Advanced Powder Technol., Vol. 15, No. 4, pp.

421 – 433 (2004)

© VSP and Society of Powder Technology, Japan 2004.
Also available online - www.vsppub.com

Original paper

Flotation of low-grade phosphate ore

F. HERNÁINZ ∗ , M. CALERO and G. BLÁZQUEZ

Departamento de Ingeniería Química, Facultad de Ciencias, Universidad de Granada,
18071 Granada, Spain

Received 22 July 2003; accepted 26 September 2003

Abstract—A study has been conducted on the flotation concentration of sedimentary phosphorite
from Sierra Espuña, in the province of Murcia (Spain), using a Denver D-12 mechanical subaeration
cell. First, the mineral was pretreated through grinding, sorting and discarding slimes. The effect on
flotation of pH, collector concentration, particle size and flotation time was then analyzed. The results
achieved show that a neutral or slightly alkaline pH and short flotation times promote the concentration
of sedimentary phosphorite.

Keywords: Flotation; phosphate ore; oleic acid; particle size; mechanical cell.

1. INTRODUCTION

Phosphate materials (phosphates) occur naturally both in water (rivers, lakes, seas)
and, in higher concentrations, in soil. Its use as a raw material in the fertilizer
industry (superphosphates) is the application of greatest interest for soil-borne
phosphate materials.
Phosphates can be grouped, according to types, in three major groups [1]:
• Marine sedimentary phosphorites. These are the most important in both amount
and volume. Their P2 O5 content may be over 30%.
• Pluton phosphorites. The apatite in these minerals comes from igneous–alkaline
complexes. These are higher in number, but poorer and smaller than marine
sedimentary phosphorites.
• Guano phosphorites. These are a result of reactions between marine bird and bat
excrements with limestone rocks, giving rise to calcium phosphate.
Phosphorus concentrations in phosphates can be expressed as their P2 O5 content,
although Ca3 (PO4 )2 content (BPL) can also be used. The equivalence between the

∗ To whom correspondence should be addressed. E-mail: hernainz@ugr.es

422 F. Hernáinz et al.

two is: 1% P2 O5 = 2.185% Ca3 (PO4 )2 . Currently, around 80% extraction rates
are being achieved for sedimentary phosphates, 18% for igneous types and 2% for
guano phosphates.
Studying the mineralogy of sedminary phosphates poses considerable difficulties
as these substances are rarely crystallized and also contain amorphous phosphates
mixed with calcareous impurities. Its structural formula is generally accepted as
being [2]: Ca10 [(PO4 )6−x (CO3 F)x ]F− 2+
2 , although part of the calcium (Ca ) may be
replaced by sodium (Na+ ) and magnesium (Mg2+ ), while part of the fluor (F− ) may
be replaced by OH− . The effects of weathering, metamorphism and geological time
may also give rise to systematic changes in the composition of the phosphorites.
The industrial requirements for superphosphates demands a P2 O5 content in the
phosphoric ore close to or above 30% (approximately 60% in BPL) so as to lower
sulfuric acid consumption [2]. The presence of free carbonates in phosphoric rock
leads to considerably higher sulfuric acid requirements in wet treatment of this raw
material, for obtaining both superphosphates and phosphoric acid. Apart from its
role as an air pollutant, the CO2 produced by the acid attack causes foaming that
gives rise to the formation of small gypsum crystals that reduce the quality of the
final phosphoric acid [3].
In the light of the above, low-grade phosphorites (P2 O5 below 20–25%) must
be concentrated prior to their industrial enrichment. The techniques generally
applied for this purpose are: calcination, when the ore has low or average
carbonate content, and flotation, when the ore has a high carbonate content and
siliceous gangue. Both techniques have been studied in depth over the last few
decades [4– 10].
Calcination methods, however, do not generally give optimum results when the
concentrated mineral is intended as the basis for superphosphate production, as
the nodules formed during calcination may hinder acid attack (Avila Roson, pers.
commun.).
Recently, Sadeddin and Abu-Eishad [11], and Abu-Eishad et al. [12] proposed
diluted solutions of acetic acid as a solubilizing agent for the carbonates in the acid
leaching of the ore. For the time being, the procedure is restricted to laboratory
experientation with poor prospects for industrial-scale implementation due to the
costs of the reagents involved.
From the above, it is clear that flotation is the most widely used treatment for the
concentration of low-grade phosphorites, although there are numerous variations
in techniques given the enormous variations in mineral composition from different
deposits, especially with regard to carbonated and siliceous ores. It is this kind of
ore that usually guides the use of flotation reagents and of one or more flotation
stages, as well as setting operational parameters [2].
The P2 O5 content of the sedimentary phosphorite of Sierra Espuña is about 5%
and is considered a low-grade ore. The concentration the low-grade phosphate
by flotation is complicated because the fattyacid collectors used to float phosphate
minerals also float carbonate minerals [13]. In recent years, several useful processes
 Flotation of low-grade phosphate ore 423

have been proposed for the concentration of low-grade phosphate ores by froth
flotation using both anionic- and cationic-type collectors [14].
In this paper, the flotation of sedimentary phosphorite from Sierra Espuña in the
province of Murcia (Spain) in a semi-industrial subaeration cell (Denver D-12)
was studied to analyze the effect of the operational parameters which have the
greatest influence on the concentration of the phosphate fraction in the mineral.
The collector used in this study is oleic acid (anionic type).

2. MATERIALS AND METHOD

2.1. Mineral

Sedimentary phosphorites from a deposit located in the north of Sierra Espuña

(province of Murcia), in the area known as Prado Mayor on the left slope of the
Malvariche ravine [15], were used for this study.
Following extraction of the mineral from the deposit in 10 × 10 cm cores taken
along a stretch of 10 m, the mineral was mixed in the laboratory to achieve
homogenization so as to obtain a reliable, representative sample of the deposit.
The mineral was then ground in a three-floating hammer Culatti micromill and
sorted according to grain size in a high-vibration machine equipped with a set of
fine ASTM sieves, with the selection of appropriate sizes. Table 1 provides the
equivalents for the sieves used during the study together with mineral size.

Table 1.

Sieve ASTM Mineral size

(mesh) (μm)
20 840
30 590
40 420
50 297
60 250
70 210
80 177
100 149
120 125
140 105
160 88
200 74
270 53
325 44
400 37
450 30
500 25
424 F. Hernáinz et al.

2.2. Flotation agents

The chemicals used for this study were as follows:

• Collector. Chemically pure oleic acid supplied by Carlo Erba. This agent was
diluted in distilled water just prior to the experiments to avoid any possible time-
induced alterations.
• pH-modifying agents. Merck sodium hydroxide and Probus hydrochloric acid.
Both were used at 4 N concentration to easily achieve the desired pH; pH was
controlled by Crison 2001 pH meter.

2.3. Experimental method and conditions

A Denver-type free-flow mechanical subaeration cell, model D-12 was used as the
flotation cell, as described in detail in [16].
The pre-prepared mineral was added to the 1.25-l flotation cell. The solution of
surfactants was then added at the desired pH and the mixture was shaken for 5 min,
i.e. sufficient conditioning time to ensure that the mineral was completely covered
by the collector. Shaking was performed by the Denver cell itself at 1000 r.p.m.
with the air valve closed. Flotation commenced upon completion of conditioning
time. The foams collected during flotation time were vacuum-filtered, heat stove
dried to a constant weight for later analysis.

2.4. Analytical method

2.4.1. P2 O5 analysis. The official method for analysis described in Annex II of

the Order dated 30 November 1976 (published in the Spanish Official Gazette on 30
January 1977) was used to determine the floated mineral concentration, expressed
in % P2 O5total .
The technique comprises a sulfonitric attack on the phosphoric acid to solublize
the phosphoric acid and precipitate the molybdenic acid and quinolein, and col-
lection and weighing of the yellow quinolein phosphomolybdate precipitate, from
which P2 O5 content can be deduced.

2.4.2. CaCO3 analysis. Calcium analysis was performed by atomic absorption

spectrophotometry, using a Perkin-Elmer model 3100. The sample solution was
prepared by alkaline fusion with lithium metaborate. A multi-element hollow
cathode lamp supplied by Perkin-Elmer was used for measurement, together with
an air-acetylene flame as required for these elements.

2.4.3. SiO2 analysis. The analysis of silicon (expressed as SiO2 ) was performed
by visible region absorption spectrophotometry using a Spectronic model 2000.
 Flotation of low-grade phosphate ore 425

3. RESULTS AND DISCUSSION

3.1. Mineral pre-treatment

Through previous tests, P2 O5 content in the mineral to be floated was proven to
depend, to a considerable extent, on mineral size. This fact has already been
addressed by Hegner and Pacl [17] when they observed that the P2 O5 content in
certain sedimentary phosphates ranged from 30 and 26% for coarse (>0.16 mm)
and fine (<0.1 mm) fractions.
In this paper, the treatment was as follows. The mineral, sampled by surface
cores from the deposit, was quartered successively to obtain a weight of 2 kg;
then sorted according to grain size in a digital electromagnetic sieve. Only grain
sizes between 20 and 60 ASTM mesh were selected as these hold the highest P2 O5
content (6–10%) and represent 40.39% of the original mineral.
Afterwards, the mineral was ground and sorted, selecting only grain sizes between
20 and 50 ASTM mesh. These were then subjected to a second grinding and were
sieved so that the original mineral’s P2 O5 content amounted to approximately 10%
in a wide range of sizes (from 60 to <200 ASTM mesh) which, in some cases, may
even increase P2 O5 content 4-fold.
It is also well established [18– 20] that the presence of ultrafine particles, known
as slimes, has a very detrimental effect on the flotation of solids, as they contaminate
foams, raise the consumption of flotation reagents, reduce the speed of the process
and cause an anarchic response in mineral separation using this technique.
For this reason, the mineral was treated to discard slimes by lavage, i.e. the ground
mineral is washed with water over a 450 ASTM mesh sieve and then the rejects are
sieved, selecting only sizes under 100 ASTM mesh. To verify the soundness of
this procedure, laser grain size analysis was performed on the particles prior to and
following discarding slimes; the results are shown in Fig. 1. As can be seen, the
presence of extremely fine particles (slimes) is considerably higher in unwashed
mineral. Furthermore, the particles below 12–14 μm are only found in unwashed
mineral.

3.2. Mineral flotation

3.2.1. Influence of pH. The effect of pH on the flotation of sedimentary phos-
phates was analyzed using oleic acid at a concentration of 1000 g/t as the collector,
with washed mineral with a particle size below 100 ASTM mesh, 5 min condition-
ing time, modified pH between 7 and 11. The results obtained are shown in Fig. 2.
The flotation recovery for the mineral is greater with a neutral or moderately
alkaline pH; recovery is severely reduced in clearly alkaline flotation baths. Hence,
at pH 8 over 50% of the mineral is recovered, while at pH 11 recovery drops to
approximately 30%.
Singh et al. [8], Hanumantha Rao et al. [21], Gong et al. [22] and Espinosa [23]
found similar results when working with different phosphate minerals.
426 F. Hernáinz et al.

Figure 1. Laser grain size analysis of the washed and unwashed particles.

As for P2 O5 , CaCO3 and SiO2 contents both in concentrate and tailing, results
show that CaCO3 generally appears in the concentrate, while P2 O5 is concentrated
in the tailing. This gives rise to CaCO3 contents between 62 and 78% in concentrate,
while tailing content amounts to between 24 and 36%. P2 O5 content is about
2–3% in the concentrate and about 6.5–8% in the tailing. There is little change
in silica content in concentrate and tailing, with content ranging from around 7% in
concentrate to slightly above 8% in the tailing.
Bearing in mind that the composition of the original mineral for this series of
experiments was P2 O5 5.56%, CaCO3 51.11% and SiO2 7.42%, it can be deduced
that flotation of the mineral leads to a significant concentration in calcite (CaCO3 )
in the floated foams (in some cases, with an increase of over 25%), while the
most valuable mineral is concentrated in the tailing, i.e. P2 O5 , with an 8% rise
in proportion. As the aim is to raise the P2 O5 content, the operation performed is a
reverse flotation given that the most valuable fraction is found in the tailing. This is
a frequently used operation in the mining industry [18].
The distribution of P2 O5 and CaCO3 , in percentage terms, in both the concentrate
and tailing has been calculated taking into account the recovery rates for total
mineral, P2 O5 and CaCO3 in the concentrate and tailing as well as content of both
in the original mineral. The results are shown in Fig. 3. The distribution of SiO2
in the ccentrate and tailing has not been provided given that SiO2 content in both
fractions is similar (7–8%), as mentioned above.
The results shown in Fig. 3 also include the percentage of the content for each
component. Bearing in mind both distribution and content, 75% of total P2 O5
remains in the tailing at pH 7 with a concentration of 7.82% and 85% at pH 10 with a
concentration of 7.28%. Concentration drops to 6.64% only at pH 11, although over
85% of the original mineral present is recovered. The P2 O5 content in concentrate is
 Flotation of low-grade phosphate ore 427

similar in all cases (ranging between 2 and 3%), and its distribution varies between
15 and 30% in the pH range studied.
The best results for CaCO3 are obtained in the concentrate; in the pH range
between 7 and 10, around 60% is recovered with concentrations ranging between
62 and 78%.
From these results, it is clear that separation of P2 O5 and CaCO3 through floation
is best performed in flotation baths with a neutral or slightly alkaline pH. As the
Sierra Espuña phosphates have the characteristic of yielding a natural pH of between
7 and 8 in the flotation bath, it was decided that the study would maintain this pH.
This has enormous advantages for industrial applications as no reagents are required
to modify pH and the possible surface attack of the mineral due to the presence of
such reagents is also avoided.

3.2.2. Influence of oleic acid concentration. To study the effect on mineral

recovery percentages of modifications in collector concentrations, a mineral size
below 100 ASTM mesh and a flotation bath with the mineral’s natural pH were
selected. Figure 4 shows the recovery percentage of the mineral according to
oleic acid concentrations ranging between 250 and 2500 g/t. As the collector
concentration rises, mineral recovery also increases, very rapidly initially (250–
1000 g/t) up to values of 60% at oleic acid concentrations above 1500 g/t. There is
no further improvement in mineral flotation above this range.
These results resemble those found by González Mantero [24] in a Hallimond
tube using the same mineral, although with the Denver D-12 cell the recovery
percentages are considerably higher. These results also agree with those reported
by most researchers showing enhanced operations with an increase in collector
concentration.
Figure 5 provides the distribution of P2 O5 and CaCO3 between the concentrate
and tailing, together with their content. As oleic acid is increased, there is a trend
towards an even distribution between the concentrate and tailing for P2 O5 , although
concentration is much higher in the tailing. A similar effect occurs for CaCO3 ,
although concentration in the concentrate remains much higher than in the tailing.
Given that the distribution of P2 O5 and CaCO3 in concentrate and tailing is the
reverse of their separation through flotation, the best results are achieved at oleic
acid concentrations close to 1000 g/t as this yields CaCO3 concentrations above
75% in the concentrate, with a distribution of over 80%, while P2 O5 is mostly found
in the tailing (at around 70%) with concentrations above 7%.
It can also be seen from Fig. 5 that very high collector concentrations, although
they improve mineral flotation in all cases, are not appropriate for separating the
different species present, as they all improve their flotation, which agrees with
reports by other authors [25].

3.2.3. Influence of particle size. Although in the preceding experiments the

mineral size selected (i.e. <100 ASTM mesh) is considered to be the most
428 F. Hernáinz et al.

Figure 2. Flotation recovery of mineral versus Figure 3. Distribution of P2 O5 and CaCO3 , in

pH with 1000 g/t oleic acid and particle size percentage terms, in both the concentrate and
< 100 mesh. tailing versus pH with 1000 g/t oleic acid and
particle size < 100 mesh.

Figure 4. Flotation recovery of mineral versus Figure 5. Distribution of P2 O5 and CaCO3 ,

oleic acid concentration at particle size < 100 in percentage terms, in both the concentrate
mesh. and tailing versus oleic acid concentration at
particle size < 100 mesh.
 Flotation of low-grade phosphate ore 429

appropriate for flotation [18], a series of further experiments was also conducted
with the <100 mesh size subdivided into four fractions, i.e. 100/160, 160/200,
200/270 and <270 ASTM mesh, so as to determine which fraction provides the best
results. An oleic acid concentration of 1000 g/t was selected for these experiments.
The results obtained are shown in Fig. 6, where mineral recovery is seen to
improve at lower mineral sizes, down to a given size below which the recovery
decreases. Accordingly, 200/270 mesh is the optimum size, giving recoveries
approaching 65%, while 100/160 size only yields recoveries of nearly 50%.
The results reported by González Mantero [24] in a Hallimond tube coincide
entirely with regard to the most appropriate particle size and recovery percentages,
which confirms that, in spite of its limitations, the Hallimond tube can estimate the
influence of some of the parameters affecting mineral flotation quickly using only a
small amount of mineral.
The fact that this study also showed that, below a given solid particle size, there
was no improvement in flotation basically agrees with Trahar’s findings [26] with
sulfide minerals, with Lay and Bell [27] using saline minerals, with Bustamante and
Warren [28] in carbon flotation, and with Hernáinz and Calero [29] in celestite ore.
Figure 7 shows distribution rates between the concentrate and tailing for both
P2 O5 and CaCO3 contents, respectively. The largest particle size of all used for P2 O5
(100/160 mesh) provides the best distribution in the tailing, with recovery rates of
almost 75% with a concentration of 8.67%. As size decreases, however, there is not
only a decrease in mineral presence in the tailing, but content also decreases down
to 6.41% for sizes below 270 mesh.
These results are absolutely consistent, as mentioned earlier, with the fact that
the grinding of the mineral concentrates the phosphate fraction in the larger size
particles. Thus, together with the fact the P2 O5 concentrates predominantly in the
tailing, the 100/160 mesh size yields the best results in the range of particle sizes
used.
For CaCO3 however, the best results are achieved at particle sizes of 160/200
and 200/270 mesh. The concentration of calcite is very similar, however, for most
particle sizes and is only slightly lower for particle sizes below 270 ASTM mesh.
From the above, it is clear that foams will concentrate CaCO3 predominantly if
the mineral is ground to particles sizes of 100–270 mesh, while P2 O5 will mainly
appear in the flotation cell residue.

3.2.4. Influence of flotation time. Two oleic acid concentrations, i.e. 1000 and
2000 g/t, together with four particle sizes, i.e. 160/200, 200/230, 230/270 and
270/325 ASTM mesh, were selected to analyze the influence of flotation time
(tF ); flotation time was set at 1–10 min. Figure 8 shows the results obtained with
1000 g/t oleic acid, plotting the accumulated recovery percentage against flotation
time for each particle size tested. As flotation time increases, the accumulated
recovery percentage is also seen to rise, with the most marked effect occurring with
430 F. Hernáinz et al.

Figure 6. Flotation recovery of mineral versus Figure 7. Distribution of P2 O5 and CaCO3 , in

particle size with 1000 g/t oleic acid. percentage terms, in both the concentrate and
tailing versus particle size with 1000 g/t oleic
acid.

Figure 8. Flotation recovery of mineral versus Figure 9. Flotation recovery of mineral versus
flotation time at four particle sizes with 1000 g/t flotation time at four particle sizes with 2000 g/t
oleic acid. oleic acid.
 Flotation of low-grade phosphate ore 431

Table 2.
[Oleic acid] = 1000 g/t

tF Size (ASTM)
(min) 160/200 200/230 [content (%)] 230/270 [content (%)] 270/325 [content (%)]
P2 O5 CaCO3 SiO2 P2 O5 CaCO3 SiO2 P2 O5 CaCO3 SiO2 P2 O5 CaCO3 SiO2
1.0 4.36 68.26 12.84 4.71 72.85 9.65 4.67 67.22 9.58 4.73 72.99 7.99
1.5 4.19 78.15 11.89 6.45 71.70 9.65 5.44 71.52 8.36 5.77 70.48 7.61
2.0 3.88 73.35 11.40 7.22 58.34 8.97 6.16 65.46 9.56 6.86 57.51 8.39
2.5 3.74 72.86 12.01 8.90 46.09 9.31 6.45 53.67 9.36 7.41 49.69 7.79
3.0 3.95 68.51 12.00 8.97 37.07 9.16 6.49 52.06 7.26 7.76 45.67 8.65
4.0 4.80 71.85 13.97 9.25 34.91 8.32 7.06 44.41 6.90 7.68 40.92 7.14
6.0 5.21 68.93 13.87 9.57 33.43 9.14 7.54 43.50 7.86 7.60 38.36 8.66
10.0 5.75 65.80 13.80 9.53 30.48 7.86 7.89 37.55 7.26 7.58 36.18 8.55
Tailing 10.11 33.29 11.08 11.65 16.38 8.12 10.41 15.54 8.31 10.16 22.94 7.54

decreasing mineral particle size. At 10 min, recovery rates of 25, 53, 55 and 59%
are achieved for the four sizes tested.
As expected, when oleic acid concentration is increased to 2000 g/t (Fig. 9), the
results are slightly higher than those obtained at 1000 g/t, but follow the same
pattern with regard to variation with particle size as stated above.
From the standpoint of P2 O5 , CaCO3 and SiO2 content, the results for 1000 g/t
(Table 2) clearly show that calcite is the species that floats best given that the
concentration found in the concentrate is always higher than in the tailing, and for
particle sizes between 160 and 200 mesh, concentrate remain at 65–78% compared
with only 33.29% in the tailing. P2 O5 content in the various concentrates ranges
between 3.74 and 5.75, while in the tailing it is 10.11%; SiO2 content, although
this does not alter to any considerable degree, is slightly higher in the concentrate
(11.40–13.97 compared with 11.08%).
For 200/230 mesh and lower particle sizes, SiO2 content remains within a similar
range as described above. However, CaCO3 content in the various concentrates and
the tailing are highly indicative of how the process occurs, i.e. during the first stage
of flotation (1 min) calcite content in the concentrate is much higher, up to over
72% in some cases, while at 10 min flotation times, the content of the same mineral
drops to below 31%.
P2 O5 content, although on a lesser scale with variations between 4 and 10%, is
low during the first stages of flotation and rises towards the end. The content in
the tailing is always around 10%. Similar results are achieved when oleic acid
concentrations are raised to a 2000 g/t.

4. CONCLUSIONS
The results obtained confirm that for particle sizes of 200/230 mesh and under, the
carbonate separates during the first moments of flotation (1.5 min) and can reach up
432 F. Hernáinz et al.

to 80% content, while these content levels drop towards the end of flotation (10 min)
down to around 31% at the least. The opposite occurs with P2 O5 , at the beginning
of the operation — content percentages are low (4–6%), and then rise during the
operation for 200/230 mesh and under to reach 8–9% at the end of flotation.
The above seems to suggest that very short flotation times (less than 2 min) should
be used when separating CaCO3 and P2 O5 through flotation, given that it is in this
time range that the greatest differences are achieved.

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