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A R T I C LE I N FO A B S T R A C T
Keywords: This work evaluated the influence of nanobubbles (150–200 nm, mean diameter) on the visual adhesion of
Flotation microbubbles (70 μm mean diameter) and macrobubbles (1 mm mean diameter) onto selected mineral particles
Nanobubbles (quartz and apatite) and on the flotation of both minerals, at bench scale. The adhesion of bubbles to high purity
Microbubbles grains of quartz and apatite was monitored using a specially designed photographic technique. The results
Macrobubbles
showed that the highest adhesion of bubbles onto the mineral grains occurred only after “conditioning” with
Apatitic ore
Quartz
nanobubbles. The nanobubbles appear to adhere to hydrophobic surfaces and confined to the rough surfaces of
the grains, probably due to the dissipation of the free surface energy of the solids. As a result, the nanobubbles
appear to serve as nuclei for enhanced adhesion of micro and/or macrobubbles, assisting the flotation of both
minerals. In the case of quartz (D50 = 290 μm), the recovery increase was about 23% compared to a standard
test of flotation with macrobubbles only. Furthermore, flotation kinetics was rapid and quartz recovery, at the
first min, was double that obtained in the absence of nanobubbles. In the case of a fine apatitic ore
(35% < 37 μm particles), best results were obtained with a combination of nano, micro and macrobubbles, with
a 500–1000 g t−1 saponified soybean oil collector and a 300–600 g t−1 gelatinized corn starch depressant of iron
bearing minerals. The P2O5 recoveries increased about 9% compared to flotation with macrobubbles only, and
separation also occurred at a higher rate. The total recovered phosphate (4 min standard test) was obtained in
the first 1.5 min, after conditioning with nanobubbles, followed by injection of and microbubbles. Results va-
lidated the reported high potential for nanobubbles in “surface conditioning”, the first stage of mineral flotation
and were explained in terms of the solution and interfacial phenomena involved.
1. Introduction Rubio et al., 2003; Fuerstenau et al., 2007; Santana et al., 2012). Yet,
microbubbles do not have enough lifting power (carrying capacity) and
Froth flotation is believed to be the most efficient and cost-effective a combination with coarser bubbles appears to be essential; un-
unit operation in mineral processing (Fuerstenauet al., 2007). Yet, se- fortunately, the practical use of a wide bubbles size distribution poses a
paration efficiency decreases for particles less than 37 µm and fall serious challenge to flotation machine manufacturers. This occurs
sharply for the ultrafines fractions (< 13), due to the low probability of mainly because of bubbles interactions themselves, usually leading to
bubble-particle capture (poor attachment). Yet, it has been reported coalescence or engulfing of the fine bubbles by the coarser bubbles
that fine particle recovery in flotation is enhanced by using micro- (Yoon, 2000; Ralston et al., 1999; Azevedo et al., 2016a; Fuerstenau
bubbles (MBs - 30–100 μm diameter) and/or nanobubbles (NBs of et al., 2007).
120–800 nm diameter) (Ahmed and Jameson, 1985; Ralston et al., Regarding nanobubbles in mineral flotation, recent studies reported
1999; Gontijo et al., 2007, Azevedo et al., 2016a,b, Etchepare et al., advantages regarding the enhancement of the contact angles after their
2017, Oliveira et al., 2018). capture by particles, assisting the probability of flotation (and its rate)
Mechanisms involved while employing microbubbles are related to by larger bubbles (> 1 mm) (Ahmadi et al., 2014; Calgaroto et al.,
a higher residence time for bubble-particle adhesion at the film-thin- 2015; Fan and Tao, 2008; Fan et al., 2012; Sobhy and Tao, 2013,
ning and disjoining pressure stage (Yoon, 2000; Ralston et al., 1999; Azevedo et al., 2016b). In other words, they would act as a conditioner
⁎
Corresponding author.
E-mail address: jrubio@ufrgs.br (J. Rubio).
URL: https://www.ufrgs.br/ltm (J. Rubio).
https://doi.org/10.1016/j.mineng.2018.08.020
Received 7 May 2018; Received in revised form 6 August 2018; Accepted 8 August 2018
Available online 20 August 2018
0892-6875/ © 2018 Elsevier Ltd. All rights reserved.
A.F. Rosa, J. Rubio Minerals Engineering 127 (2018) 178–184
a b
Table 1 phosphate were the reagents used for the quantitative determination of
Conditions of bubbles-particles (apatite/quartz) interac- P2O5.
tions. The adhesion of bubbles onto quartz was studied High purity lumps of apatite (Ca5 (PO4)3(OH, F, Cl)) and quartz
under conditions 1, 2 and 3. (SiO2), both from southern Brazil, were used to investigate bubble-
Condition Bubbles injected mineral interactions. Samples of phosphate ore for the flotation studies
were collected from Tapira (Vale Fertilizers, South Brazil), from a feed
1 MaBs flotation circuit, after comminution, classification, low intensity mag-
2 NBs
netic separation, attrition and desliming stages. More than 98% of the
3 NBs + MaBs
4 MBs sample consisted of particles smaller than 200 # (75 μm), with 37% in
5 NBs + MBs the 400 # fraction (37 μm). The mean diameter (D50) of the particles
6 MBs + MaBs was 55 μm, while the D80 was 100 μm. The average sample content was
7 NBs + MBs + MaBs
8.4% P2O5. Quartz samples for flotation were prepared from rock
crystals from Lajeado (South Brazil). The quartz particles were frac-
tioned using Mesh Tyler sieves, and the particle-size distribution of each
Table 2
fraction was measured in a Cilas 1064 laser particle size analyzer. A
Flotation studies conditions at 28% w/w.
−48 + 100# fraction was used in the flotation studies with a mean
Conditions Reagents dosage [collector]a; [depressant]b (g·t−1) diameter (D50) of 290 µm.
1 1000; 600
Fatty acid soap from soybean oil was used as the collector for
2 500; 300 phosphate and gelatinized corn starch was used as gangue mineral
depressant. A 10% NaOH solution was used for pH adjustment. In the
a
Fatty acid soap from soybean oil. quartz flotation studies, the collector was the commercial reagent
b
Gelatinized corn starch. Flotigam EDA 3B (Clariant®), an alkyl ether monoamine.
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A.F. Rosa, J. Rubio Minerals Engineering 127 (2018) 178–184
Fig. 2. Micrographs of bubbles - apatite particle adhesion: (a) Only with MaBs; (b) with NBs + MaBs; (c) with MBs; (d) with MBs + MaBs; (e) with NBs + MBs; (f)
with NBs + MBs + MaBs.
MBs). The steel saturation vessel was equipped with an internal con- temperature. The microbubbles, were measured using the LTMBSizer
tainer made of glass (40 cm high, 10 cm diameter, and 0.5 cm thickness; following the technique developed, in our group, by Rodrigues and
0.7 L effective capacity). The concentration, mean size and size dis- Rubio (2003).
tribution of the NBs were measured in quadruplicate in a nanoparticle- The depressurization-cavitation stage was performed at a 2-mm
tracking analysis (NTA) instrument (NanoSight LM10 & NTA 2.0 internal diameter needle valve (Globo 012-Santi®, São Paulo, Brazil)
Analytical Software, Malvern Instrument Ltd, Salisbury, UK) at room and MBs and NBs were generated in a glass column, as described by
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A.F. Rosa, J. Rubio Minerals Engineering 127 (2018) 178–184
Fig. 3. Micrographs of bubbles - quartz particle adhesion: (a) Only with MaBs; (b) with NBs + MaBs.
Table 3
Flotation of apatitic ore: P2O5 recoveries and grades at different conditions. SD = standard deviation.
Condition [Collector]; [Depressant] (g·t−1) Distribution of bubbles used P2O5 Recovery (%) SD P2O5 Content (%) SD
Fig. 4. Apatitic ore flotation studies: P2O5 recovery as a function of time in the STD (MaBs) tests and with combinations of different sized bubbles (NBs + MaBs,
MBs + MaBs, NBs + MBs + MaBs); pH 9.5. (a) Condition 1–28% solids; [collector] = 1000 g t−1; [depressant] = 600 g t−1; (b) Condition 2–28% solids; [col-
lector] = 500 g t−1; [depressant] = 300 g t−1. For standard deviations, see Table 3.
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A.F. Rosa, J. Rubio Minerals Engineering 127 (2018) 178–184
Fig. 6. Graphical representation of main mechanisms involved in the flotation assisted by nanobubbles. Modified from Pourkarimi et al. (2017) and Xiong (2014).
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