XVII.

BMPC-2017 Antalya / TURKEY

APATITE FLOTATION USING SORGHUM AS DEPRESSANT

E.M.S. Silvaa; A.E.C. Peresb; A.C. Silvac; T. Elwertd; S. Tuchtfelddd

a
-
LO HORIZONTE-BRAZIL
b
-
-BRAZIL
c
-DOC -
88881.119296/2016- -BRAZIL
d
-ZELLERFELD-
GERMANY

ABSTRACT
The flotation of Phosphate ore with silicate-
Alkaline Ultramafic and Carbonatitic Complex has low selectivity between apatite mineral family and
carbonate. Starches are widely used as depressant in froth flotation operations in Brazil due to their
efficiency, increasing the selectivity in the process. Starches market have been growing and improving in
recent years, leading to better products attending the requirements of mineral industry. The major source
of starch nowadays is cornstarch, which need to be gelatinized, by heat or sodium hydroxide addition,
prior to its use. In the search for a new, cheap and reliable starch source for apatite microflotation tests
using Hallimond tube were carried out. The recovery of apatite was measured in the presence and absence
of depressants. Three different depressants were tested, sorghum flour and starch, and cornstarch. Flotigam
5806 (300 g/t) from Clariant were used as collector. Four different pH values were tested (9.5, 10, 10.5,
and 11) and four dosages of the depressants (0, 400, 800, and 1200 g/t), totalling 144 assays. The apatite
sample was characterized by SEM, EDS, XRD, XRF, and had its zeta potential measured. The results for
sorghum were compatible with the results for cornstarch, indicating that this cereal can be a feasible
substitute for corn as a starch source.

Key words: Apatite, Froth Flotation, Depressants, Starch.

INTRODUCTION
Agriculture has had a major participation in Brazil's trade balance on the last decades, being one of the
most important global players for soy, corn, coffee, poultry and beef, among others. Brazilian dependence
on fertilizers has been debated for years. Most of phosphorus bearing minerals present in the phosphate
rock belong to the group of apatite (Ca5(Cl, F, OH)(PO4)3), a crystalline calcium phosphate, with P2O5
content between 4% and 15%. Igneous deposits mostly compose Brazilian phosphate rock mines (in
operation or prospection), with P2O5 grades above sedimentary deposits. Brazilian phosphate originated
from igneous deposits has simultaneous occurrence of several gangue minerals. The most frequent are
iron oxides, micas, vermiculite, titanium bearing minerals, and carbonates. Currently, the most used
et al., 2006).
The complex mineralogy of the igneous deposits compared to the sedimentary ones, for example in
Florida (USA) or in Morocco, has led to the definition of specific reagents for phosphate rock froth

economi
411
[Link]-2017 Antalya / TURKEY

According to Liu et al. (2000), polysaccharides are condensation polymers of high molecular weights
based on simple monosaccharide (sugar) units. Many different types of polysaccharides exist in nature but
only a small number of them have been used by mineral industry, especially in flotation. In Brazil,
cornstarch is widely used in many industries as the depressant for iron ore (Peres and Correa, 1996).
Starch is a major storage form for carbohydrates and consists of two major polysaccharides, amylose
(20-30% of its composition in weight) and amylopectin (70-80%) and some impurities such as fibres,
mineral matter, oils and proteins (usually <1%) (Liu and Laskowski, 1989; Kar et al., 2013). Peres and
Correa (1996) point out that the oil content (popular designation of triacylglycerol) present in conventional
starch act as an antifoam agent spoiling the flotation process if its content exceeds 1.5%. To be used as
depressant in flotation starch needs to be gelatinized using heating and/or an alkali solution. This process
corresponds to the irreversible disruption of the molecular order within the starch granules when aqueous
diluted suspensions of starch granules are heated above
in Brazil only performs gelatinization with sodium hydroxide addition. According Fillipov et al. (2014)
the effectiveness of the alkali gelatinization is strongly affected by the starch/NaOH ratio used in the
gelatinization. The last authors even suggest that alkali gelatinization has been studied less than the thermal
method.
Other vegetable species, such as cassava, potato, wheat, rice, arrowroot, can produce starch with
potential to be used in flotation. According to Fillipov et al. (2013), cassava starch shows higher viscosities
than cornstarch, which is an indication of higher molecular weight that can lead to more effective
depressant action. Potato flour has been used industrially in Europe, but there are no records of its use in
the mining industry so far, mainly due the fact that potato degrades much faster than corn and has a high
price (Ibrahim and Abdel-Khalek, 1992).
Sorghum (Sorghum bicolor L. Moench) is a crop that is widely grown over the world for production of
food and feed.
barley. It is mostly cultivated across the world in the warmer weather areas. Sorghum is the main staple
food for the worl
up about 60 80% of normal (non-waxy) kernels. Nowadays sorghum is cultivated in Brazil only for animal
food despite the fact of its possible usefulness in different food products (Elkhalifa et al., 2004).
According to the Brazilian Agricultural Research Corporation (EMBRAPA), a state-owned research
corporation affiliated with the Brazilian Ministry of Agriculture, sorghum culture is fully mechanized and
the same equipment used with other cultures, such as corn, rice, wheat, or soy, can be used on it. Sorghum
is marketed with prices 70 to 80% smaller than corn, which can be a major feature considering the
necessity of cost reduction in mining companies, driven by the economic crisis that Brazil has been facing
in the last years. Because of the similarity between corn and sorghum, its few industrial applications and
low price compared to corn, the aim of this study was to analyse the sorghum potential to be used as
depressant on apatite flotation.

METHODOLOGY
[Link] characterization

by the Brazilian company Agroceres. Sieving was initially used to clean the grains from straw residues
and other impurities. In order to remove residual moisture the grains were dried in the drying oven at 35

with a sieving stage) to generate the sorghum flour. The methodology proposed by Rupollo (2011) was
used to extract sorghum starch. Starches morphology were analysed using a SEM JSM-6610 from Jeol
412
[Link]-2017 Antalya / TURKEY

coupled with EDS probe from Thermo Scientific NSS Spectral Imaging at UFG Labmic laboratory. The
particle size was performed dry with a HELOS laser diffraction particle size analyser from Sympatec and
coupled with RODOS dry disperser. The method 61-03.01 (AACC, 1995) was used to determine the
starches amylose content. The protein amount was determinate according to the methodology proposed
by Bradford (1976), and the lipids amount according to Bligh-Dyer (1959) method. Ash content, defined
as the residue remaining after controlled incineration of the flour and corresponding to the mineral content
of the flour, was determinate using the method 08-21.01 (AACC, 1997).

[Link] sample characterization

Apatite samples were comminuted in a jaw crusher followed by a ball mill, and granulometric separated
through wet sieving using a Tyler sieving series during 15 minutes. The samples were then dried in an

contamination from the previous stages. The mineralogical phase characterization was performed at
UNIFESSPA using an X-ray Diffractometer Empyrean from PANalytical with graphite monochromator,

composition was determined at Copebras S/A laboratory using an X-ray Fluorescence spectrometer
AXIOX MAX series DY 5001 from PANalytical. Samples images were acquired with a SEM JSM-6610
from Jeol coupled with EDS probe from Thermo Scientific NSS Spectral Imaging at Labmic /UFG. The
particle size was performed wet with addition of Na2P2O7 (1 g/L) as dispersant agent and tap water at
IFAC/TUC using a HELOS laser diffraction particle size analyser from Sympatec. The apatite zeta
potential was measured at LPI/EM/UFOP from pH 3.5 to 12.5 with distillate water and having KCl at 10-
3
mol/L as indifferent electrolyte using a ZS90 Zetasizer Nano from Malvern.

[Link] tube tests

Microflotation tests were performed on Hallimond modified tube (addition of an extender between the
bottom and upperparts of the tube in order to reduce the effects of hydraulic entrainment) with 320 mL of
interna
kept at 40 cm3/min, pressure at 10 psi, apatite sample at the size range of +106- -100 #), as
et al. (2015). The apatite mass used in each test was 1.0 g. Flotigam 5806
from Clariant, a synthetic mix of fatty acids, at a dosage of 300 g/t were used as collector. Three different
depressants (sorghum flour, sorghum starch, and cornstarch) with four dosages (0, 400, 800, and 1200 g/t)
were tested. Four different pH values were tested (9.5, 10, 10.5, and 11) totalling 144 assays. The pH was
adjusted with hydrochloric acid and sodium hydroxide, both at 1%. The conditioning time was 7 min for
the collector and 5 minutes for the depressant. The flotation time was 1 min. Distillate water was used
throughout the experiments.

RESULTS AND DISCUSSION

founded by Biduski et al. (2017) for native sorghum starch (37.20%). Usually the major fraction of starch
is composed of amylose and amylopectin at an approximate ratio of 3:1 (Peres and Correa, 1996). Pinto
et al. (1992) showed that amylopectin is more efficient depressant for hematite than amylose in
microflotation tests. For apatite, the same authors showed that pure amylose has lower depressant action,
followed by amylopectin and starch. According to Nunes and Peres (2011), the starch depressant action is
due to the presence of hydroxyl groups presents on starch chemical structure.
413
[Link]-2017 Antalya / TURKEY

ied for cornstarch (0.79%) and

higher than potato starch (0.13%) (Dhital et al., 2011). Sorghum flour presented the higher lipids content
et al
a ected when oil content is lower than 4%, possibly due the fact that the collector used in this flotation
system, normally ionized fatty acids soap species, is also a frothing agent.
Protein amount in sorghum starch (0.85%) was almost the same when compared to cornstarch (0.86%)
protein amount found by Naguleswaran et al. (2012) and lower than sorghum flour (1.86%). The ash
rch (0.09%) (Dhital et al., 2011)
and cassava (0.10%) (Moore et al., 2005), but lower than potato starch (0.16%) (Dhital et al., 2011), and

protein amount, a low ash content and protein amount lead to a high quality starch. The results indicated
that the extract sorghum starch present a high purity degree and the extraction process in laboratory scale
was efficient (Rocha et al., 2008).
Sorghum starch gra
et
al. (1993) cornstarch granules shape found in the literature are typically angular and spherical shapes, with

results.

(a) (b)
Figure 3. (a) Starch characterization (cornstarch results extracted from literature) and (b) sorghum
granulometric analyses results

Figure 2 shows the SEM results for the size and morphology of the starches. No protein ribbons were
seen for the starches but some broken grains were detected. It is possible to notice that sorghum flour
shows particles from the cereal shell since the flour is just the cereal milled. Sorghum starch granules
observed were small, with varied shapes. Although the predominant shape is spherical, some of the
granules were irregular, tending to an oval or semi-spherical shape, or even presenting an irregular
polyhedral shape.
Table 1 shows the results of X-ray fluorescence of apatite sample. The follow oxides were analysed but
not found in the apatite sample: Co3O4, Ta2O5, Cr2O3, CuO, HfO2, MgO, Nb2O5, TiO2, WO3, Y2O3, Yb2O3,
ZnO, and ZrO2. Since pure apatite contains amounts CaO and P2O5 of 55.07 and 41.82%, respectively, is
possible to estimate that the apatite sample has 95.5% of purity, regarding its chemical composition.

414
[Link]-2017 Antalya / TURKEY

Figure 3 shows scanning electron microscope images from apatite samples using backscattered and
secondary electron imaging. It is possible to notice the association of apatite with an acicular mineral
phase. Energy-dispersive X-ray spectroscopy results are show for two points, one on the acicular phase
(3c) and the other on the apatite phase (figure 3d). The presence of fluorine in the sample suggest that the
mineral sample is composed by fluorapatite. The acicular phase could not be correct identified based only
on this result.
Figure 4a shows the X-ray diffraction results for the apatite sample. Since the objective of the XRD
was to confirm the mineral phases present in the sample, a simple search in the Bragg peaks allowed the
confirmation of the apatite phase. Nevertheless, a refinement step of the results was performed to check
the sample composition. The found results did not indicate the presence of other mineral phase in the
sample. Regarding the Zeta potential measurements (figure 4b), the apatite zero charge point was not
detected in the tested pH range (3.5 to 12.5) and superficial charge was negative. According to Oliveira
(2007) apatite has negative superficial charge at alkaline pH and the adsorption of anionic collectors on
its surface is due chemisorption. Figure 4c presents the granulometric analyse of the apatite sample using
HELOS analyser. Even though the samples had being wet sieved (+106-

the imperfection of the sieving process. Figure 4d shows an image acquired using an optical microscope
of the apatite sample.

(a) (b)

(c) (d)

415
[Link]-2017 Antalya / TURKEY

(e) (f)
Figure 4. SEM images for cornstarch magnification (a) x500 and (b) x3,000, sorghum starch (c) x500
and (d) x1,000, and sorghum flour (e) x500 and (f) x1,000

Table 2. XRF results in percentage for apatite sample

CaO P2O5 K2O SiO2 SO3 I Cl Na2O ThO2 Fe2O3 MnO BaO SrO
54.02 38.49 4.20 1.10 0.63 0.39 0.34 0.27 0.18 0.11 0.11 0.10 0.06

(a) (b)

416
[Link]-2017 Antalya / TURKEY

(c) (d)

(d) (e)

Figure 5. SEM images for apatite samples (a) BEC and (B) SEI image at x190 and (c) BEC and (d)
SEI image at x750 magnification. EDS results for points 1 (e) and 2 (f) marked on figure 2c

Figure 5 shows the apatite recovery in the flotation tests. As expected, low dosages of the depressant
leaded to a high recovery of apatite and high dosages end up depressing almost all apatite. This was
expected since there were no other minerals for the depressant to react with it. It is possible to notice that
for all tested pH the sorghum flour had recovery lower than the other two tested depressants. This fact
could be related with the lower amylose content of it. On the other hand, cornstarch showed higher
recoveries as expected, once it has the higher amylose content of the three depressant tested. Since what
is desired is that the depressant acts against the flotation, forcing the mineral to sediment, sorghum starch
and flour had superior results when compared with cornstarch, even for dosages bellow the adopted in the
phosphate rock industrial plants (700 g/t).
Another result that agrees with the proposed in the literature is the influence of the pH in the flotation
system. The pH reduced drastically the apatite recovery even without the presence of the depressants.

417
[Link]-2017 Antalya / TURKEY

(a) (b)

(c) (d)
Figure 6. Results for apatite samples characterization: (a) X-ray diffraction, (b) Zeta potential, (c)
particle size, and (d) optical microscope image

pH 11.5, around 42 and 90%

lower recovery than compared with cornstarch, respectively. Similar results were obtained for sorghum
flour. Despite this values not being the lower recovery obtained, they were produced with the lower dosage
of depressant, which can be industrially more cost effective. At pH 10 sorghum starch produced results
higher than cornstarch, although sorghum flour had similar results compared with cornstarch.

(a) (b)

418
[Link]-2017 Antalya / TURKEY

(c) (d)

Figure 7. Apatite recovery as function of the depressant dosage at pH (a) 9.5, (b) 10, (c) 10.5, and (d) 11
CONCLUSIONS
The characterization of sorghum starch and constituents regarding the contents of amylose and protein
showed that the tested sample showed similar results compared with cornstarch data from literature. As
expected, the protein content of sorghum flour was 219% higher when compared with the sorghum starch.
This result is due the fact that the sorghum grain was integrally present in the flour and only comminution
stages were performed in order to produce it. Lipids content was higher in sorghum flour than suggested
in literature for use in the flotation process, since the oil on it could affect the froth inhibiting the flotation
itself. However, the microflotation tests performed with Hallimond tube no such interference was
observed. Even more, the visual aspect of the froth was no different between the froth formed when using
the three depressants. This result endorse et al. (2004) hypothesis regarding flotation using
fatty acids as collector and their frother capability.
The lower recovery of apatite in the flotation tests with sorghum starch were observed for a dosage of
onditions using

sorghum starch. When comparing with cornstarch at the same conditions sorghum flour produced an
apatite recovery 91% lower.
The results indicate that sorghum, no matter if milled as a flour or purified as a starch, can be used in
apatite flotation as a depressant and its depressant action is similar, or higher, than observed for cornstarch.
Since sorghum price is lower than corn, the flotation results can be seen not only technically but also
economically important.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the financial support of the Brazilian agencies CNPq, CAPES,
FAPEG e FUNAPE. In addition, we would like to thank the Copebras, Labmic, UNIFESSPA, UFOP,
UFG, and TUC.

REFERENCES
AACC - Approved methods of the American Association of Cereal Chemistry, 1995. 61-03.01 Amylose
content of milled rice, 4 p.
AACC - Approved methods of the American Association of Cereal Chemistry, 1997. 08-21.01 Prediction
of ash content in wheat flour - near-infrared method, 4 p.

419
[Link]-2017 Antalya / TURKEY

Bertolini, A. C., 2010. Starches: Characterization, Properties and Applications, Taylor & Francis Group,
Boca Raton, 290p.
Biduski, B., Silva, F. T., Silva, W. M., Halal, S. L., Pinto, V. Z., Dias, A. R., Zavareze, E. DA R., 2017.
Impact of acid and oxidative modifications, single or dual, of sorghum starch on biodegradable films,
Food Chemistry, v. 214, pp.53-60.
Bligh, E. G., Dyer, W. J., 1959. A rapid method of total lipid extraction and purification, Canadian Journal
of Biochemistry and Physiology, v. 37, n. 8, pp.911-917.
Bradford, M. M., 1976. A rapid and sensitive method for the quantitation of microgram quantities of
protein utilizing the principle of protein-dye binding, Analytical Biochemistry, n. 72, pp.248-254.
Dhital, S., Shrestha, A. K., Hasjim, J., Gidley, M. J., 2011. Physicochemical and structural properties of
maize and potato starches as a function of granule size, Journal of Agricultural and Food Chemistry,
v. 59, n. 18, pp.10151-10161.
Elkhalifa, A. E. O., Schiffler, B., Bernhardt, R., 2004. Selected physicochemical properties of starch
isolated from fermented sorghum flour, Starch, v. 56, n. 12, pp.582-585.
Fillipov, L. O., Severov, V. V., Fillippova, I. V., 2013. Mechanism of starch adsorption on Fe-Mg-Al-
bearing amphiboles, International Journal of Mineral Processing, v. 123, pp.120-128.
Fillipov, L. O., Severov, V. V., Fillippova, I. V., 2014. An overview of the beneficiation of iron ores via
reverse cationic flotation, International Journal of Mineral Processing, v. 127, pp.62-69.

Minerals Engineering, v. 18, n. 2, pp. 199-204.

raujo, A. C., Peres, A. E. C., 2006. Column Flotation: a key to the production of
apatite concentrates from slimes, In: Beneficiation of phosphates Technology and Sustainability, 1st ed.,
Society of Mining, Metallurgy, and Exploration Inc., Littleton, v. 1, pp.135-143.

phenomenon in microflotation, In: 2nd International Symposium on Sustainable Mineral Processing,

Antalya, Turkey, pp.186-192.
Ibrahim, S. S., Abdel-Khalek, N. A., 1992. The action of different types of corn starchcornstarch on the
flocculation of phosphate slimes, Minerals Engineering, v. 5, n. 8, pp.907-916.
Kar, B., Sahoo, H., Rath, S. S., Das, B., 2013. Investigations on different starches as depressants for iron
ore flotation, Minerals Engineering, v. 49, pp.1-6.
Liu, Q., Laskowski, J. S., 1989. The role of metal hydroxides at mineral surfaces in dextrin adsorption, I.
Studies on modified quartz samples, International Journal of Mineral Processing, v. 26, n. 3-4, pp.297-
316
Liu, Q., Zhang, Y., Laskowski, J. S., 2000. The adsorption of polysaccharides onto mineral surfaces: an
acid/base interaction, International Journal of Mineral Processing, v. 60, n. 3-4, pp.229-245.
Moore, G.R.P., Canto, L. R. Do, Amante, E. R., Soldi, V., 2005. Cassava and corn starch in maltodextrin
production, , v. 28, n. 4, pp.596-600.
Naguleswaran, S., Li, J., Vasanthan, T., Bressler, D., Hoover, R., 2012. Amylolysis of large and small
granules of native tritica -amylase and glucoamylase,
Carbohydrate Polymers, v. 88, n. 3, pp.864-874.
Nunes, A. P. L, Peres, A. E. C., 2011. , CETEM, Rio
de Janeiro, 47 p.
Oliveira, M. S., 2007. -carbonatado: estudo fundamental, UFMG, Belo Horizonte,
207 p.
Peres, A. E. C., Correa, M. I., 1996. Depression of iron oxides with corn starches, Minerals Engineering,
v. 9, n. 12, pp.1227-123.
., PerES, A. E. C., 1992. The effect of starch, amylose and amylopectin on
the depression of oxi-minerals, Minerals Engineering, v. 5, n. 3-5, pp.469-478.

420
[Link]-2017 Antalya / TURKEY

Rocha, T. S., Demiate, I. M., Franco, C. M. L., 2008. Structural and physicochemical characteristics of
-
628.
Rupollo, G., Vanier, N. L., Zavareze, E. R., Oliveira, M., Pereira, J. M., Paraginski, R. T., Dias, A. R. G.,
Elias, M. C., 2011. Pasting, morphological, thermal and crystallinity properties of starch isolated from
beans stored under different atmospheric conditions, Carbohydrate Polymers, v. 86, n. 3, pp.1403-
1409.
Wang, Y.J., White, P., Pollak, L., Jane, J., 1993. Characterization of starch structures of 17 maize
endosperm mutant genotypes with Oh43 inbred line background, Cereal Chemistry, v. 70, n. 2, pp.171-
179.

421