International Journal of Mineral Processing 134 (2015) 7481

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International Journal of Mineral Processing

journal homepage: www.elsevier.com/locate/ijminpro

Reactive oily bubble technology for otation of apatite,

dolomite and quartz
Fang Zhou a,c, Louxiang Wang b, Zhenghe Xu b,, Qingxia Liu b, Ruan Chi a,c,
a
School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, Hubei, P.R. China 430073
b
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4, Canada
c
School of Minerals Processing & Bioengineering, Central South University, Changsha, Hunan, P.R. China 410083

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

Article history: Reactive oily bubble technology was applied to selectively oating apatite from dolomite and quartz. Kerosene
Received 2 January 2014 containing 100 ppm fatty acid was chosen to generate reactive oily bubbles. Zeta potential and contact angle
Received in revised form 6 September 2014 were measured to investigate the surface properties of reactive oily bubbles and single minerals. The induction
Accepted 11 November 2014
time was determined to evaluate the effect of different bubbles on bubblemineral attachment. This novel
Available online 22 November 2014
technology was compared with conventional air bubble otation in which collectors were added in the pulp. A
Keywords:
shorter induction time and hence a stronger collecting power of the reactive oily bubbles attaching to the uncon-
Reactive oily bubble otation ditioned minerals than the air bubbles attaching to the collector-conditioned minerals were observed.
Phosphate ore otation With the addition of sodium silicate as depressant at pH 9, the induction time of reactive oily bubble attaching to
Fatty acid collector dolomite becomes much longer than that attaching to apatite as a result of smaller contact angle of dolomite than
Induction time apatite, which is opposite to the case of conventional air bubble otation with collectors added in the pulp. There-
Zeta potential fore, a novel phosphate otation technology is proposed and tested. In this novel technology, apatite is separated
from dolomite and quartz using reactive oily bubble with sodium silicate as depressant, followed by separation of
dolomite from quartz with conventional air bubble otation. The results of micro-otation tests demonstrated a
better otation separation using the proposed novel technology.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Phosphate rock, a main raw material of phosphatic fertilizer and phos-
phorus chemical industry, is one of the most important non-renewable
mineral resources. The only way to provide phosphate is through
the mining and beneciation of natural resources. Most of the world's
phosphate reserves are in the sedimentary and igneous deposits, which
contain a considerable amount of gangue minerals. The treatment of
phosphate ores is therefore needed to reduce these indigenous gangue
minerals to meet the requirement of the phosphate industry (Sis and
Chander, 2003a). The separation of apatite [Ca5(PO4)3(F,Cl,OH)], a
valuable mineral of phosphate ores, from the gangue minerals such as
dolomite [(Ca,Mg)(CO3)2] and quartz [SiO2] is the most critical step in
the phosphate processing.
Many beneciation methods such as heavy media separation,
roasting, calcinations, leaching and otation are applied to phosphate
rock processing. When silica is the main gangue mineral, conventional
otation is the most widely used mineral processing technology. For
the Jordanian phosphate ore, for example, collectors are added in the
pulp, and air bubbles or oil droplets are used as carrier to separate the
Corresponding authors. Tel.: +1 780 492 7667; fax: +1 780 492 2881.
E-mail addresses: zhenghe.xu@ualberta.ca (Z. Xu), rac@mail.wit.edu.cn (R. Chi).
phosphate minerals from gangue with sodium silicate [Na2SiO3] as the
depressant of silica (Salah et al., 2011). When carbonate is the main
gangue mineral, the presence of carbonates in the phosphate rock re-
quires the addition of sulphuric acid during the production of phosphoric
acid and results in a low quality product of phosphoric acid. It is difcult
to separate the carbonate gangue minerals efciently from such phos-
phate ores by conventional otation technology (Gharabaghi et al.,
2010). Due to the similarity of the physicalchemical properties of the
carbonate gangue minerals and phosphate valuable minerals (apatite
[Ca5(PO4)3(F,Cl,OH)]) and complex solution chemistry from the dissolu-
tion of salt minerals, the processing of such phosphate ores has always
been a big challenge (Abouzeid et al., 2009).
Many researchers have devoted their efforts to developing a suitable
and economic approach to improve the phosphate recovery from low
grade and high dolomite content phosphate ores. The methods include
the use of novel otation systems, development of new otation equip-
ment, and use of high temperature to improve the solubility of collector
or alternative otation reagents. Calcination and selective leaching with
organic acids are also used to upgrade the phosphate ores which are dif-
cult to be treated (Abouzeid, 2008; Gharabaghi et al., 2010). However,
all these methods either increase the energy consumption or have lim-
ited operability. None of these methods have been proven economically
competitive to the conventional otation and sufciently efcient to

http://dx.doi.org/10.1016/j.minpro.2014.11.009
0301-7516/ 2014 Elsevier B.V. All rights reserved.
 F. Zhou et al. / International Journal of Mineral Processing 134 (2015) 7481
upgrade poor grade ores. Thus, further improvement of the current
technology or a novel method is required.
In past few years, addition of oil in otation as otation carrier has
been proven to be a great success to some extents. Ralston et al.
(1984) used polymer-stabilized oil droplets to efciently separate ne
calcite particles from ne quartz gangue. Another technique of using
aerosol (air or nitrogen bubbles coated with silicone oil) to enhance
de-inking efciency was demonstrated, where oil-coated bubbles act
as carrier. It is believed that using oily bubble instead of pure air bubble
facilitates the liquid lm drainage between air bubble and mineral sur-
faces, thus increasing the otation rate (Gomez et al., 2001; Maiolo and
Pelton, 1998). A novel concept of reactive oily bubbles (i.e., bubbles
covered by a thin layer of oil containing oil-soluble collectors) was
proposed and successfully used to oat sulde minerals (Liu et al.,
2002). The results showed a great improvement in otation efciency
by the reactive oily bubbles. Compared with air bubble, oil droplet and
oily bubble used in conventional otation, the advantages of using reac-
tive oily bubbles include: ne-tuning surface properties of reactive oily
bubbles; less consumption of collectors and oil; larger buoyancy force
than otation using simple oil droplets; and increased hydrophobicity
of solid surfaces. More importantly due to the addition of oil-soluble
collectors in the oil phase the reactive oily bubble technology can
avoid unnecessary synergistic interactions and undesired activation of
gangue particles by other inherent chemical species present in the
pulp and the collectors added in the aqueous phase (Liu et al., 2002).
Considering these distinct features, reactive oily bubble technology is
believed to be a good alternative to process phosphate ores, especially
the high dolomite content phosphate ores.
It is well established that the wetting properties of mineral surface
control the selective otation. The most basic measure of wettability
for a particular liquid/mineral combination is the contact angle (David
and Neumann, 2014). The induction time has been proven to be a criti-
cal parameter to evaluate the efciency of particlebubble attachment
and hence otation as it incorporates the dynamic nature of bubble
particle interactions. Under a given hydrodynamic condition, the
shorter the induction time, the higher the otation recovery (Yoon
and Yordan, 1991; Gu et al., 2003). In this study, contact angle of the
mineral solid and the induction time of reactive oily bubbles attaching
to mineral particles were measured to investigate the feasibility of ap-
plying reactive oily bubble technology to the separation of phosphate
ores by otation. Zeta potential of the mineral particles and oil droplet
were measured to investigate the properties of the interested interfaces.
The micro-otation test was conducted to demonstrate the use of reac-
tive oily bubble in the processing of phosphate ores.
2. Materials and methods
2.1. Materials
Kerosene (Fisher Scientic) was used as the model oil. Fatty acids
and sodium silicate (Fisher Scientic) were used as collectors and de-
pressant, respectively. Reagent grade HCl and NaOH (Fisher Scientic)
were used as pH modiers, while ultra-high purity KCl (N99.999%)
also from Fisher Scientic was used as the supporting electrolytes to
prepare 1 mM KCl solutions. The single minerals of apatite, dolomite,
and quartz were purchased from Ward's Natural Science Establishment
(Canada). The single mineral chunks were hand-crushed by a hammer,
ground and sieved to obtain particles in different size fractions suitable
for various measurements. The composition of the single minerals was
analyzed by the X-Ray Fluorescence micro-probe (EDAX ORBIS XRF)
and the results are shown in Table 1.
2.2. Zeta potential measurement
The zeta potential distribution of the oil droplets and mineral parti-
cles was measured using a Zetaphoremeter III (SEPHY/CAD). To prepare
75
Table 1
Composition of single minerals used in this study (wt %).
Components Apatite Dolomite Quartz
Na2O 2.19
MgO 36.06 1.30
Al2O3 0.21 0.77 1.00
SiO2 1.36 1.25 96.02
P2O5 46.06 1.18
SO3 1.11 0.68 0.27
CaO 48.18 60.27 0.23
CeO2 0.77 0.07
Fe2O3 0.12 0.91
an oil-in-water emulsion for zeta potential distribution measurement,
5 droplets of kerosene with and without fatty acid were placed in
100 mL 1 mM KCl solutions. The mixture was then placed under a 550
sonic dismemberator (Fisher) for 15 min to make micron size oil drop-
lets. The obtained emulsion was then creamed for 30 min to stabilize
the oil droplets. The oil droplets remained in the emulsions had an
average diameter of 504.2 73.7 nm, suitable for zeta potential distri-
bution measurement using the Zetaphoremeter. Before zeta potential
distribution measurement, the oil emulsion was diluted with 1 mM
KCl solutions to an oil droplet concentration that was suitable for the
test. The mineral particles with diameter smaller than 20 m were
mixed with the test solution to prepare a 0.010.1 wt.% suspension
and used for zeta potential distribution measurement. Once prepared,
the suspension was left for 10 min for the mineral particles to reach
equilibrium. The upper layer of the suspension was then used for zeta
potential distribution experiment.
The Zetaphoremeter III (SEPHY/CAD) consists of a rectangular elec-
trophoresis cell containing a pair of hydrogenated palladium electrodes
at both ends, a laser-illumination and a digital-video-viewing system.
The details on the experimental procedures can be found elsewhere
(Liu et al., 2002). About 30 mL of the prepared suspension or emulsion
samples at a given pH was used for zeta potential distribution measure-
ment. The zeta potential distributions obtained were used to calculate
the average zeta potential values for each measurement. The measure-
ments were repeated for three times for the same suspension/emulsion
and three sets of suspensions/emulsions were used for a given experi-
mental condition. The average values as well as the standard deviations
of nine measured average zeta potential values of a given sample were
reported. The measurement was conducted at ambient temperature of
22 0.5 C.
2.3. Contact angle measurement
The contact angle of reactive oily bubble on the mineral surfaces was
measured in testing solutions using the technique described by Liu et al.
(2002). In this method a block of mineral was rstly ground and then
polished to create a smooth surface. After polishing, the surface was
rinsed with ethanol followed by de-ionized water and dried under an
ultra-pure nitrogen stream to remove all possible contaminations on
the surface. The cleaned mineral surface was placed in a 2 cm 2 cm
square-shape glass cell lled with the testing solutions. A reactive oily
bubble, i.e., air bubble covered by a thin layer of kerosene with desired
concentration of fatty acid was generated and placed on the mineral
surface. After 1 min of contact with the mineral surface, the bubble
was retracted back slowly, while the images of bubble in contact with
mineral surface were recorded by a CCD camera. An image analysis soft-
ware was then used to analyze the video images, and the frame right be-
fore the three phase contact (TPC) moves was analyzed to obtain the
advancing contact angle. As illustrated in Fig. 1, the oil/aqueous solution
interface was advancing on a mineral surface, a tangent line was drawn
on the oil/aqueous solution interface at the TPC point. The angle be-
tween the tangent line and the mineral/water interface was measured
and considered as advancing contact angle (a). The contact angle on
76 F. Zhou et al. / International Journal of Mineral Processing 134 (2015) 7481

Fig. 1. Illustration of advancing contact angle measurement: a 100 ppm fatty acid-in kerosene reactive oily bubble on a mineral surface in 1mM KCl solution.

both sides of the reactive oily bubble was measured and the averaged
value was reported. As shown in Fig. 1, the advancing contact angles
at the left and right hand sides of the reactive oily bubble were 117.8
and 115.9, respectively, showing a good symmetry of the system. The
measurements were conducted at three different locations on a mineral
surface. The average values and standard deviations were reported.
2.4. Induction time measurement
to the bubble was plotted as a function of contact time. The contact
time at which the probability of mineral particles being picked up by
the bubble equals 0.5 (50%) was determined and dened as the
induction time. The induction time measured as such consists of liquid
lm drainage time, rupture time and the TPC line expending time. A
detailed description of the method can be found elsewhere (Yoon and
Yordan, 1991; Ye et al., 1989; Wang et al., 2010).

The induction time measurement was conducted by an in-house- 2.5. Micro-otation

built induction timer. For induction time measurement, the mineral
particles within size range of 150212 m were used. At the beginning To demonstrate the feasibility of reactive oily bubble otation, a
of each experiment, the conditioned solid suspensions were transferred modied micro-otation cell as shown in Fig. 2 was used in this study.
into a square shape glass cell using a plastic pipette. The mineral parti- Single mineral particles (particle diameter 4575 m) of apatite,
cles settled down quickly and formed a mineral bed on a piece of silica dolomite and quartz were mixed at the mass ratio of 1:1:1 and used
wafer (1 cm 1 cm) sitting on the bottom of the glass cell. An air, oily in the micro-otation test. In each micro-otation test, 5 g of the miner-
or reactive oily bubble was generated at the end of a glass capillary al sample mixture was dispersed in de-ionized water of pH 9 with re-
tube (inner diameter of 0.89 mm and outer diameter of 1.33 mm) agents (collectors and/or depressant) in a beaker for 5 min at pH 9.
using a micro-syringe. The other end of this glass capillary tube was The bottom chamber of the micro-otation cell was rst lled with
xed on the diaphragm of a speaker to drive the bubble. With the aid 20 mL kerosene containing 100 ppm fatty acid, and then 900 mL of con-
of a macro lens connected to a CCD camera, the bubble size and position ditioned mineral suspensions were added from the top into the cell. The
can be well monitored and controlled. To generate a reactive oily bub- mineral suspension in the otation cell was under mixing with a mag-
ble, the end of the glass tube was rstly immersed into the kerosene netic stir bar rotating at 350 rpm on the fritted disk to keep mineral
with or without fatty acid. A small volume of the kerosene was sucked
into the glass tube under the capillary force. The end of the glass tube
was then immersed into the mineral suspension in the glass cell, and
a reactive oily bubble, i.e., an air bubble covered outside with a thin
layer of kerosene was generated using the micro-syringe (Zhou et al.,
2014). It should be noted that only a small amount of kerosene should
be sucked into the glass tube to generate a thin layer of kerosene on
the air bubble.
The contact of mineral particle bed with the bubble was achieved by
moving the bubble towards and then in contact with the mineral parti-
cle bed for a given period of time before retracting the bubble away from
the mineral particle bed. In this study, the bubble approach and retract
speed was xed at 40 mm/s. The attachment of mineral particles to the
bubble was observed by the macro lens connected to the CCD camera.
The probability of particle attachment to the bubble, i.e., the number
of the trials (contacts) that particle (s) was (were) picked up by the
bubble divided by the total number of trails (contacts) made for a
given contact time was determined. Apparently, if the contact time be-
tween the bubble and the mineral particles is short, there would be no
bubbleparticle attachment, leading to a zero probability of attachment.
If the contact time is sufciently long, on the other hand, every contact
would lead to picking up the particles by the bubble, equivalent to a
probability of 1, i.e., 100% attachment. Therefore, one may expect a tran-
sit region of contact time where the probability of attachment increases
from 0 to 1 (or 0% to 100%). In the measurement, 20 trials were
attempted at each contact time. The probability of particle attachment Fig. 2. Schematic illustration of microotation using reactive oily bubble (Liu et al., 2002).
 F. Zhou et al. / International Journal of Mineral Processing 134 (2015) 7481
particles suspended in the suspension and break air stream entering the
cell into small (reactive oily) bubbles. The compressed air entered
the otation cell from the bottom of the cell at a ow rate of 300
mL/min. With the magnetic stir, the reactive oily bubble was generated
and released into the mineral suspension. The desired mineral particles
attached to the reactive oily bubbles oated to the top of the micro-
otation cell and overowed into the launder where the froth was col-
lected. After 5 min otation, the concentrates and tailings were ltered,
dried, weighed and then analyzed using XRF to determine its composi-
tion, which allows the calculation of concentrate grade and mineral re-
covery. During the experiment, the reactive oily bubbles with a layer of
kerosene can be visually observed with initial thickness around 1 mm.
The thickness of the kerosene layer decreased with time. Some kero-
sene was left in the chamber at the end of the experiment. It is therefore
believed that the reactive oily bubble was generated during the course
of the otation.
3. Results and discussion
3.1. Zeta potentials
3.1.1. Reactive oil droplet
Due to the difculties to make micron size reactive oily bubbles, the
zeta potentials of kerosene droplets containing different concentrations
of fatty acid (0 ppm, 50 ppm, 100 ppm, and 200 ppm) were measured to
understand the electrokinetic properties of reactive oily bubbles. Fatty
acid is a hydrolysable, weak acid type of surfactant. In aqueous solu-
tions, fatty acid dissociates to produce negative fatty acid anions as
shown in the following dissociation equation with pKa around 4.9
(Brennand et al., 1989):
RCOOHRCOO H
As shown in Fig. 3, the zeta potential of all kerosene emulsions in
aqueous solutions of pH above 6 becomes increasingly more negative
with increasing fatty acid concentration up to 100 ppm in kerosene
due to the increased adsorption of fatty acid groups at the kerosene/
water surface, indicating the potential to form reactive oily bubbles.
More fatty acid groups at kerosenewater interface would lead to
more powerful collecting powers of reactive oily bubbles to mineral
particles, which is benecial to phosphate otation. Further increasing
fatty acid concentration above 100 ppm in kerosene did not show
further increase in negative zeta potential value of kerosene droplets,
suggesting saturated adsorption of fatty acid at kerosenewater inter-
face with 100 ppm fatty acid in kerosene, which could be considered
Fig. 3. Zeta potential of kerosene droplets containing different concentrations of fatty acid
as a function of pH in 1 mM KCl solutions.
77
as optimal fatty acid concentration for generating reactive oily bubbles.
Therefore, 100 ppm of fatty acid was added in kerosene to generate
reactive oily bubble and used for experiments.
3.1.2. Mineral ores
The electrokinetic properties of the three single minerals (apatite, do-
lomite, and quartz) were determined by measuring their zeta potentials
in 1 mM KCl solutions. As shown in Fig. 4, the zeta potential of all min-
erals decreases with increasing pH of solutions. Compared with the
other two single minerals, quartz exhibits more negative zeta potential
without iso-electric point (iep) over the pH range studied. The iep of do-
lomite and apatite was determined to be around pH 6.2 and 4.2, respec-
tively, similar to the values reported in literatures (OforiAmankonah and
Somasundaran, 1985; Marouf et al., 2009).
Based on electrostatic interaction theory, the results of zeta potential
measurement in Figs. 3 and 4 suggest that dolomite could be separated
from apatite and quartz in 1 mM KCl solution between pH 4.5 and
pH 6.5 using fatty acid reactive oily bubbles, as there exists electrostatic
attractive forces between positively charged dolomite and negatively
charged reactive oily bubbles, while the electrostatic forces between
negatively charged quartz or apatite and fatty acid reactive oily bubble
are repulsive. However, it is well known that the electrostatic force is
not the only force that determines the selectivity attachment of mineral
particles to reactive oily bubbles. The chemical adsorption force could
play a critical role in particle attachment to reactive oil bubbles. This
chemical bonding force is more selective and hence often utilized in
conventional otation where phosphate minerals are oated at weakly
alkaline pH by anionic collectors (Tanaka et al., 1988; Sis and Chander,
2003b).
1 3.2. Contact angle
Effect of the reactive oily bubble on the wettability of the mineral
particle was studied by measuring the advancing contact angle of the
reactive oily bubble on the mineral surface. As shown in Fig. 5, the
advancing contact angles of the reactive oily bubble on apatite and
dolomite increased dramatically with pH, suggesting an increase of
mineral hydrophobicity due to the increased adsorption of reactive
fatty acid groups (RCOO) at the mineral/kerosene/water interface.
Very similar contact angle values of apatite and dolomite were observed
at the same pH values which are believed to be linked with the similar
binding nature of fatty acid reactive (carboxylate) groups with mineral
surface species (mostly calcium) at the dolomite and apatitewater
interface (Mohammadkhani et al., 2011). No TPC can be established
Fig. 4. Zeta potentials of apatite, dolomite and quartz in 1 mM KCl solutions as a function of
pH.
78 F. Zhou et al. / International Journal of Mineral Processing 134 (2015) 7481
Fig. 5. Advancing contact angles of reactive oily bubbles on ore surfaces in 1 mM KCl
solutions as a function of pH.
between the reactive oily bubble and quartz, demonstrating the absence
of reactivity between fatty acid on oily bubble surfaces and quartz sur-
faces. As shown in Fig. 5, the absence of fatty acid adsorption on quartz
surface translates to a zero advancing contact angle over entire pH
range studied. The results from the contact angle measurement indicate
that quartz can be easily separated from dolomite and apatite using the
reactive oily bubbles, and the separation will be more efcient at higher
pH due to a higher solid hydrophobicity. This observation agrees well
with the conventional otation results by Elgillani and Abouzeid
(1993). However, due to the similar contact angle values between
apatite and dolomite over the entire pH range studied, the separation
between these two minerals using fatty-acid reactive oily bubbles with-
out dispersant addition is difcult if not impossible.
3.3. Induction time
Flotation is a multiphase separation process, where solid mineral
particles suspended in a liquid contact with and attach to air bubbles
which carry the attached mineral particles to the top of the slurry to
form mineral froth. Particlebubble attachment, a process controlled
by solid hydrophobicity and surface charge, is a key element of otation.
Induction time can be used to evaluate the effectiveness of bubblemin-
eral particle attachment, which can be effectively used as an indicator to
Fig. 6. Induction time of mineral particle attachment to air bubbles, oily bubbles or reactive oily bubbles in 1 mM KCl solutions with and without fatty acid at pH 6 and pH 9.
predict the otation performance. The results of zeta potential mea-
surement in Figs. 3 and 4 suggest the conditions of separating apatite
from dolomite using reactive oily bubbles at pH around 6 in contrast
to pH 9 for the conventional otation separation reported in literature.
Induction time of single minerals attaching to three different bubbles,
i.e., air bubble, oily bubble (kerosene) and reactive oily bubble (kero-
sene containing 100 ppm fatty acid) was measured at pH 6 and pH 9.
As shown in Fig. 6, there is no attachment within 10 s of contact time
between all three mineral particles and air bubbles or oily bubbles with-
out fatty acid addition at both pH 6 and 9, indicating that these minerals
are naturally hydrophilic and non-oatable at these two pHs. With the
addition of 100 ppm fatty acid either in the pulp or in kerosene oily bub-
ble, the induction time of apatite and dolomite particles attaching to the
three kinds of bubbles decreased dramatically at pH 6 and further at
pH 9, possibly due to the increased surface hydrophobicity with increas-
ing pH (Fig. 5). Although both the reactive oily bubble and mineral sur-
faces are highly negatively charged (Figs. 3 and 4), the strong long range
electrostatic repulsive forces between bubble and particles are weaker
than the attractive force due to the increased solid hydrophobicity,
demonstrating a vital role of solid wettability in the mineral otation.
The adsorption of fatty acid at quartz surface was minimal as shown
by the absence of three phase contact line formation (i.e., 0 of contact
angle in Fig. 5). As a result, no attachment between quartz and bubbles
was observed as shown in Fig. 6.
As shown in Fig. 6, the induction time of apatite attaching to the reac-
tive oily bubble at pH 6 is shorter than 10 ms, which is much shorter than
the induction time of air bubble or oily bubble attaching to apatite condi-
tioned in 100 ppm fatty acid solutions. This nding suggests that the re-
active oily bubble would be much more effective in oating apatite than
using conventional otation methods. The induction time of apatite
attaching to the reactive oily bubble is 25 ms at pH 9, only marginally lon-
ger than the induction time of b 10 ms at pH 6. This difference in the mea-
sured induction time at these two pHs is too small to have a signicant
impact on the micro-otation of apatite by the reactive oil bubbles.
To investigate the effect of collector released from reactive oily bub-
ble on the reactive oily bubbleparticle attachment, the induction time
of oily bubblemineral attachment was measured in solutions where
reactive oily bubble had been immersed for 40 min. No attachment
between oily bubble and mineral particles was observed, showing that
the release of collector from kerosene layer on the reactive oily bubble
surface was marginal. The attachment between collector and minerals
is not due to the collector dissolved from reactive oily bubble. This result
also clearly demonstrates the minimal activation effect of collector on
unwanted minerals in reactive oily bubble otation.
 F. Zhou et al. / International Journal of Mineral Processing 134 (2015) 7481
Fig. 7. Comparison of zeta potentials of apatite, dolomite and quartz in 1 mM Na2SiO3 and
1 mM KCl solution as a function of pH.
As shown in Fig. 6, the induction time of apatite attaching to reactive
oily bubble at pH 6 (b10 ms) is much smaller than the case of dolomite
(250 ms) and quartz (N10 s). It appears that apatite separation from
dolomite and quartz could be accomplished by otation using reactive
oily bubbles at pH 6. However, with the induction time values in the
order of 250 ms, the dolomite can still be oated. It is conrmed in the
single mineral micro-otation tests. The otation recovery of dolomite
using reactive oily bubble at pH 6.14 is about 71%, in comparison to
85% for apatite. Therefore, the effective separation of apatite from dolo-
mite using the reactive oily bubble otation is difcult due to the similar
dolomite and apatitewater interfacial properties, both containing rich
calcium ions (Mohammadkhani et al., 2011). However, dolomite
contains a signicant amount of magnesium ions, which provides an
opportunity to search for magnesium-specic depressant to enhance
the differences in oatability between apatite and dolomite. About a
dozen of reagents have been studied as the depressant for phosphate
otation with sodium silicate and sodium carbonate being identied
to be practically promising (Zheng and Smith, 1997). In this communi-
cation, sodium silicate (Na2SiO3) was chosen as the depressant to sepa-
rate apatite from dolomite.
3.4. Effect of depressant
The zeta potentials of the three minerals in 1 mM Na2SiO3 + 1 mM
KCl solutions were determined and compared with the zeta potential
measured in 1 mM KCl solution. As can be seen in Fig. 7, the zeta
Fig. 8. Induction time of mineral particle attachment to: (a) air bubble and (b) reactive oily bubble in 1mM KCl solutions at pH 9 with 1 mM sodium silicate, and corresponding advancing
contact angle.
79
potentials of apatite and quartz with 1 mM Na2SiO3 addition were com-
parable to the values measured in 1 mM KCl solutions, while the zeta
potentials of dolomite with 1 mM Na2SiO3 addition were much more
negative than that in 1 mM KCl solutions, indicating the adsorption of
Na2SiO3 at dolomite surfaces. In the absence of depressant as shown
in Fig. 4, zeta potentials of dolomite over the entire pH range evaluated
were higher than that of apatite. However, with the addition of 1 mM
Na2SiO3, the zeta potentials of apatite became higher than that of dolo-
mite. Such observation suggests Na2SiO3 being a better depressant for
dolomite than for apatite, showing the potential to use Na2SiO3 as the
depressant in selective otation of apatite from dolomite and quartz.
The possible use of Na2SiO3 in phosphate mineral otation is further
investigated by determining the induction time of bubblemineral par-
ticle attachment. In this set of tests, both collector (100 ppm fatty acid)
and depressant (1 mM Na2SiO3) were added in 1 mM KCl solution,
while air bubbles were used to mimic the conventional otation pro-
cess. The results in Fig. 8(a) show that the induction time of apatite
and dolomite were 10 ms and 20 ms, respectively, corresponding well
with the observed similarity in advancing contact angle, which were de-
termined to be 67.0 and 72.5 for apatite and dolomite, respectively.
These results indicate that dolomite cannot be separated from apatite
by conventional air bubble otation even with the addition of 1 mM
Na2SiO3 as the depressant. It is possible that fatty acid has a stronger
afnity to dolomite than Na2SiO3, making the depressant ineffective.
Fig. 8(b) shows the induction time of reactive oily bubblemineral
attachment and advancing contact angles in 1 mM Na2SiO3 + 1 mM
KCl solutions. As can be seen, the quartz surface remained hydrophilic
in the presence of Na2SiO3 and no attachment can be made between re-
active oily bubble and quartz. In the presence of Na2SiO3, the advancing
contact angle of dolomite dramatically decreased from 105 (Fig. 5) to
5.7 (Fig. 8), illustrating that the dolomite surface was greatly depressed
by Na2SiO3. In contrast, the addition of Na2SiO3 had a negligible effect on
contact angle of reactive oil bubbles on apatite, which is anticipated
from the minimal change in zeta potential of apatite with Na2SiO3. As
a result, the induction time of dolomite (3900 ms) was much longer
than apatite (10 ms), as anticipated from much smaller advancing con-
tact angle of dolomite (5.7) than apatite (85.3). Under this condition,
the dolomite is basically non-oatable, making it possible to separate
apatite from dolomite using the reactive oily bubbles.
With reactive oily bubbles, the addition of collector to the aqueous
phase can be avoided, minimizing undesired synergetic interaction be-
tween collectors and depressants present in slurry. The results of both
induction time and contact angle measurements presented here suggest
that reactive oily bubble system is better than conventional air bubble
otation. With stronger collecting power of reactive oily bubbles,
apatite may be better separated from dolomite by this novel otation
system than by conventional method when 100 ppm fatty acid and
1 mM Na2SiO3 are used as collectors and depressants, respectively.
80 F. Zhou et al. / International Journal of Mineral Processing 134 (2015) 7481

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Fig. 9. Proposed ow scheme for otation separation of apatite, dolomite and quartz using reactive oily bubbles.

3.5. Micro-otation results
Based on the previous results, a new otation separation scheme of
apatite, dolomite and quartz using reactive oily bubble and air bubble
was proposed as shown in Fig. 9. First of all, apatite will be separated
from dolomite and quartz using reactive oil bubble in the presence of
Na2SiO3 at pH 9, followed by separation of dolomite from quartz using
air bubbles with the addition of 100 ppm fatty acid in the pulp.
Micro-otation of mineral mixture was designed and performed
based on the proposed ow scheme. The mineral mixture of apatite,
dolomite and quartz at 1:1:1 mass ratio was rst oated by reactive
oily bubble at pH 9 for 5 min, and the froth was collected as concentrate
1. After recovery of apatite, 90 L fatty acid was added in the slurry at
pH 9 and stirred for 10 min. The slurry was then oated for 5 min
using air bubbles and the froth was collected as concentrate 2. The
two concentrates and tailings samples were analyzed using the XRF.
The results in Table 2 show CaO and P2O5 contents of 57.11% and
35.85%, respectively, with a negligible amount (0.92%) of MgO content
for concentrate 1, indicating a high concentration of apatite. The MgO
content in concentrate 2 was as high as 20.75%, in contrast to 0.92%
and 1.83% in concentrate 1 and tailings, respectively, showing a high
concentration of dolomite in concentrate 2 with a minimal misplace-
ment in concentrate 1 and tailings. The SiO2 contents in concentrates
1 and 2 were very low at 2.13% and 7.91%, respectively, in comparison
to 90.70% in tailings. The results collectively indicate high recovery of
Table 2
XRF results of micro-otation products (wt.%).
Components Mixed material sample Concentrate 1 Concentrate 2
apatite and dolomite in concentrates 1 and 2, respectively, and good
quality of apatite and dolomite concentrates. The XRF results clearly in-
dicate that the three minerals can be separated using the proposed o-
tation scheme.
In fertilizer industry, it is necessary to produce phosphate concen-
trate of following specications: (1) P2O5 N 30%, (2) MgO b 1%, and
(3) the mass ratio of CaO to P2O5 b 1.6 (Sis and Chander, 2003b;
Heidarpour, 2009). As shown in Table 2, concentrate 1 contained
35.85% P2O5 (N30%) and 0.92% MgO (b1%), with a CaO/P2O5 ratio of
1.59 (b1.6), all meeting the requirements of industrial productions.
Therefore, the micro-otation results demonstrated the feasibility of
the proposed process owsheet for apatite, dolomite and quartz separa-
tion using reactive oily bubble otation followed by conventional air
bubble otation.
Our study clearly shows some advantages of using reactive oily
bubble than the conventional air bubble, i.e., smaller induction time
and larger contact angle. Another key advantage of using reactive oily
bubble is its minimal undesired synergetic interaction between collec-
tor and other chemical species such as depressant added to the aqueous
phase in conventional otation systems. Such feature is the key to
separate apatite from dolomite with the addition of depressant using
reactive oily bubbles, which cannot be achieved by adding fatty acid
and depressants in the aqueous phase as in the conventional otation
with the results shown in Fig. 8. In this study, kerosene was used as an
example of oil phase. In practice, other immiscible oil or solvent such
as waste vegetable oil or biodiesel can be used as the source of oil
phase to meet some special requirements.
4. Conclusions
Tailings

Al2O3 0.14 0.00 0.19 0.00 The use of reactive oily bubble to separate apatite from dolomite and
BaO 0.30 0.70 0.33 0.04 quartz was proposed and tested. Reactive oily bubble, the air bubble
CaO 35.15 57.11 54.65 5.07
Fe2O3 0.48 0.27 1.21 0.20
covered by a thin layer of kerosene containing 100 ppm fatty acid was
K2O 0.09 0.21 0.14 0.10 used in this study. The induction time of reactive oily bubble attaching
MgO 7.89 0.92 20.75 1.83 to mineral particles was found to be much shorter than that of the air
Mn3O4 0.05 0.00 0.16 0.01 bubble and oil droplet, demonstrating a higher mineral collecting
Na2O 0.37 1.46 0.79 0.41
power using the reactive oily bubble. Depressant was found to be essen-
P2O5 14.84 35.85 13.02 1.40
PbO 0.07 0.30 0.14 0.11 tial to separate apatite from dolomite using the current reactive oily
SO3 0.30 0.74 0.52 0.11 bubble otation technology. The induction time measurement indicated
SiO2 40.21 2.13 7.91 90.70 selective depression of dolomite by 1 mM Na2SiO3 in 1 mM KCl solu-
SrO 0.07 0.21 0.08 0.00 tions with a negligible effect on the attachment of apatite to reactive
TiO2 0.02 0.01 0.05 0.01
oily bubbles. A new otation scheme combining reactively oily bubble
 F. Zhou et al. / International Journal of Mineral Processing 134 (2015) 7481
otation and conventional air bubble otation was proposed to separate
apatite from dolomite and quartz. Micro-otation tests conrmed effec-
tive separation, producing apatite concentrate that meets the industrial
standard at a high apatite recovery or minimal loss of apatite in tailings.
Acknowledgment
Financial supports for this work from Natural Sciences and Engi-
neering Research Council of Canada (NSERC-Discovery), Ministry of Ed-
ucation of the People's Republic of China Program for Changjiang
Scholars and Innovative Research Team in University (IRT0974) (China)
and National Natural Science Foundation of China (51404171) (China)
are greatly appreciated.
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