Effect of Seawater on Solid-Liquid Separation and

Transport Properties of Magnetite Tailings

Matas lvarez1,2, Christian Ihle1,2, Willy Kracht1,2 and Cristian Reyes1,2
1. Department of Mining Engineering, Universidad de Chile
2. Advanced Mining Technology Center, Universidad de Chile

ABSTRACT
It is well known that seawater affects mineral flotation, especially in the presence of clays. A
comparatively less studied problem is the effect that seawater on the behavior of tailings in light of
the solid-liquid separation at the thickening stage, and the subsequent flow properties towards
tailings placement. In the present study both settling tests and rheology measurements have been
performed between iron ore magnetite tailings samples, whose P80 is close to 40 m, and different
seawater fractions. The outcomes of experimental measurements focus on the turbidity of the
supernatant layer and the settling velocity in the case of settling tests, and, in the case of rheology
viscosity and yield stress. Settling tests have been made using a video-based system to track the
interface between the supernatant layer and the settling pulp region. Rheology measurements have
been made using a concentric cylinder rheometer, considering test times significantly smaller than
the settling time scale. Results show that yield stress, plastic viscosity and settling velocity depend
on the seawater fraction and the particles concentration in the suspension. In regard to the
rheological parameters is possible to determinate that yield stress and plastic viscosity are sensitive
to seawater fraction, especially for 75% and 100% and both parameters increase when increases the
solid fraction by weight. Settling tests allowed to determinate that seawater fraction is significant in
this parameter, generating a minimum value for a seawater fraction of 50%. By contrast, the pH
value in the slurry is less relevant to explain the changes in yield stress, viscosity and settling
velocity.

1
INTRODUCTION
Understanding the rheological properties of tailings is of vital importance in the mining processing.
Little is known about the interplay between tailings and different electrolytes including seawater.
These electrolytes have direct impact on viscosity and yield stress of suspensions. The yield stress
of particulate suspensions is typically related to particle shape and size distribution, solid
concentration and surface chemistry (Kapur et al., 1997; Zhou et al., 1999; Ancey & Jorrot 2001) and
it is expected that these factors affect the settling of particles. The viscosity and yield stress of
suspension have been routinely measured and several authors have explored the relationship of
these properties with the interaction potential between particles (Channell & Zukoski, 1997; Scales
et al., 1998; Johnson et al., 2000; Franks et al., 2000; Zhou, Scales & Boger, 2001), and it is expected
that these factors affect the settling of particles.
The viscosity and yield stress of suspensions have been measured by several authors in relation
with the interaction potential between particles (Channell & Zukoski, 1997; Scales et al., 1998;
Johnson et al., 2000; Franks et al., 2000; Zhou, Scales & Boger, 2001).
When particles are in suspension with seawater, different reactions that involve the cations and
anions in seawater with the minerals through exchange happen. This process is complex because
depends on the different bonding energies of Ca2+, Mg2+, K+ and Na+ ions, whereas the effect of the
cations originally resides in the exchange positions, the ionic activity of the seawater, the buffer
mechanism of seawater and the physical properties of particles (i.e. diameter, shape). As a result,
the inter-particles charge and the strength and range of this change is determining by the
electrolytes.
In the simplest case, the inter-particle interactions are governed by the sum of the attractive van der
Waals and the repulsive electrical double layer forces, as defined by the DLVO theory (Derjaguin,
Landau & Others, 1941; Verwey & Overbeek, 1948). The van der Waals attraction is due primarily
to the interaction of instantaneous dipoles generated within the atoms comprising each particle.
This attraction is the major force responsible for aggregation of metal oxide particles in most
processing situation. In the case of repulsive force, the most common interactions between colloidal
particles are electrical repulsive forces which are the result of like surface charges on the particles.
The electric repulsive force can easily be manipulated for controlling suspension rheology. For
metal oxide suspensions, changing the suspension pH will alter the magnitude and/or sign of the
zeta potential, while the addition of electrolyte will affect both the Debye length and the magnitude
of the zeta potential. When there are no repulsive forces between the particles, the strong van der
Waals attraction and/or other attractions will result in an interconnected network of substantial
mechanical strength. These networked flocculated suspension can exhibit a high viscosity and yield
stress, extreme shear thinning, and thixotropy in some cases (Zhou, Scales & Boger, 2001).
In non-dilute system, where the surface separation is short, when the particles approach each other,
the repulsive force increases gradually due the extension of the double layer (Krieger & Eguiluz,
1976). As a result, the electrical double layer repulsion increases the effective volume fraction of the
particles and this brings an increase in the yield stress of this suspension. The behavior of the
particles in a suspension with large electrolyte is different in terms of settling and rheological
properties, even the suspensions are typical of flocculated ones, though at the pH far away from the
isoelectric point (IEP), where the repulsive force is zero. Some studies of the rheological behavior of
metal oxide suspensions containing large electrolyte concentrations has been examined in (Leong et
al., 1993; Chang, Lange & Pearson, 1994; Channell & Zukoski, 1997; S. B. Johnson, 1998). Other
studies mentioned the maker and breaker salts, which change the structure of water. The maker

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ions such as Li+, Na+, Mg2+, and Ca2+ are small and thus have a strong electric field causing water
molecules around these ions to become highly structured. Breaker ions such as Cs+, K+, Cl- and I-
generally have a larger size than the maker ions and weaker electric fields. It is generally observed
that the relative viscosity of a suspension increases in the presence of maker salts because of the
strengthening of the water bonds. Also It is interesting to note that the viscosity of seawater is
higher than for pure water for all temperatures, which could be postulated to be due to its structure
maker salts (Jeldres et al., 2014)
In the absence of flocculant, both the viscosity and yield stress are increased by the presence of
maker salts for suspensions of both silica (Colic, Fisher & Franks, 1998) and alumina (Colic &
Fisher, 1998). These experimental results suggest that maker counter ions give rise to inter-particle
pair potentials leading to stronger particle networks.
In the present paper, the effect of seawater in the rheological properties of dense magnetite
suspensions is analyzed.

Rheological models
A number of models have been proposed in the past to estimate the yield stress. The linear
Bingham plastic model is very often used,
= b +
Where is the measured shear stress, is the imposed shear rate and is the plastic viscosity. To
take into account the shear thinning characteristic of these suspensions at sufficiently low shear
rates, nonlinear models such as Herschel-Bulkley model have been used.
= HB + K n
This model uses three rheological parameters, the Herschel-Bulkley yield stress (HB ), the flow
consistency index (K) and the flow behavior index (n)
There are investigators that uses the Bingham model in the full rheological data, meanwhile
another uses only in the linear portion of the curve. There are several reports showing the disparity
between theoretical and experimental results using the Bingham plastic model for the flow of many
non-Newtonian fluids (Hansen et al., 1999; Coussot, 1994; Fordham, Bittleston & Tehrani, 1991) and
a reason for the discrepancies could be the different Bingham yield stresses obtained by the
extrapolation of flow data. On the other hand, the use of Herschel-Bulkley model has proven to be
good choice for many cases (Kelessidis et al., 2007). In this paper the Bingham model was used in
the linear portion and the Herschel-Bulkley in the non-linear portion to get a better fit.

Magnetic separation
The magnetic separation process features the three-way competition between tractive magnetic
forces, gravitational, frictional or inertial forces, and attractive or repulsive interparticle forces. The
feed is split in the magnetic separator into two or more components. If the separator is to produce a
magnetic concentrate, then the tails are the nonmagnetic components (Figure 1). The magnetic
concentrate is called the mags and other less magnetic components are called madlings. The
magnetic and competing gravitational, friction, hydrodynamic, or inertial forces tend to separate
the particles, while attractive interparticle forces tend to reduce the degree of separation
(Oberteuffer et al., 1974).

3
 Figure 1 Diagrammatic illustration of dry drum separator

In a magnetic separation system, the force on a particle toward increasing field intensity (F) is
expressed by:
dH
F V (Sp So )H
dt (1)

Where V is the volume of the particle, Sp and So are the magnetic susceptibility of the particle and
surrounding media, respectively, H is the magnetic field intensity and dH/dt is the magnetic field
gradient (Song et al., 2002). This equation shows that the difference of magnetic force between
magnetic minerals and non-magnetic minerals considerably decreases with the reduction of particle
size, thus the separation efficiency of magnetic separation collapses in the fine size range. The poor
efficiency of magnetic separation of weakly magnetic mineral fines can be improved through
increasing magnetic field gradient, field intensity and particle size.
The iron magnetite separation process involves fine grinding. Downstream the thickening process,
the iron ore tailing can be either transported to an aerial disposal place or below at the sea bottom
(Ramrez-Llodra et al., 2015; Dold, 2014 & Ellis et al., 1995). In the present paper, we discuss the
impact of electrolyte in the rheology and settling in this ultra-fine grinding system.

METHODOLOGY
The magnetite tailings particles used in this study had a P80 close to 48 m and had a density of 2,9
ton/m3 . These particles were dried to 80C for 24 hours. to eliminate the humidity content in the
sample. The water used for all experiments was a combination of two different sources: Process
water (PW) and Seawater (SW), in different combinations. The water was protected from light, to
avoid the generation of organic matter.

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Settling tests
The experiments were made using a glass test tube of 1 L and a video-based system to track the
interface between the supernatant layer and the settling pulp region and being processed with the
tool Matlab. The experiments were done using at tailing solid fractions by weight of 45%, 50% and
55%, respectively. The water used for these experiments was a combination of process water and
seawater in different compositions: 0, 25, 50, 75 and 100% of seawater, measured by mass balance.
The height of the interface was registered for 24 hrs. Before to start the tests, the glass test tube
(containing the solid and the water), was stirred during 5 min to get a homogeneous concentration
of the slurry along the test tube.

Rheology test
The experiments were conducted using an Anton Paar RheolabOC Couette viscometer, fitted with a
cup-and-bob CC39/S-SN32517 accessory (internal/external cylinders with internal/external
diameters of 26,66 mm and 28,92 mm, respectively). While the cup is kept fixed, the internal
cylinder angular velocity has been imposed between 0 and 24.3 rad/s-with the corresponding
conversions following ISO 3219 standard. The experiments were done using three different solid
fractions by weight: 45, 50 and 55%, measured by mass balance. The water used for these
experiments was a combination of process water and seawater in different compositions: 0, 25, 50,
75 and 100% of seawater, measured by mass balance. Different shear rate, linear sequences between
0 and a maximum value of 300 s were tested. The particles and the water were mixed during 5 min
-1

to get a homogeneous concentration in the cup before to start the tests. Each test was performed by
triplicate and before to start each test, the slurry was mixed during 45 s to prevent the
sedimentation of particles in the slurry.
A preliminary analysis showed that the viscosity was stable in test times between 40 and 60 s, hence
it was decided to perform shear rate ramps at 50 s. For the analysis of flow curves, shear rates
between 4 and 130 s-1 were chosen. In a first range, shear rates between 4 and 40 s -1, the Herschel -
Bulkley behavior was observed, while in a second range, shear rates between 40 and 130 s -1, the
Bingham behavior was observed. In any case, the parameters were obtained, yield stress and plastic
viscosity in the Bingham behavior, and the yield stress and consistency index in the Herschel -
Bulkley behavior.

RESULTS AND DISCUSSION

Figure 2 shows that the shapes of the flow curves depend on the seawater fraction and the particles
concentration in the suspension. The yield stress and the plastic viscosity for all cases was higher, in
the range studied, at 100% seawater for the Bingham and Hershel Bulkley model, probably because
the presence of maker salts that change the water structure and for the decrease of the repulsion
between the particles by the cations adsorption that causes. It is observed than the case of 50%
particle concentration and 75% seawater presents a shear stress equal to the case of 100% seawater
in the beginning, but slightly higher for shear rates greater than 50 s-1.

5
 Figure 2 Experimental flow curves vs fraction of seawater (SW) for 50% solids fraction (by weight)

Tables 1 and 2 summarize the fitted rheology results obtained from the flow curves. In particular,
the yield stress and the plastic viscosity increase with the particle concentration. For the cases
studied we could see that the effect of the particle concentration is higher than the effect of the
seawater fraction in the yield stress and the viscosity but it is necessary keep studying this topic to
use this kind of water in the industry.

Table 1 Parameters according to Bingham model

Solid fraction by weight, %

SW fraction
45 50 55
%
[Pa s] b [Pa] [Pa s] b [Pa] [Pa s] b [Pa]
0 0.0134 3.477 0.0221 8.566 0.0578 30.960
25 0.0140 3.652 0.0229 8.700 0.0585 30.836
50 0.0136 3.669 0.0231 8.873 0.0580 31.110
75 0.0141 4.146 0.0245 9.863 0.0578 31.159
100 0.0152 4.924 0.0249 10.324 0.0628 35.117

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Table 2 Parameters according to Herschel - Bulkley model

Solid fraction by weight, %

SW fraction 45 50 55
%
K [Pa s-0,55] HB [Pa] K [Pa s-0,55] HB [Pa] K [Pa s-0,55] HB [Pa]
0 0.177 2.733 0.384 6.414 1.164 24.363
25 0.182 2.883 0.403 6.500 1.196 23.989
50 0.169 2.938 0.425 6.854 1.216 24.120
75 0.196 3.251 0.460 7.597 1.200 24.280
100 0.231 3.799 0.470 7.533 1.455 26.506

Regarding to the pH in the slurry, according Figure 3, this parameter is less relevant to explain
changes in viscosity, yield stress and settling velocity. This includes slurries with different solid
fraction by weight. The adsorption or desorption (especially of OH- ions), is negligible. The slight
decrease of pH could be due the particles adsorb cations causing the release of H+, this adsorption
process is due that the ions seek to compensate the charge of the surface and brings a decrease of
the repulsion inter particles that affect the shear stress of the solution and also the settling of
particles.

Figure 3 pH value of slurry to different seawater fraction and solid fractions (by weight)

In relation to ions concentration, according Table 3, there is greater increase of Cl - respect to other
ions. The change in the concentration should generate a decrease in the viscosity (as a breaker ion).
Nevertheless, the viscosity increases with increasing of seawater (SW), especially in fractions of 75
and 100%. It is possible to considerate, in this case, that breaker ions are less important than maker
ions, even when the variation of maker ions is much lower. The maker ions are more important for
to explain the change in the viscosity than breaker ions. It is possible to explain this effect if it

7
considered than the potential around particles is equal sign than Cl- and opposite to ions as Mg2+ or
Ca2+, that have greater charge, are more important in viscosity and yield stress changes.

Table 3 Ions concentration and water conductivity

SW fraction Cl- Ca2+ K+, Mg2+ Na+ Conductivity

% mg/L mg/L mg/L mg/L mg/L s/cm
0 2254 763 151 208 835 9560
25 6692 1911 213 407 5309 27710
50 11420 1866 260 517 6816 32700
75 15568 1925 299 614 8953 43200
100 20227 1904 354 723 9714 52800

In the figure 4 it observes that the effect of the seawater fraction in the settling process is significant.
It was expected that the settling velocity increase with the increasing of seawater fraction because
the decreasing of repulsion drives the formation of aggregates and probably this happen from 50%
seawater, for the case of 25% and 0% the behavior could be explaining for the use of process water
that have a different concentration of fresh water and could cause the formation of flocs, with
different shapes and diameter, and for this reason is faster than the another seawater fraction. To
explain this in a complete way is necessary make another studies to check if exist other elements
that affect the particles behavior. A studies of formation of aggregates and zeta potential
measurement could be necessary.

Figure 4 Settling velocity vs seawater fractions for 50% solids fraction (by weight)

8
CONLUSIONS
The sea water has an effect in the rheological properties and settling velocity of magnetite tailings.
For the case of yield stress and viscosity, when the sea water fraction increases both increases, but
this effect is lesser than the effect of the particles concentration. Meanwhile the settling velocity of
particles first decreases and then increases when the sea water fraction increases, probably due to a
coagulation-flocculation process induced by the superficial chemistry of the particles and the ions
in the water. For the full understanding of this, is necessary to investigate deeply the changes in the
superficial chemistry due the ions concentration in the liquid by zeta potential measurement,
agglomerate sizes, distribution size of particles or another similar studies.

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