FEATURE ARTICLE
Multifunctional Flocculants
Advanced Polymer Flocculants for Solid–Liquid Separation
in Oil Sands Tailings
Sarang P. Gumfekar, Vahid Vajihinejad, and João B. P. Soares*
The generation of tailings as a by product of the bitumen extraction process
is one of the largest environmental footprints of oil sands operations. Most
of the tailings treatment technologies use polymer flocculants to induce
solid–liquid separation. However, due to the complex composition of tailings,
conventional flocculants cannot reach the same performance achieved in
other wastewater treatments. Over the last couple of decades, the oil sands
industry has used acrylamide-based flocculants to treat tailings, achieving
major progress in process optimization and integration with mechanical
operations, but they still could not reach the required land reclamation
targets. Over the last 5 years, the group designed, synthesized, and tested
several novel polymer flocculants tailored for oil sands tailings treatment.
This feature article communicates recent developments in these innova-
tive polymers. The article first provides a background on tailings generation
and treatment, followed by the description of advanced polymer flocculants
categorized according to their microstructures such as linear, branched, and
graft. The other tailings remediation technologies and one of the initial works
on modeling of tailings flocculation is discussed.
1. Introduction
1.1. Generation of Oil Sands Tailings
Oil sands deposits in Canada are the third largest oil reserve
in the world, with deposits estimated at 28.3 billion cubic
meters.[1] In the Clark hot water bitumen extraction process, oil
sand ores are mined, crushed, and mixed with warm alkaline
water, followed by the separation of bitumen using a flotation
process.[2] Figure 1 shows the schematic of oil sands extraction
emphasizing the main elements of the process. The extraction
of bitumen from oil sands using the process shown in Figure 1
forms waste tailings that cause technical and environmental
problems when discharged into tailing ponds. Currently, the
tailing ponds in Canada have polluted more than 200 km2,
which is approximately equivalent to 111 000 hockey rinks. The
Dr. S. P. Gumfekar, V. Vajihinejad, Prof. J. B. P. Soares
Department of Chemical and Materials Engineering
University of Alberta
Edmonton, AB T6G 2V4, Canada
E-mail: jsoares@ualberta.ca
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/marc.201800644.
DOI: 10.1002/marc.201800644
Macromol. Rapid Commun. 2019, 40, 1800644 1800644  (1 of 18)
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volume of tailings is projected to reach
two billion cubic meters in 2034 if tail-
ings management procedures remain the
same.[3]
When fresh tailings consolidate for a
few years after their transfer to tailings
ponds, gravitational forces cause the coarse
components (sands) to settle, releasing a
limited amount of the water to the surface.
The bottom part of the remaining suspen-
sion is called mature fine tailings (MFT).
Typically, MFT contains negatively charged
clays (≈30–35 wt%), water (≈65 wt%), and
residual bitumen (3–5 wt%).[4] Compared
to fresh tailings, which still contain coarse
particles that consolidate over time, MFT
is a gel-like suspension that consolidates
extremely slowly. Clays in MFT con-
tain mainly kaolinite, illite, and mixed-
layer clays such as interstratified illite–
smectite and kaolinite–smectite.[5] Fine
clays are mostly responsible for the water
retained in MFT due to their high sur-
face area. Additionally, fugitive bitumen
binds clay particles, constricting interparticle pathways and
trapping water.
1.2. Colloidal Stability of Tailings and Challenges
in Dewatering
Since MFT contains a mixture of negatively charged clays, it
shows strong negative zeta potential that causes colloidal sta-
bilization. Generally, clays contain hydroxyl and oxide func-
tional groups that make their particles negatively charged at
neutral pH (pH = 7) and even more negative as pH increases.
Thus, the stability of clays in MFT increases with increase in
pH. Current bitumen extraction processes use caustic addi-
tives to liberate bitumen from oil sands, generating alkaline
tailings with pH of approximately 8.5. This alkaline medium
increases the electrostatic repulsive forces between clays
and significantly increases MFT stability. Surface charges
also arise when ions from the neighboring solution adsorb
on an initially neutral solid surface. Another source of sur-
face charges is the dissociation of surface groups. The silica
surface of clays can react with water to form silicic acid,
which can then dissociate to form a silicic anion, as shown
below.
(SiO2 )S + H2O ↔ (H2SiO3 )S ↔ (HSiO3− )S + H+ (1)
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As the reaction shown in Equation (1) proceeds in alkaline pH,

negative charges build up on the solid surface and H+ ions dif- Sarang P. Gumfekar is a
fuse into the bulk solution. The negative charges generated on postdoctoral fellow at the
clay surfaces via this mechanism induce significant repulsive University of Alberta, Canada.
forces to make them colloidally stable. His work focuses on the
Polymer flocculants and coagulants reduce the repulsive design of new polymers and
forces via charge neutralization and bridging. The current control of their microstruc-
polymer-based technologies, however, struggle to meet the fol- tures. He obtained his Ph.D.
lowing multiple requirements for effective MFT treatment: in chemical engineering from
the University of Alberta,
i. Settling: The extremely slow settling rate of MFT is attributed
under the supervision of Prof.
to the use of caustic additives during the bitumen extraction
João Soares. He also received
process that gels ultrafine particles (50–400 nm) in MFT, in-
an M.A.Sc. degree from the
creasing its viscosity and making it difficult to consolidate.
University of Waterloo, Canada, and a B.Eng. degree from
The surface charge of the fine particles is also responsible for
the University of Pune, India, both in chemical engineering.
stabilizing the MFT suspension.
Alongside polymer synthesis, he is interested in physico-
ii. Dewaterability: MFT holds a significant amount of water at
chemical processes such as flocculation, nanofiltration,
alkaline pH. Commonly employed polymer flocculants are
and advanced oxidation processes for water treatment.
usually water soluble and aggravate this problem, trapping
water even after floc formation. The presence of residual bi- Vahid Vajihinejad is a
tumen on the surface of clays further limits the adsorption Ph.D. candidate at the
of conventional water-soluble flocculants, making porous and University of Alberta, Canada,
fragile aggregates holding a large amount of water. under the supervision of
iii. Quality of recovered water: The water recovered from tailings Prof. João Soares. His
should be recycled back to the bitumen extraction process, research focuses on studying
but its quality affects the efficiency of bitumen extraction polymer microstructure–
from oil sands. Although charge neutralization of clays using flocculation performance rela-
inorganic cations such as Ca2+ or Al3+ may seem to be an easy tionships, flocculation mode-
solution for tailings consolidation by coagulation of particles, ling, and reaction engineering
these cations are detrimental to the bitumen extraction pro- of water-soluble polymers.
cess as it reduces the recovery and quality of the froth by a He obtained his M.E.Sc. in
mechanism known as slime coating. Presence of even small chemical engineering from Western University, Canada, and
amount of fines in the supernatant (turbidity) causes damage B.Sc. from the Sharif University of Technology, Iran.
to the process equipment.
iv. Solids content of the sediments: Current polymer flocculants João B. P. Soares is a
can treat MFT to a certain extent, but MFT needs to be di- professor in the Department
luted to promote effective interactions between polymer and of Chemical and Materials
clay particles. Thus, it is imperative to remove both internal Engineering at the University
and externally-added water from MFT to produce trafficable of Alberta, Canada. He is a
sediments. Additionally, the water entrapped in the flocs re- Campus Alberta Innovates
duces the solids content of the sediments, requiring further Program Chair in Interfacial
expensive mechanical treatments such as centrifugation and Polymer Engineering for
filtration. Oil Sands Processing, and
a Tier I Canada Research
1.3. Conventional Technologies Chair in Advanced Polymer
Reaction Engineering. His
The major methods used to treat MFT include the use of lime, main research interests are polymerization reaction
inorganic coagulants, polymer flocculants, pH control, and engineering, polyolefin synthesis and characterization, and
freeze–thaw cycles. The following section outlines two of the polymer flocculation engineering.
industrial methods that are currently being used. Consolidated
tailings and paste technology are the two technologies adopted
by the industry.
The consolidate tailings method involves mixing densified
extraction tailings (cyclone underflow) and MFT with a coagu- divalent ions that negatively affect the bitumen extraction pro-
lant (typically gypsum) to produce non-segregating tailings, cess.[6] Moreover, H2S may be released after treatment due to
which when discharged into a tailings pond form a rapidly the anaerobic reduction of SO42− with the residual bitumen in
consolidating deposit. This approach, however, suffers from a the tailings.[7]
few drawbacks. Gypsum significantly changes the chemistry Paste technology involves the settling of suspended fines
of the recycled water by imparting a high concentration of within a process vessel (thickener) promoted by polymer

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Figure 1.  Schematic of the oil sands extraction process.

flocculants. Depending on the type of polymer, the flocculated
fines settle quickly and form a stable solids bed that can be
deposited in tailings ponds for land reclamation, allowing the
supernatant water to be recycled to the bitumen extraction pro-
cess. The choice of the flocculant and the associated parameters
such as dosage and mixing conditions determine the effec-
tiveness of paste technology. Although promising, paste tech-
nology does not provide yet an effective solution for the existing
MFT inventory (legacy tailings) because they are convention-
ally designed to handle thickening of low solids effluent. It is
also capital-intensive since it requires design, construction,
and maintenance of thickener, and purchase of state-of-the-art
polymer flocculants.
Even though current technologies for sewage water treat-
ment, dewatering of clay suspensions, removal of the organic
content in water, and treatment of ceramic wastewater are
mature, this is far from the truth for oil sands tailings reme-
diation: no technology can effectively treat oil sands tailings
and eliminate tailings ponds. Although acrylamide-based floc-
culants are widely used in the industry, the sediments formed
after flocculation still hold a significant amount of water. This
knowledge gap calls for innovative multifunctional flocculants
that can effectively flocculate MFT clays, form
sediments with high solids contents, and
release recycle water with adequate chem-
istry. This article describes some of the new
polymer flocculants developed in our group
to treat MFT. We also discuss remediation
strategies that are not entirely based on floc-
culation. Recent results on the modeling of
floc formation in oil sands tailings using in-
house flocculants are also discussed.
also been used to quantify floc formation in tailings. Since the
subsequent sections in this review describe the performance of
recently synthesized polymer flocculants, it is important to first
describe how their efficiency is assessed.
Settling rate measures how quickly a flocculant can settle
solids in suspension by tracking the solid–liquid interface
(mudline) as a function of time, forming a settling profile,
such as the one shown in Figure 2A. Often, the initial settling
rate (ISR), the slope of the initial linear section of the settling
profile, is reported instead of the average settling rate. ISR is a
simple measurement of the initial flocculation kinetics.
CST quantifies how easily suspensions or sediments can
be dewatered. This technique can be used immediately after
the polymer is mixed with tailings or after the sediments are
recovered by removing the supernatant. Figure 2B shows an
image of a CST instrument, which measures the time required
for water to move through a sheet of filter paper positioned
between the two electrodes. A higher CST value indicates lower
dewaterability (high water retention) of the suspension or sedi-
ments. Indirectly, it reflects the aggregates network formed
by the polymer flocculant, an indication of how fast the inter-
aggregate water can drain.

2. Performance Matrix for

Flocculant Evaluation
Flocculant performance is evaluated with
a few measurements such as settling rate,
supernatant turbidity, capillary suction time
Figure 2.  A) Schematic of a settling rate experiment and calculation of the initial settling rate
(CST), specific resistance to filtration (SRF), (ISR). Reproduced with permission.[8] Copyright 2015, American Chemical Society. B) Capillary
and solids content. More recently, focused suction time unit (CST, model 319 Triton Electronics). Reproduced with permission.[9] Copy-
beam reflectance measurement (FBRM) has right 2005, American Chemical Society.

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Supernatant turbidity measures the fraction of fine particles
that remained suspended in the supernatant after flocculation.
Often turbidity is measured using turbidimeter and expressed
in Nephelometric Turbidity Unit (NTU). Some researchers have
used UV spectrophotometers to monitor the transmittance of
the solution, but this technique is limited by a lower upper limit
for the concentration of suspended particles.[10] Although sev-
eral researchers have developed empirical correlations between
turbidity and volume fraction of particles,[11] turbidity alone
provides a quick and reliable way to evaluate how efficiently the
flocculant can capture fine particles.
The term specific resistance to filtration or filtration resist-
ance is derived from Darcy’s law. It is a purely hydrodynamic
concept. The instrument only measures the volume or mass
of water released from polymer-treated tailings as a function of
time, t. Then, this data is used in Equation (2) to calculate the
SRF.
2 b P A2
SRF = (2)
µω
where A is the filter area (m2), P is the applied pressure (Pa),
µ is the viscosity of the filtrate (Pa·s), ω is the mass of solid
cake formed per unit filtrate volume (kg m−3), and b is the slope
determined from t/V against V curve. SRF quantifies the filter-
ability of a suspension. A small SRF value indicates that the
filter cake is highly permeable. SRF and the mass of the solid
cake (ω) are inversely proportional: the higher the mass of the
solid cake, the lower the SRF.
One of the objectives of polymer-assisted flocculation of tail-
ings is to remove as much water as possible, thus increasing
the solid contents of the sediments. Solid contents are usually
measured by a simple gravimetric method, wherein a sample
of known mass is heated until all liquid is evaporated. The dif-
ference between initial and final masses is used to calculate
the solids content. Since often tailings are diluted to allow for
better interactions between polymer chains and clay particles,
the added water must be accounted for when measuring the
effectiveness of the flocculant. The net water release (NWR) is
calculated with the expression
V f − VP
NWR = (3)
VMFT
where Vf is the volume collected, Vp is the volume of water
added to the system, and VMFT is the volume of water contained
in MFT.
Figure 3.  Schematic of FBRM. Reproduced with permission.[13] Copyright 2006, IWA Publishing.
Macromol. Rapid Commun. 2019, 40, 1800644 1800644  (4 of 18)
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FBRM is used to measure aggregate size without the need
for sampling and dilution. Figure  3 shows the working prin-
ciples of FBRM. The instrument measures the chord length
and also provides the real-time distribution of aggregates. It
is important to note that FBRM measures chord length and
counts, but not number and size of aggregates. One can, how-
ever, correlate chord length with actual particle size measured
by other techniques such as laser diffraction spectroscopy.[12]
Recently, some researchers have used surface force measure-
ments to indirectly assess the effectiveness of a flocculant in
terms of its adsorption on clay surfaces. Typically, surface force
apparatus (SFA) or atomic force microscopy (AFM) are used
to obtain force–distance curves. Lu et al. synthesized poly(2-
lactobionamidoethyl methacrylamide) of various molecular
weights to dewater kaolin suspensions, a major component of
tailings.[14] They studied the effect of molecular weight on the
interaction of polymers and kaolin surfaces using SFA. Poly-
mers with molecular weights of 83, 186, and 456 kDa had adhe-
sion forces of 3, 8, and 11 mN m−1, respectively. These results
indicated that higher molecular weight polymers, having more
hydroxyl groups per chain, adhered more strongly to the sub-
strate via hydrogen bonding. The authors also verified these
results using conventional settling tests.
3. Multifunctional Linear Polymer Flocculants
The most common flocculants used in the oil sands industry
are copolymers of acrylamide and acrylic acid known as anionic
polyacrylamides (A-PAM), (Table  1) typically having molecular
weight averages of several million.[15] During flocculation, the
polymer may be applied directly to the MFT or after destabi-
lizing it via coagulation.[16] Prior coagulation with divalent
cations helps overcome repulsive forces between negatively
charged clay particles, giving access to bridging flocculation
and reducing the required dosage of the polymer.[17] A system-
atic investigation on the role of cations and clay particle size
on MFT flocculation is crucial to select appropriate polymers
and to optimize their dosages to treat tailings efficiently and
economically. MFT flocculation is a complex process, which
requires the use of statistical tools to allow more systematic
studies. Motta et al. used surface response methodologies to
investigate the impact of cation concentration (Na+ and Ca2+)
and anionic PAM dosage, as well as their interactions, in MFT
dewatering MFT.[18] They also examined the effect of clay par-
ticle size during the flocculation of samples with distinct par-
ticle size distributions (PSDs). Their results are summarized in
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Table 1.  Summary of chemical structures of polymers. Table 1. Continued.

Polymer Chemical structure Polymer Chemical structure

Anionic polyacrylamide Chitosan-g-CTA

Poly(acrylamide-DADMAC)
Chitosan-g-PAM

P(NIPAM-MATMAC-BAAM)

Bis(3-trimethoxysilylpropyl)
amine (aminosilane)

P(NIPAM-AA-NTBM)

Figure  4. The first row in Figure 4 shows the effect of cation

concentration (Na+ and Ca2+) and anionic PAM dosage on CST.
The dewaterability increased (low CST) with increasing anionic
Hyperbranched- PAM dosage and Na+ concentration, but it decreased (high
functionalized CST) when the concentration of Ca2+ increased, indicating that
polyethylenes (HBfPE) the addition of Ca2+ to MFT promotes water retention in the
Poly(PCL3ChMA) sediments. The second row in Figure 4 illustrates the effect of
cation concentration (Na+ and Ca2+) and anionic PAM dosage
on solids content. Optimum values for solids content were
obtained when Na+ concentration varied from 400 to 800 ppm,
Poly(PLA4ChMA) the Ca2+ concentration was lower than 800 ppm, and anionic
PAM dosage ranged from 1200 to 2000 ppm.
From a fundamental perspective, the effects of cation con-
centration (Na+ and Ca2+) must be isolated from that of anionic
PAM dosage to differentiate the role of each parameter on floc-
culation. Motta and coworkers combined particle size and zeta
potential measurements to investigate the mechanism of floc for-
Poly(PLA4ChA) mation.[18] Figure 5 shows a schematic representation of changes
in particle surface area, zeta potential, and particle size. Increase
in cationicity changed zeta potentials from negative to positive
values, whereas addition of anionic PAM reduced the zeta poten-
tial. Addition of cations did not significantly change particle sizes,
but the addition of anionic PAM increased it considerably. These
PAM-g-PEOMA
observations revealed that cations alone can neutralize the clay
particles, but cannot settle them due to their inability to form
flocs. The synergistic effect of cations and anionic PAM, on the
other hand, can help floc formation and subsequent settling.
The linear copolymer of acrylamide (AM) and diallyl dime-
thyl ammonium chloride (DADMAC) has been explored as a
potential alternative to conventionally used hydrolyzed PAM
PAM-g-PPO (HPAM) to avoid the use of salts.[19] Table 1 shows the chemical
structure of P(AM-DADMAC). The use of P(AM-co-DADMAC)
for MFT treatment and its effective dewatering performance
has been recently patented.[20] However, the effect of polymer
microstructure on the dewatering performance of P(AM-
DADMAC) is still not well quantified. In general, the number
of studies evaluating the influence of copolymer microstruc-
ture on flocculation and dewatering of MFTs is quite limited,
(Continued) although a few studies have been published for other similar

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Figure 4.  Effect of dosage of anionic PAM and concentrations of Na+ and Ca2+ on A) capillary suction time and B) solids content of MFT. Reproduced
with permission.[18] Copyright 2018, Elsevier.

systems, such as pulp wastewater, sludge dewatering, and
model clays.[21–23] Vajihinejad et al. systematically evaluated
the influence of copolymer microstructure on flocculation and
dewatering behavior of MFT.[19] They modeled the copolymer
composition of P(AM-DADMAC) using the Mayo and Lewis
equation.[24]
concentration of the initiator added to the polymerization
reactor. The classic free radical polymerization relationship
between the number-average chain length of the polymer and
the initial initiator concentration at low conversions (Equa-
tion (5)) can be used to control the molecular weight, assuming
chain termination by disproportionation only.[25]

r1 f 12 + f 1 f 2 kt0.5
(2 f kI [I ]0)
0.5
F1 = (4)
r1 f 1 + 2 f 1 f 2 + r2 f 22
2
1 kp km
= + tr (5)
rn [M ]0 (1 − x n ) kp
where F1 is an instantaneous molar fraction of monomer 1
in the copolymer, f1 and f2 are the instantaneous comonomer
molar fractions of monomers 1 and 2 in the reactor, and r1 and where, r n̅ is the instantaneous number-average chain length of
r2 are the reactivity ratios. Equation (4) relates the molar frac- the polymer, kI, kp, kt, and ktrm are rate constants for initiator
tion of monomer 1 in the copolymer to the molar fraction of decomposition, propagation, termination, and transfer to mon-
monomer 1 in the reaction medium. The average molecular omer, respectively, and f is the fractional initiator efficiency.
weight of the copolymer was controlled by varying the initial Further, they investigated the effect of copolymer composition,
molecular weight, and the dosage on the
ISR of sediments and the turbidity of the
recovered water, as shown in Figure 6.
Although flocculants containing posi-
tive charges have shown promising
flocculation performance, additional func-
tionalities can be added to the copolymers
to enhance the dewaterability of their
sediments. Gumfekar and Soares syn-
thesized a terpolymer, poly(N-isopropyl
acrylamide/2-(methacryloyloxy) ethyl
trimethyl ammonium chloride/N-tert-
butylacrylamide) [P(NIPAM-MATMAC-
BAAM)], containing the hydrophobic
BAAM monomer.[26] The chemical struc-
ture of P(NIPAM-MATMAC-BAAM) is
shown in Table 1. They demonstrated
that the hydrophobic BAAM comon-
omer helped in expelling water from the
sediments, while the cationic MATMAC
Figure 5.  Effect of cations and anionic PAM on A) physical state of clays in MFT, B) zeta potential, comonomer promoted charge neutrali-
and C) particle size. Reproduced with permission.[18] Copyright 2018, Elsevier. zation of negatively charged particles

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Figure 6.  Effect of copolymer composition, molecular weight, and dosage of P(AM-co-DADMAC) on A) initial settling rate of MFT and B) turbidity of
recovered water. Reproduced with permission.[19] Copyright 2017, American Chemical Society.

suspended in MFT. Since the fraction of each comonomer in
the terpolymer determined the performance of the functional
flocculant, it was important to determine and systematically
control the composition of the terpolymer. Gumfekar and
Soares first experimentally measured and later estimated the
binary reactivity ratios using the Mayo–Lewis equation (Equa-
tion (4)). Thus, they could minimize compositional drift and
guarantee the synthesis of terpolymers with narrow chemical
composition distributions, suitable as model flocculants for
MFT dewatering. Moreover, they estimated the composition of
the terpolymers based on the binary reactivity ratios estimated
using Equation (4), using the Alfrey–Goldfinger equation
(Equation (6))
FN : FM : FB = f N λN : f M λM : f B λB (6)
where F is the monomer fraction in terpolymer, f is the
monomer fraction in the feed, and λ is the function of f and
reactivity ratio r.[27] Figure  7 compares the copolymer com-
position measured experimentally and estimated using the
Mayo–Lewis model as a function of feed composition in binary
copolymers. The investigation showed how polymer reaction
engineering tools can be used to develop a framework for the
systematic design of multifunctional flocculants.
Use of a hydrophobic comonomer adds a degree of hydro-
phobicity to the flocculant that can be controlled at the syn-
thesis stage only. On the other hand, hydrophobicity-on-demand
can have additional benefits in the treatment of tailings. Such
hydrophobicity can be induced in the polymer upon applica-
tion of external stimuli such as changes in temperature and
pH. Polymers that change conformation from hydrophilic
to hydrophobic above a certain temperature are called lower
critical solution temperature (LCST) polymers. Gumfekar
and Soares synthesized a terpolymer flocculant poly(N-
isopropyl acrylamide/acrylic acid/N-tert-butylacrylamide)
[P(NIPAM-AA-NTBM)], which contained the permanently

Figure 7.  Comparison of copolymer composition measured experimentally and estimated using the Mayo–Lewis model as a function of feed composi-
tion. Reproduced with permission.[26] Copyright 2018, Elsevier.

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Figure 8.  Lower critical solution temperature (LCST) of the homopoly­mer,
copolymer, and terpolymer of the NIPAM. Reproduced with permis-
sion.[28] Copyright 2018, Elsevier.
hydrophobic NTBM comonomer and the thermosensitive
NIPAM comonomer that becomes hydrophobic above its
LCST.[28] The chemical structure of P(NIPAM-AA-NTBM) is
shown in Table 1. P(NIPAM-AA-NTBM) is soluble in water at
room temperature, but it becomes hydrophobic (water insol-
uble) above 30 °C. The authors added this thermosensitive
terpolymer to model tailings at room temperature and raised
the temperature to 50 °C to make the flocculant hydrophobic.
The additional hydrophobicity due to the NIPAM comon-
omer promoted the dewatering of sediments as evident by
CST measurements. The comonomers NIPAM (above LCST)
and NTBM helped expel water out of sediments due to their
hydrophobicity. Although this was an attractive solution, the
copolymerization of NIPAM with other monomers affected
the LCST of the flocculant due to changes in the hydrogen
bonding ability of the polymer chains. P(NIPAM) showed an
LCST of 33 °C, whereas P(NIPAM-AA) and P(NIPAM-AA-
NTBM) showed an LCST of 36 °C and 30 °C, respectively, as
shown in Figure 8.
A temperature-responsive copolymer of NIPAM and
2-aminoethyl methacrylamide hydrochloride (AEMA) was
used to flocculate and dewater MFT.[29] The linear copolymer
poly(NIPAM-AEMA) was synthesized using free radical polym-
erization with several copolymer compositions. The copolymer,
mixed with MFT at 25 °C, was able to bridge the fine particles
together, and copolymer adsorption increased further when the
temperature was raised to 50 °C. Although the authors claimed
an increase in adsorption due to hydrophobic interactions, the
flocculation tests did not show a significant difference in per-
formance between 25 and 50 °C. It was also necessary to add a
cationic copolymer, poly(acrylamide-diallyldimethylammonium
chloride), to increase the clarity of the supernatant.
A hydrophobic monomer, 5-methacrylamido-1,2-ben-
zoboroxole (MAAmBo), was copolymerized with NIPAM
and AEMA to increase the hydrophobicity of poly(NIPAM-
AEMA).[30] The LCST of the terpolymer decreased due to the
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hydrophobicity of the benzoboroxole moieties, resulting in
strong hydrophobic interaction above the LCST. The fastest set-
tling rate was obtained at a polymer dosage of 25 ppm, pH 9,
and temperature of 50 °C. The enhanced settling was attributed
to the strong adhesion of benzoboroxole groups to the kaolin
hydroxyl groups and an increase in the hydrophobic force.
Considering the distinct roles of anionic and cationic poly-
mers, Lu et al. flocculated oil sands tailings in two steps.[31]
First, they added commercial A-PAM, Magnafloc-1011, followed
by the addition of the natural polymer chitosan (dissolved in
acidic medium). Their results indicated that the anionic APAM
induced preliminary bridging among the clay particles, but
could not collect a significant fraction of the fine particles.
The subsequent addition of the cationic chitosan neutralized
the fine particles and also increased the floc size, possibly by
inducing the interfloc aggregation. One must note that chitosan
becomes cationic only in the acidic medium; therefore, it needs
to be dissolved in acids such as acetic acid. The addition of
acidic media to oil sands tailings may possibly limit the applica-
tion of such new flocculant systems.
Linear (homo-, co-, ter-) polymers have performed well for
the dewatering of MFT due to their abilities to form very high
molecular weights and selection of functional comonomers
that enhance the flocculation. It should also be noted that linear
polymers do have pendant groups that are considered small
branches due to the intrinsic structure of repeating units. If the
branches can be controlled by controlled polymerization tech-
niques, these modified flocculants may offer distinct benefits
that are not offered by linear polymers. Some of the benefits
are low viscosity compared to that of similar molecular weight
linear polymers and very high charge density at low molecular
weights.
4. Branched Polymer Flocculants
Branched flocculants have been synthesized mainly using
multifunctional initiators or controlled polymerization tech-
niques such as atom transfer radical polymerization (ATRP)
and reversible addition–fragmentation chain-transfer (RAFT)
polymerization, but other techniques such as catalyzed polym-
erization and macromonomer polymerization have been less
explored.
Botha et al. made a series of novel hyperbranched func-
tional polyethylene (HBfPE) flocculants consisting of a hydro-
phobic backbone containing anionic (carboxylic acid) func-
tional groups ranging from 35 to 50 mol% using a specifically
designed palladium catalyst.[32] The catalyst enabled the copo-
lymerization of ethylene and methyl acrylate (MA) to form
the hyperbranched microstructure. Since the MA-function-
alized polyethylenes were hydrophobic, base hydrolysis was
performed to generate anions and increase their solubility in
water. The chemical structure of HBfPE is shown in Table 1.
Their polymers had significantly lower molecular weights and
viscosities than typical PAM flocculants, and were easier to be
adequately dispersed in high solids MFT. The HBfPE could also
be dosed over a wider optimum range and were not sensitive to
overdosing, which improves the practical application of these
polymers, since overdosing often leads to deleterious effects
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Figure 9.  Comparison of changes in floc size after the addition of conventional polyacrylamide and hyperbranched-functionalized polyethylene. Repro-
duced with permission.[32] Copyright 2017, Elsevier.
in flocculation. FBRM comparative studies showed that PAM
formed larger flocs, but their size changed over time; HBfPE,
on the other hand, formed relatively smaller but uniformly
sized flocs, as shown in Figure 9.
One of the strategies to make hyperbranched polymers is to
use a chain transfer agent (CTA) during the polymerization.
Wang et al. prepared a temperature-responsive hyperbranched
copolymer of AEMA and NIPAM using 4-cyanopentanoic acid
dithiobenzoate as CTA.[33] The hyperbranched copolymer pro-
moted secondary consolidation at temperatures above its LCST,
as compared to similar linear copolymers. They hypothesized
that hyperbranched structure exposed the buried positive
charges during the polymer coil-to-globule transition, providing
additional electrostatic interactions and enhancing the capture
of fine particles.
In another approach to design branched polymers, mac-
romonomers consisting of desired functionalities (length,
functional groups, charge density) can be synthesized as a
building block, which can be further polymerized using a suit-
able technique to control the molecular weight of the whole
polymer. In a series of works published in collaboration by the
Soares and Hutchinson groups, a short-chain polyester mac-
romonomer [polycaprolactone choline iodide ester methacrylate
(PCL3ChMA)] was synthesized and further polymerized to
form a novel comb-like, cationic flocculant for MFT floccula-
tion.[34] The structure of poly(PCL3ChMA) is shown in Table 1.
Interestingly, the flocculant [poly(PCL3ChMA)] was hydro-
philic in its synthesized state, but became more hydrophobic
in response to hydrolytic degradation in MFT sediments. The
cationic chain ends of poly(PCL3ChMA) accelerated the settling
rate of oil sands tailings, while partial hydrolysis of the poly-
ester grafts exposed the hydrophobic segments that reduced
CST by 30%. The schematic structure of macromonomer and
subsequent polymerization using aqueous free radical polym-
erization is shown in Figure 10A. Figure 10B shows the mecha-
nism of ex situ hydrolytic degradation of poly(PCL3ChMA) and
corresponding photos showing solubility effects. This tech-
nology combined the material properties of polyesters with
the productivity of free radical polymerization to form dual
functional flocculants with characteristics that can be easily
tuned to control flocculation performance, such as polymeric
cation density, hydrophobic content, and polymer architecture.
Macromol. Rapid Commun. 2019, 40, 1800644 1800644  (9 of 18)
www.mrc-journal.de
However, polyester hydrolysis occurred only after keeping the
tailings sediments at 85 °C for 9 days. Thus, this technology
still requires further improvements before it can be adopted at
a commercial scale because heating a vast amount of tailings
for a longer period is not practically feasible.
Since poly(PCL3ChMA) contained an average of three poly-
caprolactone units in the methacrylic ester side chain, degra-
dation and its subsequent effect (more water release) on floc-
culation required relatively higher temperatures and longer
times. Gumfekar et al. synthesized a similar flocculant with
an average of two polycaprolactone units in the methacrylic
ester side chain, poly(PCL2ChMA), to facilitate degradation at
lower temperatures and shorter times.[35] To validate the phe-
nomenon of hydrolytic degradation of polyester side chains
in poly(PCL2ChMA), they compared the flocculation per-
formance with a structurally similar, yet hydrolytically non-
degradable poly(trimethylaminoethyl methacrylate chloride)
[poly(TMAEMC)]. Since the degradable polycaprolactone
units were reduced to two, the poly(PCL2ChMA) degraded in
7 days instead of 9 days for poly(PCL3ChMA). This observa-
tion confirmed that both the flocculant’s hydrophobicity and
degradation time could be tuned by changing the average
number of polyester units defined in the macromonomer
synthesis. The comparison of CST obtained using degradable
poly(PCL2ChMA) and non-degradable poly(TMAEMC) showed
that the CST of the sediments dramatically decreased after the
degradation of poly(PCL2ChMA) in 7 days (Figure  11). How-
ever, there was no change in CST of the sediments obtained by
poly(TMAEMC) even after 7 days because the polymer did not
degrade hydrolytically.
Although reducing the number of degradable polycaprol-
actone units to two reduced the degradation time, the overall
degradation conditions (85 °C and 7 days) to achieve better
water release is still not adequate for field applications. To over-
come this difficulty, Younes and coworkers synthesized similar
flocculants replacing caprolactone (CL) with easily degradable
lactic acid (LA) and using acrylate (less hydrophobic) func-
tional groups instead of methacrylate (more hydrophobic).[36]
The structure of their polymers [poly(PLA4ChMA) and
poly(PLA4ChA)] are shown in Table 1. The sediments obtained
using LA-based flocculants displayed a higher CST (22 s) than
that obtained using CL-based flocculants (14 s), since LA is
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Figure 10.  A) Schematic structure of macromonomer (in box) and its polymerization using aqueous free radical polymerization to form comb-like,
cationic polymer, and B) mechanism of ex situ hydrolytic degradation of poly(PCL3ChMA) and corresponding photos showing solubility effects.
Reproduced with permission.[34] Copyright 2016, Wiley-VCH.

more hydrophilic than CL. Poly(PLA4ChMA) degraded at 50 °C
(in 5 days) as compared to degradation of poly(PCL2ChMA) at
85  °C in 7 days. Alternatively, poly(PLA4ChMA) also degraded
at room temperature in 12 weeks, not requiring the use of
higher temperatures. It is evident from Figure 12 that changing
the type of polyester can have a pronounced effect on the degra-
dation of the flocculant.
It is evident from these studies that the effective use of
branched polymers for MFT dewatering requires precise control
of branch lengths and adequate choice of functional groups in
the flocculants. Although these branched polymers show some
promise as high-tech MFT flocculants, scale-up challenges and
economic viability still needs to be carefully assessed.
5. Graft Polymer Flocculants
Unlike branched polymers, graft polymers do not essentially
require the synthesis of building blocks to form a multifunc-
tional flocculant. Often, the purpose of graft polymers, in the

Figure 11.  Comparison of capillary suction time obtained using degradable poly(PCL2ChMA) and non-degradable poly(TMAEMC), before and after the
degradation. Reproduced with permission.[35] Copyright 2017, American Chemical Society.

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Figure 12.  Visual record of MFT dewatering using poly(TMAEMC), poly(PCL2ChMA), and poly(PLA4ChMA). Reproduced with permission.[37] Copyright
2018, American Chemical Society.

context of flocculants, is to have two functionalities (backbone
and graft) in the same polymer and to modify the rheology
in comparison with linear polymers. Typically, grafting from
and grafting onto approaches are used to synthesize graft poly-
mers.[8,38] Additionally, the monomer that forms the backbone
can be copolymerized in the presence of the already-synthesized
grafts to prepare a graft copolymer.
Hripko et al. synthesized polyacrylamide-g-poly(ethylene
oxide methyl ether methacrylate) (PAM-g-PEOMA) with dif-
ferent comonomer compositions, hydrophobic graft chain
lengths, and molecular weights.[39] The chemical struc-
ture of PAM-g-PEOMA is shown in Table 1. The authors
copolymerized AM with already-synthesized PEOMA grafts
using free radical polymerization. A central composite design
was used to evaluate the effects of comonomer compositions,
graft length (PEOMA), and molecular weights. Their results
revealed that adding hydrophobic PEOMA grafts (>30 wt%)
to PAM backbones can effectively increase ISR and reduce
CST, but may not capture all of the fine particles, leading to a
higher supernatant turbidity. This even contradicted the most
common assumption about molecular weight, that is the higher
(≈106 Da) the molecular weight, the better the flocculation.
PAM-g-PEOMA of low molecular weight (<2 × 105 Da) was still
effective at flocculating MFT at optimum conditions. Figure 13

Figure 13.  Effect of polymerization conditions on the CST of PAM-g-PEOMA: A) Ln(CST) versus Log[I] and PEOMA wt% and B) Ln(CST) versus PEOMA
length and wt%. Reproduced under the terms of the Creative Commons Attribution License CC-BY.[39] Copyright 2018, The Authors. Published by
Wiley-VCH.

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Figure 14.  Comparison of the CST of sediments obtained using several PAM-g-PPO samples and commercial PAM at A) 2 wt% and B) 20 wt% MFT.
Reproduced with permission.[40] Copyright 2016, Elsevier.

shows the effect of polymerization conditions on the CST of The technique of graft polymerization is also effective in
PAM-g-PEOMA. Lowering the initiator concentration (higher the case of natural polymers. Many natural polymers such as
polymer molecular weight) and maintaining the PEOMA chitosan, cellulose, alginate, and starch are used as backbones
length between 15 and 22 significantly reduced the CST. The to form graft copolymers useful for flocculation.[8,41,42] Hydro-
results also indicate that the length and percentage of hydro- phobic, anionic, or cationic functional groups can be grafted
phobic PEOMA have to carefully optimized to obtain the best onto natural polymers to transform them in multifunctional
dewatering performance. flocculants.
Further fine-tuning of the properties of graft copolymers Oliveira et al. grafted the small cationic molecule 3-chloro-
may require precise designing of grafts by building macromon- 2-hydroxypropyltrimethylammonium chloride (CTA) and PAM
omers with desired functionalities. Reis et al. synthesized pol- onto chitosan and used them to flocculate MFT.[43] The chem-
yacrylamide-g-poly(propylene oxide) (PAM-g-PPO) by first syn- ical structures of chito-g-CTA and chito-g-PAM are shown in
thesizing hydrophobic PPO grafts with vinyl groups, followed Table 1. Increasing the CTA concentration increased the zeta
by aqueous free radical initiated micellar copolymerization of potential of the polymer, which was beneficial to neutralize
AM and PPO.[40] Micellar polymerization was essential because clays in MFT. Chito-g-PAM settled MFT solids faster than
even though AM was soluble in water, PPO is not. Since the chito-g-CTA because the longer PAM grafts formed larger flocs
amount of hydrophobicity plays a crucial role in MFT floccu- (Figure  16A). The authors also compared the SRF of MFT
lation, they selected PPO with two molecular weights, 300 g
mol−1 and 1000 g mol−1. The chemical structure of PAM-g-PPO
is shown in Table 1. Their PAM-g-PPO flocculants had two
distinct features. First, PAM-g-PPO could be used for MFT as
high solids loadings (20 wt%) with the minor compromise of
dewaterability as compared to diluted MFT (2 wt%). From an
industrial perspective, this is an important feature because sev-
eral polymers cannot dewater MFT efficiently at higher solids
concentrations.
Figure  14 shows the CST of sediments obtained using sev-
eral PAM-g-PPO and commercial PAM at 2 wt% and 20 wt%
MFT. Since flocs formed by PAM are known to hold signifi-
cant water, often filtration or centrifugation are employed in
the industry to obtain stackable solids. However, mechanical
treatments have challenges to remove bound water from PAM-
treated MFT. To evaluate the applicability of PAM-g-PPO in
mechanical treatments, Reis et al. flocculated MFT using PAM-
g-PPO and centrifuged the sediments for 2 min to remove the
water from flocs.[40] Interestingly, they obtained higher solids
percentage (more water removal) using PAM-g-PPO than the
sediments treated with commercial anionic PAM (Figure  15).
The results indicated that PAM-g-PPO graft copolymers could Figure 15.  Solids content of the sediments obtained by flocculation and
significantly improve the densification of MFT when integrated centrifugation using PAM-g-PPO and commercial anionic PAM. Repro-
with mechanical methods such as centrifugation. duced with permission.[40] Copyright 2016, Elsevier.

Macromol. Rapid Commun. 2019, 40, 1800644 1800644  (12 of 18) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 16.  A) Initial settling rate of MFT using chito-g-CTA and chito-g-PAM, and B) specific resistance to filtration of MFT using chito-g-CTA, chito-
g-PAM, and commercial cationic PAM. Reproduced with permission.[43] Copyright 2018, American Chemical Society.
using chito-g-CTA, chito-g-PAM, and commercial cationic PAM
(C-PAM) (Figure 16B). The graft polymers had the lowest SRF
above 7000 ppm, which showed the tendency of sediments
formed by graft polymers to expel water as compared to C-PAM.
Several researchers have used ultraviolet (UV) radiation to
initiate grafting reactions onto the backbones of natural poly-
mers.[44–46] UV radiation presumably generates radicals that
initiate the free radical polymerization of the desired monomer
onto the backbone of another polymer. Recently, Liu and cow-
orkers grafted acrylamide and itaconic acid onto chitosan back-
bones using UV and 2,2′-azobis(2-methylpropionamide)dihy-
drochloride initiators.[47] It was unclear why the authors used a
free radical initiator in combination with UV radiation, which
should generate abundant free radicals on itself. The graft
poly­mer was used to flocculate kaolin suspensions with the aid
of Ca2+ ions. A loading of 30 mg L−1 graft polymer was neces-
sary to flocculate a kaolin suspension of 500 mg L−1.
6. Other Tailings Remediation Strategies
Most of the literature on MFT remediation focus on the use
of polymers to induce solid–liquid separation. The efficiency
of this approach depends on several parameters related to the
polymer, MFT, and operational conditions. Nevertheless, inef-
ficient flocculation may result in the generation of secondary
sludge that requires further action, such as mechanical treat-
ment. Despite advancements in innovative polymeric floccu-
lants, the issue of MFT dewatering does not seem to have a
single step solution.
Inspired by polymeric composites wherein filler material
improves the properties of the composite, Vajihinejad and
Soares exploited a novel approach of using MFT as a filler
material to form a composite material with polyurethane (PU)
matrix.[48] Previously, PU composites have found applications
in cushioning, thermal insulation, footwear, buoyancy prod-
ucts, and packaging. The authors prepared PU-MFT composite
foams by catalyzed polyaddition reactions between polyol and
isocyanate, in the presence of MFT solids and using water as a
blowing agent to form the foam structure. To use the composite
Macromol. Rapid Commun. 2019, 40, 1800644
www.mrc-journal.de
for thermal insulation application, compression, tension, and
thermal properties were measured. The increase in MFT solids
in composite increased the mechanical properties up to a cer-
tain extent, beyond which they deteriorated. The authors sug-
gested a positive effect due to clay reinforcement, and a nega-
tive effect due to the disruption of hydrogen bonds between
polymer chains. Further, they also attributed the enhanced dis-
persion of MFT solids to van der Waal and ionic interactions
between residual bitumen of MFT and polyol matrix. Figure 17
shows the TEM image of PU-MFT composite and schematic
model demonstrating how polymer chains and MFT particles
interact.
The presence of water in MFT substantially hinders most
of the polymerizations and thus requires the removal of water
prior to the polymerization of monomers. The removal of water
from MFT to use MFT solids in the polymer may defeat the
purpose of using whole MFT as it is. Moran and Soares formed
packaging films made up of plasticized starch and MFT,
without altering the physical properties of MFT.[49] They plas-
ticized the starch using glycerol as a plasticizer, a reaction that
requires water as a medium. The addition of MFT to the starch
plasticization facilitated the reaction due to the presence of
water in MFT and did not negatively affect the reaction. More-
over, the exfoliation of MFT clays in the starch matrix enhanced
the mechanical and thermal properties of the composites. They
compared the MFT-starch composite with typically used mont-
morillonite-starch composites. MFT-starch composites made
with up to 20% filler content reached the same tensile mod-
ulus achieved by composites made with 5% montmorillonite,
which is a positive feature of these composites in terms of MFT
utilization and tailing pond land reclamation. The dynamic
mechanical analysis of composites identified a glass–rubber
transition, but also the heterogeneity of the composites by the
presence of a second transition at higher temperatures. None-
theless, the use of MFT as a filler material for starch can be a
cost-effective approach compared to the use of purified clays.
Thompson et al. adopted a unique approach of using alkox-
ysilanes to induce the flocculation in MFT.[50] They hypoth-
esized that alkoxysilanes can form oligomers or polymers after
sequential hydrolysis and condensation reactions in aqueous
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Figure 17.  A) TEM image of PU-MFT composite and B) schematic model demonstrating how polymer chains interact with MFT particles. Reproduced
with permission.[48] Copyright 2016, Wiley-VCH.
alcoholic solution. Moreover, they can also bond to other mate-
rials, including those with SiOSi bonds, such as clay min-
erals in MFT via silicate bonding. Alkoxysilanes could polym-
erize and bond with suspended clay particles in MFT, in a
manner similar to conventional polymer flocculants, although
via a different mechanism. Once bonded together by alkox-
ysilane bridges, the clay particles might undergo flocculation
if they could be brought close together by the tendency of the
alkoxysilane polymer to minimize its surface area. The detailed
experimentation using central composite rotatable design indi-
cated that among the alkoxysilanes tested only those containing
an amine group showed a clear, dose-dependent improvement
of dewatering properties of undiluted MFT. The chemical struc-
ture of aminosilane is shown in Table 1. The positive charges of
the alkoxysilanes containing amine groups might have readily
attracted to the negatively charged clay particles in MFT by
electrostatic interactions. As a result of this charge neutraliza-
tion, the electrostatic repulsion between clays can be reduced,
allowing them to come closer to each other and settle. Although
there was a noticeable increase in the solids content of sedi-
ments after aminosilane treatment of MFT, the dewaterability
measured in terms of CST was still significantly lower than
PAM-based flocculants. Even though this approach did not pro-
vide the ultimate solution to MFT dewatering, the combined
use of alkoxysilanes with other technologies such as polymeric
flocculants and mechanical treatments may have the potential
to reach the desired dewatering criteria.
7. Aggregate Structure Quantification and
Modeling the Floc Formation in Tailings
7.1. Flocculation Monitoring Using Population
Balance Approach
Innovative polymer flocculants for solid–liquid separation in
oil sands tailings are useful only if the flocculation could be
adequately optimized and monitored for various conditions.
It is plausible using mathematical models that describe the
flocculation process, which is ultimately linked to the physical
properties of the aggregates such as size, density, and fractal
dimension. For example, larger aggregates quickly dewater
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MFT by increasing the settling velocity, hence reducing the size
of the treatment unit while maintaining the high throughput.
Several parameters such as mixing energy, flocculant dosage,
initial solids concentration, suspension chemistry, polymer’s
physical properties, and geometry of treatment unit (e.g.,
stirred vessel vs pipe flow) affect the size of aggregates.
Vajihinejad and Soares used a population balance model
(PBM) to describe the flocculation of MFT with poly(vinylbenzyl
trimethylammonium chloride) [P(VBTMAC)].[12] The size
and distribution of aggregates in a flocculating suspension
were tracked by PBM. Since flocculation involves the simul-
taneous aggregation and breakage of aggregates, their PBM
involved functions for both aggregate and breakage distribu-
tion. Equation (7) is the continuous form of PBM as applied to
flocculation.[51]
∂n ( v , t ) 1
v
= ∫ Q ( v − v ′ , v ′ ) n ( v − v ′ , t ) n ( v ′ , t ) dv ′
∂t 20
∞ ∞
+ ∫ Γ ( v , v ′ )S ( v ′ ) n ( v ′ , t ) dv ′ − ∫ Q ( v , v ′ ) n ( v , t ) n ( v ′ , t ) dv ′ − S ( v ) n ( v , t )
(7)
v 0
where n(v, t) and n(v′, t) are number concentrations of aggre-
gates (number per unit volume) of size (volume) v and v′at time
t, Q(v, v′) is the aggregation rate coefficient (aggregation kernel),
S(v) is the fragmentation kernel, and Γ(v, v′) is the breakage
distribution function (simply how many v-sized daughter
aggregates are formed when a v′-sized aggregate, v′ > v, is frag-
mented). The first two terms in Equation (7) account for the
formation of aggregates of size v, whereas the two last terms
account for the disappearance of aggregates of size v.
The aggregation kernel between two aggregates of a size di
and dj was defined as Equation (8).
Q i , j = β i , j × α i , j (8)
where βi,j and αi,j are collision frequency and capture efficiency
(the probability of aggregation upon collision), respectively. Col-
lision frequency term included the role of fluid motion (mixing)
and aggregates structure, and capture efficiency included the
colloidal forces and hydrodynamic repulsions in the floccula-
tion suspension.
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Table 2.  Summary of kinetic terms defined in the population balance model to predict flocculation.[12]

Kinetic term Expression

Aggregation kernel Q i , j = 0.162 G (d i + d j )3 [(α max − α min )e − k d t + α min ] (9)

i −1
d i = d 0,1 2 dF

G is the verage turbulent shear rate, dF is aggregates mass fractal dimension, di is the effective dimeter of a fractal aggregate that equivalently
i −1
contains 2 dF smallest primary particle. Term (α max − α min )e − k d t + α min (=αi,j ) was included in the PBM to address the S-shaped (Figure 18)
response of aggregate size evolution in time, with αmax and αmin representing the maximum and minimum capture efficiency, respectively, and
kd is a decay coefficient.
Breakage kernel[52] S i = s1 G s 2 d i (10)
Constants s1 and s2 represent the strength of aggregates
Average shear rate 1
 ε × ρ sus  2 (11)
G=
 µ sus 

( )
−2
N pN 3D 5 ∅
ε= , ρ sus = ρ s ∅ + ρ w (1− ∅), µ sus = µ w 1− eff
V 0.65
ρsus, ρs, ρw, μsus, μw are the density of suspension, solids, water, and viscosity of suspension[53] and water, respectively. ε is fluid average energy
dissipation rate,[54] Np,N, V are impeller power number, rotation speed, and suspension volume, respectively. ∅eff is aggregates effective
volume fraction[55]

3− d F
 d 
∅ eff = ∅  i,ave 
 d 0,i,ave 

where di,ave is average aggregates size (over the whole mixing time), d0,i,ave is average primary particles size obtained from laser diffraction to be
16.5 µm.

Their systematic approach involved four steps: i) defining i −1

the appropriate kinetic terms for PBM, ii) deciding initial d0,i = 0.27 × 2 3 µm (14)
conditions of PBM, iii) solving PBM, and fitting the model to
experimental data, and iv) predicting flocculation using the Solving the model and fitting it with experimental data
model. (step iii) estimated parameters related to aggregation rate,
The kinetic terms defined for PBM (step i) are summarized breakage rate, and fractal dimension. The model was fit to
in Table 2. the experimental data by minimizing the objective function
Laser diffraction technique was used to obtain the data F in Equation (15) using the particle swarm optimization
needed to define the initial conditions for PBM (step ii). Equa- (PSO).
tion (12) gave an initial number concentration of particles (N0,i)
in MFT.[12] max
F (α max , …, s2 ) = ∑ ( dexp − dmodel ) (15)
2

∅ × v ( d0,i ) t =0
N 0,i =
π 3 (12)
d0,i dexp was obtained by calibrating the FBRM chord length data
6
with laser diffraction spectroscopy. dmodel was calculated using
where ∅ is the total volume fraction of primary particles in Equation (16).[12]
MFT. v(d0,i) is the initial volume fraction of particles with a size
d0,i, which was obtained using Equation (13).[12]
∑
max
N i di 4
dmodel = i =1
(16)
∑
max
v ( di +1LD ) − v ( di −1LD ) N i di 3
(d ) + v (d ) (13)
i =1
v ( d0,i ) = 0,i − di −1 LD
i −1
LD

di +1LD − di −1LD
Their model successfully predicted the effect of polymer
where v(di − 1LD) and v(di + 1LD) are the experimental volume frac- dosage on capture efficiency and mean aggregate size of
tion of primary particles obtained by the laser diffraction PSD particles. Moreover, the model also predicted the mean
appearing immediately before and after d0,i, respectively. aggregate size as a function of shear rate (Figure 18). Indus-
The smallest particle size d0,1 in their MFT was 0.27 µm, trially, these parameters are most relevant and the model
so geometrical discretization with progression factor of 2 was could serve as a soft sensor to predict the performance of
obtained by Equation (14).[12] flocculation.

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Figure 18.  Experimental and predicted mean aggregate size as a function of A) shear rate, B) polymer dosage, and C) the effect of dosage on capture
efficiency of the particles in MFT. Reproduced with permission.[12] Copyright 2018, Elsevier.

7.2. Quantification of Aggregate Microstructure where U is terminal settling velocity of the aggregate of equiv-
alent size (dst); μ, ρl, and g are fluid viscosity, fluid density,
Understanding the impact of polymer microstructure on phys- and the gravity constant, respectively. dst was calculated using
ical characteristics of the aggregates allows for the optimum Equation (18).[57]
design of novel flocculants with tuned properties targeted
for the unique environment of oil sands tailings. One of the  2 
 a  a
important characteristics of aggregates is their density, which  0.8248 + 0.168   + 1.033 × 10 −2   
 b  b
directly affects the sedimentation rate, resistance to shear, and dst =   b (18)
 −3  a 
3
−5  a 
4

dewatering.  −1.264 × 10   + 3.728 × 10   
After Botha et al.[32] showed promising flocculation per-  b b 
formance of hyperbranched polyethylenes (HBfPE) in MFT
flocculation, which is described in Branched Polymers sec- Figure  19A compares free settling velocity as a function of
tion, Costine et al.[56] quantified the structure of aggregates size for MFT flocculated with HBfPE polymers and commercial
formed by HBfPE using a combined application of FBRM and anionic PAM, as measured by FDA. Aggregates formed with
floc density analyzer (FDA). They monitored the evolution of HBfPE polymers generally settled faster than those with A-PAM
aggregate size by FBRM over the full duration of the floccula- of an equivalent size, although the estimated molecular weight
tion process. Simultaneously, undisturbed free settling veloci- of the A-PAM was 100 times more than HBfPE, reflecting the
ties and structures of hundreds of individual aggregates were importance of the right chemistry of the flocculant (balance of
quantified by use of a digital camera, connected to image pro- hydrophobicity/hydrophilicity). Figure 19B also compares the
cessing software of FDA. Further, they calculated the density estimated densities of aggregates formed as a function of aggre-
of an individual free settling aggregate (ρa) using Stokes law gate size, derived from the settling data by Equation (14). Aggre-
(Equation (17). gate densities were generally larger for HBfPEs than for A-PAM
at an equivalent size, up to the size of 150 µm. The results indi-
18 µ U cated that MFT treated with the HBfPE polymers had a higher
ρa = + ρl (17)
g dst2 proportion of inter- rather than intra-aggregate liquor, that is,

Figure 19.  A) free settling velocity as a function of aggregate size and B) estimated densities of aggregates formed as a function of aggregate size using
HBfPE polymers and commercial anionic PAM. Reproduced with permission.[56] Copyright 2018, John Wiley & Sons.

Macromol. Rapid Commun. 2019, 40, 1800644 1800644  (16 of 18) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
more liquor between aggregates rather than within the struc-
tures, as the author suggested, an important implication to the
solids dilution in MFT prior to flocculation.
8. Summary and Outlook
Current flocculation technologies for MFT still need much
improvement from fundamental and industrial perspectives.
Limitations of emerging polymer-based technologies occur in
terms of scale-up, cost, effectiveness over conventional mate-
rials, or poor understanding of tailings/polymer interactions
and their control. Authors also note a major barrier to obtaining
the desired set of performance matrix for new polymers from
industry to match with their expectations. Most current tail-
ings management practices employ mechanical treatments
after polymer-assisted flocculation to reach the desired levels
of dewatering. However, the sediments generated by floccula-
tion do not necessarily suit the mechanical operations and their
working principles. The microstructure of polymers and thus
the properties of sediments can be customized to match the
requirements of these mechanical operations. As experimental
research on tailings flocculation is rapidly growing, the mode-
ling studies of flocculation processes are very sparse. Modeling
of MFT flocculation process using new polymers is imperative
to understand the interactions among various components in
MFT and polymer and to validate them. Further, such models
come in handy for on-field operations and act as soft sensors.
Considering the current generation rate of oil sands tailings in
addition to existing legacy tailings, there is an urgent need for
advancements in terms of innovative polymers, their control
strategies, and performance.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
dewatering, flocculation, oil sands tailings, water-soluble polymers
Received: August 30, 2018
Revised: October 4, 2018
Published online: November 12, 2018
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