) 2016)
P(AM-DAC) Alum sludge 7.0 ± 0.1 8.52 8.94 48.2 0.23 (Sun et al.,
2016)
CPAM with Sewage sludge 7.04 ± 0.12 ~2.1 ± 0.15 21.6 ± 0.6 ~70 >10.5 1.99 1.90 (Chen et al.,
microblock 2016a)
structure
Cationic polyamidine Sewage sludge 6.7 0.6 77.67 10 (Guo et al.,
2016)
P(AM-DAC-BA) Sewage sludge 6.80 ± 0.12 1.80 ± 0.36 24.2 ± 0.4 67.8 >6.75 5.51 2.22 (Zheng et al.,
2014)
P(AM-DAC-BA) Textile sewage 11.57 1.5 73.2 3.33 (Zheng et al.,
sludge e11.63 2013)
P(AM-DMC-DAC) Thickened 7.0 4.5 ~-18.5 63.5 0.5e1 (Zhu et al.,
sludge 2013)
P(AM-AA-AMPS) Sewage sludge 7.3 ~5.4 65.1 2.5 (Ma et al.,
2013)
PAA Sewage sludge 7.53 3.54 24.7 ~47.4 11.5 ~8.9 5 (Lu et al.,
2017)
Nonionic polymer WAS 7.38 ~1.07 11.1 11 0.01 52 14 5-10 for CST20 (Lee and Liu,
(NP-800) for SRF 2001)
Nonionic polymer WAS 7.07 ~1.03 7.1 8.3 0.27 127 39 5.8 (Lee and Liu,
(NP-800) 2000)
a
0e2 digits kept after the decimal point of all data based on the original reports.
b
DS means dry solid.

3.2.2.1. Cationic polymeric flocculants. Given that the fine particles
in WAS are commonly negatively charged, cationic polymeric
flocculants are efficient in destabilizing sludge particles through
charge neutralization due to the dual-function of cationic poly-
meric flocculants (coagulation and flocculation). One of the typical
cationic polymeric flocculants is CPAM. Two methods are generally
applied to synthesize CPAMs (Jaeger et al., 2010). One is through the
post-polymerization functionalization of PAM, and the other is
through the copolymerization of cationic monomers and acryl-
amide (AM) (Zhao et al., 2016). CPAMs synthesized by post-
polymerization are limited by short preservation time and high
residue of monomers, which is highly toxic and can cause severe
neurotoxic diseases (Bolto and Gregory, 2007; Dao et al., 2016; Yang
et al., 2016b). Copolymerization is more popular than post-
polymerization. CPAMs are usually synthesized by copolymeriza-
tion of AM and one or more cationic monomers, such as 2-(acryl-
oyloxy)ethyl trimethylammonium chloride (DAC),
methacryloxyethyltrimethyl ammonium chloride (DMC), and
dimethyldiallyammonium chloride (DMDAAC) (Jiang and Zhu,
2014; Sun et al., 2016; Yang et al., 2010; Yang and Ni, 2012; Zheng
et al., 2013, 2014; Zhu et al., 2013).
CPAMs exhibit efficient dewatering performance due to their
effective mechanisms of particle flocculation, including charge
neutralization, particle bridging, and depletion flocculation (Bolto
and Gregory, 2007). The former two effects depend on the ab-
sorption of polymers on the particle surface, and the last one de-
pends on the presence of free, un-adsorbed polymers that are
probably not significant in water treatment practice (Bolto and
Gregory, 2007). CPAMs are thus widely used in many water and
wastewater treatment plants (Bolto and Gregory, 2007; Jin et al.,
2016; Lu et al., 2017; Yang et al., 2016a). Sun et al. (2016) found
that CPAMs synthesized with DAC and AM through microwave and
UV initiation are more effective than thermal and ultrasonic
initiating ones in terms of dewatering capability, fractal dimension
of the flocs, and the zeta potential. Although the addition of CPAMs
increases the sludge floc size for settleability and corresponding
filterability (Jin et al., 2016), it increases the viscosity of sludge,
which implies increased difficulty in piping the polymer-treated
sludge (Chen et al., 2005). Moreover, flocs with a network struc-
ture formed by PAM or CPAM in WAS have a strong water-
preservation capability, which worsens the dewaterability of WAS
(Zhang et al., 2017b).
In addition to normal CPAM, several cationic polymeric floccu-
lants with special structures have been reported (Chen et al., 2016a;
Guo et al., 2016). A conditioner with a cationic microblock structure
was synthesized with AM and DAC by applying template poly-
merization, which can achieve a low SRF of 1.99  1012 m/kg and an
MC of 71% at a dose of 40 mg/L and pH of 7.0 (Chen et al., 2016a).
When cationic units exhibit a blocky distribution, the adsorption
sites between the copolymer and negatively charged particle seg-
ments become stronger due to higher utilization of cationic charges
than randomly distributed ones (Chen et al., 2016a). Guo et al.
(2016) studied the synthesis, characterization, and sludge dew-
aterability of a novel cationic polyamidine that consisted of a five-
membered ring-like structural unit (Fig. 8). This flocculant with a
strong cationic degree and hydrophobic regions could reduce MC in
sludge cake to 77.7% at a dose of 60 mg/L.
3.2.2.2. Anionic polymeric flocculants. Anionic polymeric floccu-
lants, such as anionic PAM (APAM), have also been used in sludge
dewatering, although they have the same negative charges as the
suspended particles in wastewaters. The main dewatering mecha-
nisms of APAMs are efficient adsorption and bridging effects (Ma
et al., 2013). Compared with CPAM and nonionic PAM, APAM has
the worst dewaterability (highest SRF) due to its electrostatic re-
pulsions with negatively charged surface particles in wastewaters
 H. Wei et al. / Water Research 143 (2018) 608e631
H2 H2 H2 H2 H2 H2 H2 H2
C C C C C C C C
CH CH CH CH CH CH CH CH
NH2
C N CN N C N C
N+H3X- N+H3X- N+H3X-
Fig. 8. Structure of a polyamidine conditioner (Guo et al., 2016).
(Besra et al., 2004; Lo et al., 2001).
Apart from APAMs, poly(acrylic acid) (PAA) can also be used as a
flocculant in sludge dewatering. PAA exhibits better performance
than CPAM in dewatering acid-treated sludge in terms of dew-
atering and dehydration degree, and the addition of PAA in sludge
can enhance the dewatering rate at filtration and expression phases
(Lu et al., 2017). An anionic copolymer [P(AM-AA-AMPS)] synthe-
sized by AM, acrylic acid (AA) and 2-acylamido-2-methyl propane
sulfonic acid (AMPS) with the molecular weight of 8  106 g/mol
showed better dewatering efficiency than commercial PAM; the
minimum filter cake's MC was reduced to 65.1% (Ma et al., 2013).
3.2.2.3. Amphoteric polymeric flocculants. Ionic polymers that
contain cationic and anionic functional groups are called ampho-
teric polymers, which usually show notable improvement in solu-
bility and salt resistance in a wide pH range (Dao et al., 2016; Lee
et al., 2014; Rabiee et al., 2014; Yang et al., 2016b). Although
several amphoteric polymeric flocculants, including synthetic and
natural ones, have been studied in the wastewater treatment field
(Dao et al., 2016; Lee et al., 2014; Rabiee et al., 2014; Watanabe et al.,
1999), the application of these flocculants in sludge dewatering is
rare (Watanabe et al., 1999).
Watanabe et al. (1999) utilized a metal coagulant for charge
neutralization and an amphoteric polymer (structure shown in
Fig. 7) for flocculation to improve organic sludge dewaterability and
obtain a high dehydration rate and low MC of the sludge cake. Their
results indicated that the charge neutralization rate determines the
type and dose of polymer to be used. The mechanism of the con-
ditioning process was as follows: (1) charge neutralization reacted
with metal salt, and formation of metal hydroxide; (2) the anionic
part of the amphoteric polymer molecule reacted with the positive
charge of metal hydroxide while the cationic part reacted with the
negative charge of the primary sludge; (3) gigantic flocs formed
through further bridging and flocculation; and (4) the uncharged
anionic part reacted with the cationic part within flocs, which made
the sludge particles tightly bound.
3.2.2.4. Nonionic polymeric flocculants. Nonionic polymeric floc-
culants with low charge density might be no match for PAC and
FeCl3. When WAS is pre-oxidated, the MC of the sludge cake could
be reduced to below 80 wt% through further treatment with inor-
ganic coagulants, whereas using PAM alone cannot achieve this due
to its low charge density (Chen et al., 2016b). However, ionic
polymeric flocculants with high charge density might prevent the
primary flocs coated by flocculants from approaching one another
due to electrostatic repulsions; thus, nonionic polymers show a
higher probability of further particle aggregation (Besra et al.,
2004).
In single polymer conditioning, a previous study demonstrated
that a nonionic polymer generates stronger bridging effect due to
its higher MW and thus unusually exhibits better dewaterability
than a cationic polymer (Lee and Liu, 2001). Moreover, in terms of
SRF and CST, sludge conditioned with a dual-polymer conditioning,
i.e. cationic polymer followed by a nonionic polymer performs
better than sludge conditioned with a nonionic polymer followed
621
by a cationic polymer and sludge conditioned with a single polymer
(Lee and Liu, 2000). By adding the cationic polymer first, sludge
particles are adsorbed, and small but compact primary flocs are
formed; then, the nonionic polymer is added to adsorb on the loops
and tails of the cationic polymer to form a larger and more com-
pacted flocs (Lee and Liu, 2000).
3.2.3. Natural polymeric flocculants
Inorganic salt coagulants and organic synthetic polymeric floc-
culants have been proven to be efficient in sludge dewatering, but
they might result in secondary pollution and entail many health
risks due to residual metal ions or the release of noxious polymeric
monomers into the target water (Bratskaya et al., 2004; Lin et al.,
2015; Song et al., 2010; Wang et al., 2016a). Therefore, natural
polymeric flocculants have attracted significant attention as envi-
ronmentally friendly, biodegradable, and nontoxic flocculants
(Kaith et al., 2010; Lanthong et al., 2006; Yang et al., 2016b).
Polysaccharide-based natural polymers consisting of hex sugar
rings have a rigid rod structure, which might improve cake
compressibility. In addition, similar structures between
polysaccharide-based EPS and polysaccharide-based flocculants
may result in good affinities (Wei et al., 2018).
However, natural materials also have many drawbacks in prac-
tical application, including small molecular weight, low charge
density, and poor water solubility (Wu et al., 2016b). To overcome
these disadvantages, various chemical modification methods, such
as etherification (Anthony and Sims, 2013; Chen et al., 2007; Heinze
et al., 2004; Kaith et al., 2010; Liu et al., 2017a; Khalil et al., 1998;
Krentz et al., 2006; Wei et al., 2008, 2018; Zhang et al., 2007),
esterification (Yang et al., 2016b), oxidation (Mathew and
Adlercreutz, 2009), and graft copolymerization (Huang et al.,
2016b; Lanthong et al., 2006; Liu et al., 2017b; Mishra et al., 2011;
Wu et al., 2016b; Yang et al., 2014), have been applied to improve
dewatering performance (Lv et al., 2014; Shogren, 2009; Wang
et al., 2013, 2016a). With the aid of these modification methods,
many natural polymer-based flocculants have been reported and
studied. However, current research on natural polymeric floccu-
lants is still inadequate, especially their application in sludge
dewatering. Table 5 summarizes various natural polymeric floccu-
lants applied in sludge dewatering processes.
3.2.3.1. Starch-based flocculants. Starch, one of the most commonly
used natural resources, cannot directly act as a flocculant in general
(Wang et al., 2013). However, it has been modified to yield various
starch-based flocculants used in wastewater treatment (Anthony
and Sims, 2013; Chen et al., 2007; Heinze et al., 2004; Huang
et al., 2016b; Khalil et al., 1998; Krentz et al., 2006; Lanthong
et al., 2006; Liu et al., 2017a, 2017b; Mishra et al., 2011; Wei et al.,
2008, 2018; Wu et al., 2016b; Yang et al., 2014; Zhang et al.,
2007). The surface of many organic pollutants and inorganic par-
ticles in WAS are mostly negatively charged. Introducing certain
cationic functional groups onto the starch backbone is highly
popular.
Grafting modification is a useful methods that introduces pos-
itive pieces onto starch at branch chains, such as the STC-g-PDMC
(starch-graft-poly[(2-methacryloyloxyethyl) trimethyl ammonium
chloride]) shown in Fig. 9 and STC-g-PDMDAAC [starch-graft-pol-
y(diallyl dimethyl ammonium chloride)] (Lv et al., 2014; Wang
et al., 2013; Wu et al., 2016b). The MW of these grafted floccu-
lants with cationic groups on long molecular chains is obviously
increased, which is conducive to producing enhanced charge
neutralization and bridging effects (Lv et al., 2014; Pourjavadi et al.,
2013; Wang et al., 2013). Lv et al. (2014) reported a novel sludge
conditioner, STC-g-PDMDAAC, which have not only hydrophilic
groups for solubility and dispersion but also hydrophobic groups
622 H. Wei et al. / Water Research 143 (2018) 608e631

Table 5
Natural organic flocculants applied in sludge dewatering process.a

Coagulants/flocculants Sludge type pH of Solid Zeta potential MC (%) SRF (  1012 m/ CST (s) Optimal condition Refs
sludge contents (%) (mV) kg) (mg/g DS) b

initial final initial final initial final initial final

Starch-g-PDMDAAC Sewage 7.53 2.15 24.3 ~50.2 75.3 ~6.3 76.53 ~11.35 4e6 (Lv et al., 2014)
sludge
Starch-CTA WAS 7.1 ± 0.2 ~1.5 12.7± 98.5 82.9 2.06 0.23 ~6e9 (Wei et al.,
1.3 e83.0 e3.67 e039 2018)
Starch-g-PDMC Anaerobic >17.84 0.40 ~13.04 (Wang et al.,
sludge 2013)
combined silicon- Secondary 6.75 ~5 95.0 9.83 0.21 120 25.8 6 (Lin et al.,
aluminum-ferric-starch sludge 2015)
Chitosan-g-PDMDAAC WAS 6.9 ~2.8 97.2 68.10 18.3 2.04 ~0.71 (Wang et al.,
2016a)
Chitosan-AlCl3 Synthesized 8.42 33.5 1.25 7.23 0.70 (Ma et al.,
sludge 2016)
PAM þ enteromorpha (EP) Sewage 6.46 ± 0.22 ~2.2 ± 0.2 9.5 12.9 97.8± ~3.63 ~13 0.68 PAM þ 0.14 EP (Zhao and Gao,
sludge 0.2 2015)
a
0e2 digits kept after the decimal point of all data based on the original reports.
b
DS means dry solid.

for building hydrophobic regions for forming drainage channels.
The sludge conditioned with STC-g-PDMDAAC thus had low SRF
and CST, and the final sludge water content was reduced to 50.6%
from 97.85% (Lv et al., 2014). Besides, a cost-effective starch-based
flocculant was recently synthesized by etherification using 3-
chloro-2-hydroxypropyl trimethyl ammonium chloride (CTA) as
etherifying agent, which exhibited good sludge dewaterability due
to not only effective charge neutralization and bridging flocculation
effects but also its good affinity to polysaccharide components in
EPS because of their similar structures; moreover, the sludge
dewatering performance of this CTA modified starch-based floc-
culant was further enhanced after combined use with FeCl3 (Wei
et al., 2018).
In addition to the cationic organic monomers mentioned above,
several inorganic materials, such as aluminum, iron, and silicon,
have been complexed and grafted onto the starch backbone to
produce starch-based composite flocculants with a high charge
density, as shown in Fig. 10 (Lin et al., 2015; Peng et al., 2017).
Combined siliconealuminumeironestarch (CSiAFS) can adapt to
large pH variations (3.0e11.0), and combined alumi-
numeferrousestarch (CAFS) can break sludge colloids easily and
release many LB-EPS proteins; both are superior to PAM, PAC, and
FeCl3 in dewatering treatment (Lin et al., 2015; Peng et al., 2017).
3.2.3.2. Chitosan-based flocculants. Chitosan (poly-b-(1 / 4)-2-
amino-2-deoxy-D-glucose) is a high-performance natural
polysaccharide material; it is derived from the deacetylation of
natural chitin, which is the second most abundant natural polymer
in the world (Guibal et al., 2006; Wang et al., 2012, 2016a; Yang
et al., 2016b). Chitosan contains abundant free amino groups
along the chain backbone that are cationically charged in acidic
media. Chitosan and its many derivatives thus exert more promi-
nent flocculating effects as flocculants than other polysaccharide
materials in wastewater treatment and sludge dewatering due to
their more efficient charge neutralization and bridging effects
(Guibal et al., 2006; Wang et al., 2012, 2016a; Yang et al., 2016b).
Wang et al. (2016a) prepared a cationic grafted chitosan-based
flocculant (chitosan-g-PDMDAAC) having a great network and an
inconsecutive appearance with numerous channels, which was
proven to be more effective than that of PAM, CPAM, and PAC in
sludge dewatering. In addition, a chitosan-AlCl3 composite coagu-
lant prepared by mixing chitosan and an AlCl3 stock solution was
investigated, and the sludge conditioned by this composite coag-
ulant had higher dewaterability than that conditioned by chitosan
and AlCl3 dosed individually due to the improvement of charge
neutralization and the bridging effect (Ma et al., 2016). However,
chitosan is more expensive than other polysaccharide materials,
such as starch and cellulose (Ma et al., 2016; Yang et al., 2016b).
3.2.3.3. Others. Aside from starch and chitosan, other poly-
saccharide materials, such as cellulose (Liberatore et al., 2016),
€
tannins (Ozacar and Şengil, 2000), enteromorpha (Zhao and Gao,

CH2OH
CH2 OH O -
Cl O
N+
O O
OH O
OH O CH3
CCH2
K 2S2 O8+N2 n
-
OH COOC2H4N(CH3)3 Cl
OH

Starch
STC-g-PDMC
Fig. 9. Preparation process of STC-g-PDMC (Wu et al., 2016b).
 H. Wei et al. / Water Research 143 (2018) 608e631 623

2015), cyclodextrins (Hartong et al., 2007), spent coffee ground biogenic flocculants, which are usually combined with energy
(Hao et al., 2018), and their derivatives, have also been investigated substance, such as Fe2þ, and need a relatively long time for incu-
in the dewatering field. Although several of them only act as bation (Murugesan et al., 2014a; Kurade et al., 2014; Wong et al.,
coagulant aid in the dewatering process, the addition of certain 2016a, 2016b). The addition of iron compound further improves
natural polymers can enhance the permeability of sludge and thus in situ production of biogenic flocculants (Murugesan et al., 2014a;
improve the dewatering performance (Hartong et al., 2007; Ozacar€ Kurade et al., 2014; Wong et al., 2016a, 2016b).
and Şengil, 2000). The different MBFs used in sludge dewatering are summarized
The combination of 15 mg/L of PAM and 3 mg/L of enteromorpha in Table 6. One normal MBF produced by Rhodococcus erythropolis
by Zhao and Gao (2015) obviously improved sludge dewatering separated from alkaline-thermal pre-treated sludge can make the
efficiency in terms of the average particle size of flocs, dehydration DS and SRF of sludge reach 22.5% and 3.4  1012 m/kg, respectively
rate, and PAM reagent required. Ozacar € and Şengil (2000) found (Guo and Ma, 2015). In a previous study, filamentous fungal strains
that combined usage of tannin and Al2(SO4)3 improves sludge were isolated from bioleaching sludge to act as a bioflocculants, one
filterability significantly compared with using Al2(SO4)3 only, and of which reduced CST of the chemically enhanced primary
tannin is more effective than a synthetic anionic polyelectrolyte as a
coagulant aid. Hartong et al. (2007) pointed out that cyclodextrins
combined with alum or CPAM can increase the solid content and
dewatering rate, which can result in a 2.8 percentage point increase OH OH H OH2 H OH2 H OH2 H OH2 H OH OH
HO O O O O O HO OH
in cake solids in a full-scale trial. They proposed that cyclodextrins
promote agglomeration by neutralizing excess charge on the Starch O Si Si Al Al Fe Fe Si Si
polymer-conditioned sludge surface (Hartong et al., 2007). OH O O O O O OH OH2
OH H H H H H
OH OH H2O H2O H2O H2O OH OH
3.2.4. Bioflocculants n
Natural polymeric flocculants are mainly derived from poly- (a)
saccharide materials, such as starch, chitosan, cellulose, etc. As
OH2 OH2
another class of green chemical conditioners, MBFs, i.e. natural H OH2 H OH2 H OH2 H OH2 H
H2 O O O O O O
organic macromolecular substances produced by microorganisms, OH2
have been obtained (Zhang et al., 2010b). MBFs have attracted Al Al Al Fe Fe Fe
O OH2
significant attention due to their advantages of biodegradability, O O
H2O H O O
non-toxicity, high efficiency, and cost effectiveness compared with H H H H
H2 O H2 O H2O H2O H2 O H2O
traditional coagulants/flocculants (Yang et al., 2012a). Based on n
cultivation of specific microorganisms and different usage condi- Starch O
O
tions in sludge conditioning, two categories of MBFs are roughly
(b)
classified in this study. One refer to normal MBFs, which have
similar conditioning processes to conventional inorganic co- Fig. 10. Schematic structures of (a) CSiAFS and (b) CAFS (Lin et al., 2015; Peng et al.,
agulants and organic flocculants; the other are complex MBFs, i.e. 2017).

Table 6
Microorganism-produced bioflocculants applied in sludge dewatering process.a

Microorganisms Sludge type pH of Solid contents (%) Oxidation- SRF CST (s) Optimal condition Refs
sludge reduction (  1012 m/
potential (mV) kg)

initial finial initial finial initial finial

b
AF Chemically 6.2 2.71 97 71.9 ~5.0 122.7 20 AF culture þ Fe2þ 10% (Wong et al.,
enhanced primary (v/v) 2016b)
treatment
Activated sludge 6.7 2.08 89.6 10 <5 12.6 7.9
b
AF Anaerobically 7.7 2.1 117.1 8.3 <3 19.5 ~7.5 AF culture þ Fe2þ 10% (Wong et al.,
digested sludge (v/v) 2016a)
AF b Anaerobically 7.45 2.05 178 16.1 <1 30.4 <20 AF culture þ Fe2þ 10% (Murugesan
digested sludge (v/v) et al., 2014a)
AF b Chemically 6.74 ± 0.05 2.59 ± 0.13 31.4 ± 1.1 272 ± 12 111 ± 13.4 ~11.1 121.2 ± 3.6 10 AF culture þ Fe2þ 10% (Kurade
enhanced primary (v/v) et al., 2014)
treatment
Filamentous Chemically 7.03 2.0 236 86.9 35.5 5% (w/v) at pH 6.85 (Murugesan
fungal strains enhanced primary e7.15 et al., 2014b)
treatment
Rhodococcus Secondary settling 6.5 13.2 22.5 11.3 3.4 12.12 mg/g DS c (pH (Guo and
erythropolis tank sludge 7.5) Ma, 2015)
Klebsiella sp. Secondary settling 8.04 13.1 17.5 10.87 3.36 6 mg/g DS c (pH 8) (Yang et al.,
tank sludge 2012a)
7
Proteus mirabilis Secondary settling 6.23 ± 0.12 3.19 ± 0.64 ~28  10 ~2.5  107 (1.7 mg TJ- (Zhang et al.,
TJ-1 tank sludge 1þ ~ 12.5 mg CaCl2)/g 2010b)
DS c (pH 7.5)
Strain GA1 Secondary settling 6.5 13.2 21.7 11.3 3.6 11.36 mg/g DS c (pH (Guo et al.,
tank sludge 7.5) 2015)
a
0e2 digits kept after the decimal point of all data based on the original reports.
b
Cultured with the energy substance FeSO4$7H2O.
c
DS means dry solid.
624 H. Wei et al. / Water Research 143 (2018) 608e631

Table 7
A brief comparison of various coagulants/flocculants.

Coagulants/ Representatives Dose (mg/ pH range Temperature Shear Floc properties Dewatering Reacting Prices/ Toxicity
flocculants g DS)a force efficiency time producing
Size Compactness
costs

Inorganic coagulant PAC, FeCl3 High Moderate Insensitive Sensitive Moderate Denser Moderate Short Low High
(>100) (5.0e9.0) (Al3þ …)
Synthetic polymeric CPAM, PAA Low Wide (2.0 Insensitive Moderate Big Moderate Good Short High High
flocculants (<100) e12.0) (AM …)
Natural polymeric Starch, chitosan Low Wide (2.0 Insensitive Moderate Big Moderate Good Short Moderate Low
flocculants (<100) e12.0)
Bioflocculants Rhodococcus Low Dependedb Sensitive Insensitive Moderate Denser Good Dependedb High Low
erythropolis, AF (<100)
a
DS means dry solid.
b
Depended on specific microorganism in bioflocculants.

treatment sludge from 83.15 s to 35.50 s, and supplementation of
metal cations, such as Ca2þ and Fe3þ, could further improve the
dewaterability (Murugesan et al., 2014b). Other studies inoculated
sludge with Acidithiobacillus ferrooxidans (AF) culture with the
energy substance Fe2þ (Kurade et al., 2014; Murugesan et al., 2014a;
Wong et al., 2016a, 2016b). Sludge treatment with isolated cells of
AF without Fe2þ exhibited no CST reduction, whereas the same
treatment with Fe2þ addition reduced the sludge CST from 122.7 s
to 72.5 s (Wong et al., 2016b). These complex MBFs could improve
the settlement of organic matter into the sludge pellet (Kurade
et al., 2014; Wong et al., 2016a, 2016b); this result was proven by
the 27% increase in the calorific value of the treated sludge (Kurade
et al., 2014).
Compared with other flocculants, such as cationic polymer, PAC,
and Al2(SO4)3, MBFs can show a similar or even better performance
for sludge dewaterability at an optimum dose (Kurade et al., 2014;
Yang et al., 2012a). The combined usage of MBF and the above-
mentioned coagulants/flocculants greatly improves the dewatering
performance due to large flocs formed through the enhanced
charge neutralization and bridging effect (Guo and Ma, 2015). A
study reported that when TJ-F1, a type of MBF, is used alone, it is
better than P(AM-DMC) in sludge dewatering in terms of both SRF
and the time to filter (TTF); the composite using these two performs
better in dewaterability (Zhang et al., 2010b). However, the draw-
backs of MBFs are worthy of note. Cultivation processes of MBFs are
usually time-consuming. The incubation time of biogenic floccu-
lants is much longer; moreover, pH of sludge system fluctuates
large in the incubation process (Kurade et al., 2014; Murugesan
et al., 2014a; Wong et al., 2016a, 2016b). In addition, many
normal MBFs were purified and obtained using lyophilization,
which are high cost and time-consuming also (Guo et al., 2015;
Yang et al., 2012a; Zhang et al., 2010b).
3.2.5. Evaluation of various coagulants/flocculants
Table 7 summarizes various kinds of coagulants and flocculants
in sludge dewatering. Inorganic coagulants and synthetic polymeric
flocculants are the most frequently used dewatering conditioners,
and they mainly include aluminum and ferric salts and PAM de-
rivatives, respectively. Although inorganic coagulants are cheap
and exert a good effect on dewatering, they also have many
drawbacks, such as high dose, sensitivity to system pH, and residual
metal ions, which may result in biological toxicity (Bratskaya et al.,
2004; Walton, 2013). Synthetic polymeric flocculants, among
which PAM derivatives are the most commonly used, are excellent
in terms of dose, floc size, and dewatering efficiency, but their cost
is relatively high. Furthermore, the addition of PAM and its de-
rivatives may lead to secondary pollution and health risks due to
their residual monomers (Lin et al., 2015; Wang et al., 2016a).
Bioflocculants require a relatively long retention time, which is
difficult in small plants (Guo et al., 2015; Wong et al., 2016b). Lastly,
polysaccharide-based natural polymers have attracted increasing
attention due to their many advantages, such as environmental
friendliness, widespread availability, biodegradability, and promi-
nent structural features. However, they still lack practical applica-
tion and need further investigation (Kaith et al., 2010; Lanthong
et al., 2006; Wei et al., 2018; Yang et al., 2016b). Therefore, high-
efficiency, cheap, and environment-friendly coagulants/floccu-
lants should be developed.
Considering the shortcomings of polysaccharide-based natu-
ral polymers, their application performance can be improved
through chemical modifications (Lv et al., 2014; Shogren, 2009;
Wang et al., 2013, 2016a). In sludge dewatering, grafted natural
polymeric flocculants are usually employed; thus, grafting
copolymerization is the most commonly used modification
method in this field (Lv et al., 2014; Shogren, 2009; Wang et al.,
2013, 2016a). When economic factors and maneuverability are
considered, other simpler modification methods (Lv et al., 2014;
Shogren, 2009; Wang et al., 2013, 2016a; Wei et al., 2018), such as
etherification, esterification, oxidation, etc., should be noted.
They can introduce various functional groups onto polymers
conveniently. Bridging flocculation is also important in sludge
dewatering aside from charge neutralization. An enhanced
bridging effect can be obtained by increasing the MW of poly-
meric flocculants. Apart from grafting copolymerization, appro-
priate chemical crosslinking can also improve the MW of
polymeric conditioners (Fig. 11).
With regard to the various introduced functional groups,
frequently studied polysaccharide-based natural polymeric floc-
culants, such as starch (Lv et al., 2014; Wang et al., 2013; Wei et al.,
2018), chitosan (Wang et al., 2016a), and cellulose (Liberatore
et al., 2016), are usually modified. Cationic pieces are grafted
onto the polysaccharide backbone to achieve efficient charge
Fig. 11. Schematic description of crosslinking modification.
 H. Wei et al. / Water Research 143 (2018) 608e631
neutralization effects because of the negatively charged surface of
mostly inorganic and organic colloidal particles in the sludge. Few
studies focused on anionic modified conditioners. Anionic poly-
meric conditioners are usually much cheaper than cationic ones,
and they have a large hydrodynamic size in water due to intra-
chain electrostatic repulsions, which are significantly beneficial
to the bridging flocculation effect (Flory, 1953). In addition to
hydrophilic ionic groups, hydrophobically associating flocculants,
which can help form hydrophobic regions within the sludge and
further develop a porous structure in a mechanical dehydrating
process, may be synthesized (Guo et al., 2016; Lv et al., 2014; Yang
et al., 2010; Zheng et al., 2013). Several reports have confirmed the
good dewatering performance of sludge conditioned with floc-
culants containing hydrophobic regions and high cationic degrees
(Guo et al., 2016; Lv et al., 2014; Yang et al., 2010; Zheng et al.,
2013).
Among the various polysaccharide-based natural polymers,
cellulose and starch cost less than chitosan and can be modified
chemically by introducing different functional groups onto their
backbone due to the large amount of hydroxyl groups on the
saccharide rings for different application purposes (Huang et al.,
2016b; Lv et al., 2014; Pourjavadi et al., 2013; Wang et al., 2013;
Wei et al., 2018). Therefore, cellulose and starch present better
application potentials in practical operations. Furthermore, due to
the distinct structures of natural polymers, natural conditioners
show different flocculation and dewatering properties from tradi-
tional inorganic ones. The flocculation mechanisms in sludge
dewatering should also be investigated in detail. Flocculant struc-
ture is a key to the involvement of different flocculation
mechanisms.
The structures of organic polymeric flocculants, including syn-
thetic and natural ones, are highly complicated due to their long-
chain features (Elias, 1984; Flory, 1953; Yang and Hu, 2001). From
the viewpoint of polymer physics, the structure of a macromolecule
should include short-range, long-range, and condensed structures,
which correspond to the repeating unit structure of the polymer
chain (type and chemical composition), long chain morphology
(shape and size), and packed polymer chains (supermolecular
structure), respectively (Elias, 1984; Flory, 1953; Yang and Hu,
2001). The multiplicity of the polymer structure accounts for the
wide performance range characteristic of polymer-based materials.
Research on polymeric flocculants, aside from type and chemical
composition (short-range structure), includes the structural
morphology and conformation of polymers in the solution (long-
range structure), which is a particularly important determinant of
the final flocculation performance because flocculants are usually
dissolved in water. Moreover, the optimal dose of organic polymeric
flocculants is usually in the range of 0.1e100 mg/L, which according
to polymer solution theory is extremely diluted (Elias, 1984; Flory,
1953). Therefore, compared with traditional polymer solution
theories (Fuoss and Strauss, 1948; Fuoss and Cathers, 1949;
Manning, 1974; Oosawa, 1971; Radeva, 2001), the new relevant
theory established from much wider polymer concentration ranges
may be more promising in studying the hydrodynamic structure of
polymers in extremely diluted concentration regions (Cheng, 1997;
Yang et al., 2012b). However, until now, this topic has been rarely
investigated.
Furthermore, the structureeactivity relationship can be estab-
lished according to the achieved flocculation mechanisms, the
structural features, and final flocculation performance of floccu-
lants. The quantitative correlations among the preparation condi-
tion, structural features, and flocculation properties can be well
constructed through the combination of the synthesis recipe for
flocculants. Accordingly, a proper flocculant can be selected or
designed through precise molecular control to achieve the desired
625
dewatering performance and optimize the dewatering process. This
strategy is a practical operational method.
3.3. Techniques combined with other pretreatments
Large amounts of organic matters, such as EPS, are crucial to
wastewater treatment and sludge dewatering (Cao et al., 2016;
Chen et al., 2015, 2016b; Zhang et al., 2017c). However, the addition
of cationic polymers can partially release EPS from the sludge
surface to the supernatant (Zheng et al., 2014). Inorganic co-
agulants, including aluminum (Cao et al., 2016) and ferric salts (Niu
et al., 2013), can make sludge cakes less compressible due to the
strong binding strength between ions and protein-like substances
(Chen et al., 2016b; Niu et al., 2013). Sole application of traditional
coagulation/flocculation cannot achieve satisfactory dewatering
performance. In China, WAS is usually conditioned with traditional
PAM before mechanical filtration in many small and medium-sized
sewage treatment plants, resulting in dewatered sludge of 30
million tons per year, with MC as high as 80% (Lu et al., 2013; Xia
et al., 2016). This fact reflects the drawback of using coagulation/
flocculation alone.
Aside from coagulation/flocculation, other pretreatments have
been confirmed to effectively improve sludge dewatering perfor-
mance by releasing bound water. These pretreatments include
skeleton builder addition (Wu et al., 2016c), sonic treatment (Bien

and Bien
, 2014; Huan et al., 2009; Zhu et al., 2018), thermal treat-
ment (Neyens and Baeyens, 2003; Wang et al., 2014, 2017; Zhang
et al., 2017a), acid and alkali treatment (Li et al., 2005), oxidation
methods (He et al., 2015; Mo et al., 2015; Yu et al., 2016; Zhen et al.,
2012a, 2012b, 2012c), and enzymatic treatment (Ayol, 2005;
Dursun et al., 2006; Thomas et al., 1993; Wu et al., 2016a), the
mechanisms and corresponding effects of which are briefly sum-
marized in Table 8. However, after pretreatment with these
methods, release of bound water and degradation of the EPS
structure simultaneously occur. Consequently, more fine particles
are produced, and organic matters are transferred to the outer
layers (Chen et al., 2015, 2016b). This is a part of reasons why using
those conditioning methods solely, such as enzymatic treatment or
oxidation (Chen et al., 2015, 2016b), cannot achieve an ideal dew-
atering performance or even deteriorates dewaterability (Thomas
et al., 1993). On this occasion, coagulants/flocculants can make
the best use of their functionality through charge neutralization
and the bridging effect. Thus, the combined usages of various
pretreatments with coagulation/flocculation show a potential for
use in efficient sludge dewatering.
3.3.1. Physical conditioning treatments
3.3.1.1. Skeleton builders. Skeleton builders can improve the
incompressibility and permeability of the sludge cake but increase
the excess sludge yield. Therefore, treatments that combine skel-
eton builders with coagulants/flocculants and other pretreatments
have been established. For example, coal fly ash (Chen et al., 2010),
biochar (Wu et al., 2016c), lime (Yu et al., 2016), lignite (Qi et al.,
2011b; Thapa et al., 2009a, 2009b), slag (Ning et al., 2013), gyp-
sum (Zhao and Bache, 2001; Zhao, 2006), and red mud (Zhang et al.,
2014a), were added in previous studies to improve dewaterability.
Thapa et al. (2009a, 2009b) showed that the structure of lignite
conditioning sludge is more porous and less compressible than that
of directly flocculated sludge through experiments with mercury
porosimetry, scanning electron microscopy (SEM), and cake yield
stress curves. Sludge dewaterability was improved due to the
porous, rigid, and less compressible structure of the sludge condi-
tioned by combining cationic polyelectrolyte residues and nega-
tively charged lignite particles (Qi et al., 2011b). The results
resembled those of a study on slag-conditioned sludge, in which
626 H. Wei et al. / Water Research 143 (2018) 608e631
Table 8
Mechanisms and corresponding effects of various pretreatments before coagulation/flocculation.
Type of pretreatment Mechanism Brief description of function
Skeleton builder addition Structure Improving incompressibility and
construction permeability of cake
Enzymatic treatment Hydrolysis effect Disrupting WAS microfloc and
transformation of EPS fractions
Oxidation (Fenton/Fenton- Chemical Degrading EPS fractions and acting as (Chen et al., 2016b; He et al., 2015, 2016; Mo et al., 2015; Yu et al., 2016; Zhang
like, nanomaterial) oxidation salt coagulant
treatment
Acid and alkali treatment Degradation Degrading EPS fractions and
influencing zeta potential
Ultrasonic treatment Degradation of floc Solubilizing organic matters, reducing
and destroying particles and inactivating
cells microorganisms
Microwave treatment Degradation Degrading organic matters and
releasing bound water
Thermal treatment Degradation Degrading organic matters and
releasing bound water
slag acted as a skeleton builder to form an incompressible and
porous structure, and sludge dewaterability was further improved
by combining with CPAM because the flocculated slag-treated
sludge reduced sludge compressibility by incorporating rigid
structures and releasing water by increasing the solids’ porosity,
whereas the flocculated sludge by itself formed a highly
compressible structure (Ning et al., 2013). Similar results were
obtained when gypsum functioned as a physical conditioner com-
bined with a polymer for conditioning a certain alum sludge
because the polymer conditioning of sludge improved the rate of
water removal, and gypsum formed a permeable and rigid lattice
structure for further dewatering under a high positive pressure
(Zhao, 2006).
Physical conditioners can be modified to obtain dual-function
materials for better utilization and further improvement of
incompressibility and permeability. For example, red mud has a
long-term persistence of alkalinity and a high surface area, which
make this material act as a skeleton builder and a neutralizer in
combination with Fenton's reagent (Zhang et al., 2014a). Raw rice
husk biochar modified by FeCl3 can not only act as a skeleton
builder but also improve the neutralization effect due to its posi-
tively charged characteristics (Wu et al., 2016c). The prospects of
combining coagulation/flocculation and skeleton building in sludge
dewatering or developing several cationic coagulants/flocculants
that contain similar features of skeleton builders are therefore
feasible. These physical conditioners can play an important role in
sludge dewatering after proper modification.
3.3.1.2. Microwave treatment. Microwave treatment is believed to
disintegrate the matrix and destroy microflocs, leading to the release
of EPS and changes in particle size distributions (Cai et al., 2017). Cai
et al. (2017) demonstrated that the dewatering performance of
antibiotic mycelial residue initially increases and then decreases
while MC substantially decreases under microwave treatment.
However, microwave application slightly enhances sludge dewater-
ability with a short contact time but significantly deteriorates dew-
atering performance with long contact time (Yu et al., 2009). This
finding may be due to the two conflicting effects of microwave
treatment, i.e., release of trapped water and formation of fine par-
ticles, and the latter effect deteriorates the filtration efficiency.
Despite the controversy, the effect of EPS concentration on dew-
aterability has been mentioned (Cai et al., 2017; Yu et al., 2009).
Therefore, an appropriate microwave intensity was proposed by Luo
et al. (2013), who pointed out that the optimal combined condition
for tannery sludge pretreatment is as follows: microwave output
Reference
(Chen et al., 2010; Ning et al., 2013; Qi et al., 2011b; Thapa et al., 2009a, 2009b;
Wu et al., 2016c; Yu et al., 2016; Zhang et al., 2014a; Zhao, 2006; Zhao and Bache,
2001)
(Ayol, 2005; Dursun et al., 2006; Thomas et al., 1993; Wu et al., 2016a)
et al., 2017c; Zhen et al., 2012a, 2012b, 2012c)
(Li et al., 2005; Raynaud et al., 2012)
(Huan et al., 2009; Zhu et al., 2018)
(Cai and Wang, 2017; Liu et al., 2016b)
(Neyens and Baeyens, 2003; Wang et al., 2014, 2017; Zhang et al., 2017a)
power of 648 W, radiation time of 60 s, and cationic CPAM dose of
8 mg/L. Sludge treated under this condition performs better than
sludge treated by CPAM alone (Luo et al., 2013). In the combined
technique, microwave radiation destroys the floc structure to release
bound water and reduce the viscosity of sludge but form many fine
particles, and CPAM plays an important role in flocculation and ag-
gregation of those fine particles (Luo et al., 2013).
3.3.1.3. Ultrasonic treatment. Ultrasonic treatment is an efficient
tool for sludge disintegration and improving sludge biodegrad-
ability (Bien
and Bien
, 2014; Huan et al., 2009; Zhu et al., 2018).
Combined ultrasound-CPAM conditioning exerts a synergistic ef-
fect in comparison with using ultrasound alone because the effect
of ultrasonic treatment mainly strips the EPS and water from the
sludge flocs (Zhu et al., 2018). Likewise, the combined use of
Fe2(SO4)3 and polyelectrolytes also results in a decrease in the hy-
dration of sonicated sludge in the process of vacuum and pressure
filtration (Bien
and Bien
, 2014). However, the ultrasonic disinte-
gration degree should be appropriately controlled, and incompact
sludge flocs can be thus disrupted to small fragments and re-
flocculated to tight particles with the help of coagulants/floccu-
lants, resulting in improved dewaterability (Huan et al., 2009).
Huan et al. (2009) found that when the disintegration degree ex-
ceeds 40%, most cells are destroyed at different degrees, thereby
deteriorating the dewatering performance; only when the sludge
disintegration degree is 2%e5% can sludge dewaterability be
improved with the conditioning of FeCl3.
3.3.2. Chemical conditioning treatments
3.3.2.1. Acid and alkali treatment. The effect of pH on dewatering
efficiency is crucial. Similarly, acid and alkali treatment disrupts floc
fragments and releases organic polymers and bound water (Li et al.,
2009). NaOH and Ca(OH)2 are generally applied during alkaline
treatment (Li et al., 2008, 2009). Ca(OH)2 can improve sludge
dewaterability, but the weight of sludge cake also increases (Li et al.,
2008). Li et al. (2008) demonstrated that low-dose NaOH (<0.2 mol/
L) deteriorates sludge dewaterability, but dewatering performance
recovers gradually with the increase in the NaOH dose. Compared
with alkali conditions, acidification decreases the CST and SRF of
sludge containing aluminum and a recover Al3þ as coagulants more
efficiently (Li et al., 2005). Alkali conditions and salt addition
decrease the filtration kinetic significantly, whereas acid conditions
improve dewatering (Raynaud et al., 2012). However, excessive
acidification significantly increases the concentration of organic
matters in sludge bulk and deteriorates the dewatering rate (Li
 H. Wei et al. / Water Research 143 (2018) 608e631
et al., 2005); the addition of only 5 mg/g of PAA in acidified sludge
can improve the dewatering rate through the re-flocculating effect
(Lu et al., 2017).
3.3.2.2. Oxidation treatments. Oxidation treatment can degrade
organic matters, such as EPS, for further improvement of dew-
atering performance (He et al., 2015; Mo et al., 2015; Yu et al., 2016;
Zhen et al., 2012a, 2012b, 2012c). Fenton/Fenton-like treatments,
which are highly popular oxidation techniques, are widely inves-
tigated in sludge conditioning because they can produce hydroxyl
radicals ($OH) for the collapse and degradation of EPS and for
improving the dewatering performance with the aid of iron species,
especially Fe3þ, as a coagulant in addition to the oxidation effect (Yu
et al., 2016). The technique of Fe2þ and activated persulfate oxida-
tion, which ruptures flocs and releases bound water (Zhen et al.,
2012a, 2012b, 2012c), has been also established to treat WAS.
Several novel oxidants have been investigated too. WAS pre-
oxidation by 20 mg of CaO2/gTSS was co-conditioned by FeCl3,
PAC, or PAM in a previous study, and sludge dewaterability was
enhanced obviously after three chemical re-flocculation (Chen
et al., 2016b). Furthermore, certain inorganic salts, such as Fe2þ
and zero-valent iron, exert a strong oxidation effect when incor-
porated with H2O2 or persulfate salt. The production of Fe3þ can act
as a coagulant, skeleton builder, and binding agent with PN. Nano-
oxidants have been also utilized in sludge dewatering. Nano-Fe2O3
prior to TSC addition can further improve sludge dewaterability and
decrease compressibility (Zhang et al., 2017c). In another study, a
nano-material, Fe@Fe2O3, which was combined with PDMDAAC
and H2SO4 with doses of 40, 4.8, and 136 mg/g DS, decreased the
MC of sludge from 78.1% to 64.8% (He et al., 2016). The authors (He
et al., 2016) explained that the Fe@Fe2O3 nanomaterial induced
molecular oxygen activation, and the hydroxyl radicals decom-
posed EPS. Thus, the bound water in sludge was converted into free
water.
3.3.2.3. Enzymatic treatment. Biological enzymes can not only sol-
ubilize the EPS components of WAS under mild conditions but also
improve its subsequent treatment and disposal (Chen et al., 2015).
Enzymatic treatment, which disrupts the sludge structure, is usu-
ally combined with coagulants/flocculants (Dursun et al., 2006;
Thomas et al., 1993). The dose of the enzyme product should be
suitable because under-dosage provokes slight hydrolysis and re-
leases a portion of bound water, whereas over-dosage creates many
hydrophilic end groups, which counteract the dewatering perfor-
mance (Thomas et al., 1993). For example, with the increase in the
dose of two enzymes in a previous work, sludge SRF decreased from
7.47  1013 to approximately 4  1013 m/kg at a protease dose of
100 mg/g and from 1.34  1015 to approximately 0.95  1015 m/kg
at an a-amylase dose of 50 mg/g; then, SRF increased with the
overdose of the two enzymes (Chen et al., 2015). The sludge
filtration rate decreased significantly after enzymatic treatments,
and the addition of inorganic coagulants could not only reconstruct
the floc structure compactly, but also removed the EPS in sludge
bulk. The results indicated that the combined technique could
make MC lower than that of sludge cake treated with coagulants
alone (Chen et al., 2015).
In summary, these physical and chemical conditioning treat-
ments disintegrate the sludge flocs more or less, but excessive
fragmentation is adverse to sludge dewaterability. Thus, combined
coagulation/flocculation is feasible in sludge dewatering. Given that
many problems exist in combination techniques for conditioning
WAS in practice, such as optimum combination ratio, operation
difficulty, and various characteristics of sludge, the synergistic and
compensation mechanisms of coagulation/flocculation with these
pretreatments should be studied thoroughly.
627
4. Conclusion
Practical operation indicates that the current dewatering per-
formance for WAS is still relatively poor, which results in high-
cost sludge treatment. The large amount of EPS, the high energy
demand for bound water drainage, and the strong compressibility
of sludge cake are considered difficulties in the dewatering pro-
cess. Other reasons include insufficient coincident standards for
testing these above parameters. However, the major reason is the
lack of well-established structureeactivity relationship due to the
highly complicated and multilevel structural features of sludge. In
sludge dewatering, various solids, including EPS, are first aggre-
gated to form flocs. Then, the flocs are further assembled in a
condensed sludge cake. The condensed structure of the sludge
cake, not the EPS and flocs, is the key to determining the final
dewatering performance, which might account for the many
inconsistent reports between the dewatering performance and
structural characteristics of EPS or flocs. To understand sludge
better, the characteristics of sludge cake should be studied thor-
oughly in addition to the water content, solid components, and
floc properties. Accordingly, a suitable porous and incompressible
structure of sludge cake could be constructed and regulated to
obtain the desired dewatering performance. However, little work
has been conducted on the quantitative or semi-quantitative
investigation of the structural information of sludge cakes,
which might be further examined by using neutron scattering,
synchrotron radiation-based techniques, and so on. In-depth
investigation of the condensed structure of sludge cake obvi-
ously depends on the development of advanced characterization
techniques and highly sophisticated instruments.
Coagulation/flocculation as an indispensable pretreatment
for sludge dewatering is widely applied in water and waste-
water plants because of its economic efficiency and strong
maneuverability. To further improve the sludge dewatering
performance, novel coagulants/flocculants should be developed
urgently and should have the characteristics of high dewatering
efficiency, low cost, and environmental friendliness. Research
and development of novel coagulants/flocculants are intrinsi-
cally based on the well-established structureeactivity relation-
ship. Dewatering mechanisms should thus be studied in detail
based on not only the structural characteristics of sludge but
also on those of the coagulants/flocculants. The effects of
various metal species of inorganic coagulants and the multilevel
structural characteristics of organic polymeric flocculants,
including various ionic or nonionic functional groups and their
contents and distributions (short-range structure) and molecu-
lar weight and various chain conformations in solutions (long-
range structure), on different target sludge types should be
investigated in detail. However, the work related to this topic is
unsystematic and even limited.
From the perspective of coagulation/flocculation processes and
conditioning methods, various inorganic and organic conditioners,
including coagulation/flocculation and composited coagulation/
flocculation, can be combined to fully make use of their respective
advantages and eventually achieve better dewatering performance.
The combination of coagulation/flocculation with other pre-
treatments is also an effective method. In addition to traditional
pretreatments, such as addition of skeleton builders, microwave
method, ultrasonic conditioning, acidification/alkalinity, oxidation,
etc., nanotechnology, advanced oxidation, and bio-treatment also
present a significant potential to be energetically developed and
applied in sludge dewatering. However, synergistic and compen-
sation mechanisms, including composite applications of inorganic
and organic coagulants/flocculants and various pretreatments with
coagulation/flocculation, should be well investigated. They are
628 H. Wei et al. / Water Research 143 (2018) 608e631
important and have great practical significance in promoting the
applications of their combined usages and obtaining a final ideal
dewatering performance.
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