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Review of the Main Factors Affecting the Flotation of Phosphate Ores

Article  in  Minerals · December 2020

DOI: 10.3390/min10121109

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Review
Review of the Main Factors Affecting the Flotation
of Phosphate Ores
Manar Derhy 1, Yassine Taha 1,*, Rachid Hakkou 1,2 and Mostafa Benzaazoua 1,3
1 Mining Environment and Circular Economy (EMEC), Mohammed VI Polytechnic University,
Lot 660. Hay Moulay Rachid, Ben Guerir 43150, Morocco; [email protected] (M.D.);
[email protected] (R.H.); [email protected] (M.B.)
2 IMED-Lab, Faculty of Science and Technology, Cadi Ayyad University (UCA). BP 549,

Marrakech 40000, Morocco

3 Institut de Recherche en Mines et en Environnement, Université du Québec en Abitibi-Témiscamingue,

445 Boulevard de l’Université, Rouyn-Noranda, QC J9X5E4, Canada

* Correspondence: [email protected]

Received: 10 November 2020; Accepted: 7 December 2020; Published: 10 December 2020

Abstract: The way to successfully upgrade a phosphate ore is based on the full understanding of its
mineralogy, minerals surface properties, minerals distribution and liberation. The conception of a
treatment process consists of choosing the proper operations with an adequate succession
depending on the ore properties. Usually, froth flotation takes place in phosphate enrichment
processes, since it is cheap, convenient, and well developed. Nevertheless, it is a complex technique
as it depends on the mineral’s superficial properties in aqueous solutions. Aspects such as
wettability, surface charge, zeta potential, and the solubility of minerals play a basic role in defining
the flotation conditions. These aspects range from the reagents type and dosage to the pH of the
pulp. Other variables namely particles size, froth stability, and bubbles size play critical roles during
the treatment, as well. The overall aim is to control the selectivity and recovery of the process. The
following review is an attempt to add to previous works gathering phosphate froth flotation data.
In that sense, the relevant parameters of phosphate ores flotation are discussed while focusing on
apatite, calcite, dolomite, and quartz as main constituent minerals.

Keywords: sedimentary phosphate ore; igneous phosphate ore; mineral processing; froth flotation;
surface charge; wettability; apatite; dolomite; calcite; quartz

1. Introduction
Phosphate ores are the only pronounced source of phosphorus. As a crucial component with
high economic importance, phosphorus remains indispensable in the phosphoric acid industry,
fertilizers, and elemental phosphorus production. The demand on phosphate has increased
throughout the years. A total of 47 million tons P2O5 were consumed worldwide in 2019. This
consumption is predicted to increase up to 50 million tons in 2023 [1]. As presented in Table 1, the
worldwide leaders of phosphate mine production are China (110 million tons/y), Morocco (36 million
tons), United States (23 million tons/y), and Russia (14 million tons/y). Countries such as Jordan,
Saudi Arabia, Vietnam, Brazil, Egypt, Australia, and Senegal produce between 1 and 8 million tons/y.
Phosphate mine production is expected to grow, especially in Jordan, Morocco, Saudi Arabia, and
Senegal following projects expansions [1].
Conventionally, phosphate deposits are classified into five major categories: Marine
sedimentary, igneous, metamorphic, weathering sedimentary, and biogenic [2]. Sedimentary
deposits are predominant, providing 80% of the world’s phosphate production. These deposit’s
grades range typically between 10% and 30% P2O5 and can be upgraded to (30–35%) P2O5. Morocco,

Minerals 2020, 10, 1109; doi:10.3390/min10121109 www.mdpi.com/journal/minerals

Minerals 2020, 10, 1109 2 of 22

China, Middle East, and United States host the biggest sedimentary deposits. Igneous deposits occur
in Russia, Brazil, South Africa, Canada, and Finland with grades ranging between 4% and 15% P2O5
and can be upgraded to (35–40%) P2O5 [3,4]. Phosphate ores can also be classified based on their major
gangue minerals as: (i) Siliceous ores if associated with silica, (ii) clayey ores if containing aluminum
silicates, (iii) calcareous ores of sedimentary origin if containing carbonates as the major impurities,
(iv) phosphate ores rich in organic matter, (v) phosphate ores with multiple gangue minerals, and
finally, (vi) igneous and metamorphic phosphate ores if containing sulfides, magnetite, carbonates,
nepheline, etc.
According to their genesis and based on the phosphate cycle, phosphate minerals can be
grouped as primary or secondary minerals. The primary minerals represent the original and
replenishing source of phosphorus. They occur in carbonatite and alkaline igneous rocks. Altered or
disintegrated and decomposed by natural agents, the primary minerals are transformed into
secondary phosphate minerals [5]. Hence, the igneous phosphate ores can hold a variety of phosphate
minerals, which are seldom found in the sedimentary ores and vice-versa. Furthermore, there are
more than 200 known phosphate minerals. The apatite group is the most abundant (95% of the
phosphorus existing in the earth’s crust). Examples of phosphate minerals are listed in Table 2. The
impurities existing in sedimentary ores are likely to differ from the ones found in igneous deposits.
Upgrading a phosphate ore of any type (e.g., sedimentary, igneous, etc.) consists of increasing
its P2O5 content and eliminating the gangue minerals (it must contain over 30% P2O5, with a CaO/P2O5
ratio lower than 1.6%, SiO2 content less than 3%, MgO content less than 1%, Fe2O3 content less than
7% [6,7]). The occurrence of impurities in the phosphate concentrate causes several complications
and a frailty for phosphoric acid production, as presented in Table 3. Phosphate ore refinement is
achieved by beneficiation processes, which depend on the characteristics of the treated ore (e.g.,
gangue minerals, particles size, hardness, etc.). Comminution and size separation, mineral
separation, chemical and thermal techniques are the most common [2,8].
Froth flotation is a mineral separation technique used industrially since the late 19th century.
Starting in 1940s, it has been included in phosphate ores enrichment processes. Froth flotation is
based on the specific physicochemical properties of minerals surfaces, precisely the hydrophobicity
and hydrophilicity of both valuable and unwanted gangue minerals. Hydrophobicity can be a natural
characteristic, but for most minerals, including phosphate minerals, the intervention of specific
reagents is required to control the flotation behavior and achieve satisfactory separation results [9].
Phosphate flotation was initially conducted using soap, then it evolved throughout the years with
the development of reagents and the improvement of process parameters. Flotation is dynamic, it is
based on the interaction of multiple scientific fundamentals such as surface and colloid chemistry,
physics, crystallography, etc. [10]. The performance of a flotation system is vulnerable to a range of
variables. These variables are gathered into three categories: (i) Operational, e.g., mineralogy/surface
properties, feed rate, particle size, pulp density, temperature, etc. (ii) chemical, e.g., collectors,
frothers, activators, depressants, pH regulators, and (iii) hydrodynamic, e.g., flotation cell design,
agitation, air flow, etc. Phosphate flotation can be direct, reverse, or a succession of direct/reverse
stages depending on circumstances. Direct flotation consists of floating the phosphate minerals by
inducing hydrophobic surface properties. The opposite is the case during reverse flotation where
gangue minerals are floated. Choosing the type of flotation depends on: (i) The phosphate mineral’s
initial grade, (ii) the economics of the reagents used, and (iii) the performance of the adopted flotation.
Froth flotation has been used to enrich sedimentary phosphate ores with siliceous impurities. It
has replaced calcination in treating calcareous phosphate ores. It is also commonly used for
processing igneous phosphate ores with usually less complications compared to sedimentary ores.
Yet, igneous phosphate ores still present complications, as a single ore might hold numerous
impurities and various types of phosphate minerals with different floatabilities [11]. Phosphate
sedimentary ores usually contain apatite as the value mineral, carbonates, silica, and clays as
impurities. The anionic–cationic flotation termed the “Crago technique” is the common method for
upgrading siliceous phosphate ores. This is used to upgrade Florida phosphate ores. In this process,
francolite is floated using a fatty acid/fuel oil mixture. The rougher concentrate is scrubbed using acid
Minerals 2020, 10, 1109 3 of 22

to renovate the particles surfaces. The remaining silica is then floated using an amine reagent [12].
For calcareous ores, separation by flotation of carbonates (calcite and dolomite) and phosphates is
challenging since the two mineral groups share similar surface chemical properties. There are also
colloidal phosphate ores, sedimentary ores containing, in general, a very small grain sized apatite
(cryptocrystal). The beneficiation of these ores is challenging. It requires fine grinding and the use of
selective reagents since apatite is incorporated with gangue minerals, forming “collophanite”.
With the depletion of rich phosphate deposits of simple compositions and the abundance of
complex poor phosphate reserves, research in phosphate froth flotation keeps evolving. At this stage,
efforts are directed toward understanding what affects phosphate flotation and the different aspects
that result in the success or the failure of a flotation operation. With these regards, the aim of this
review is to focus on the factors affecting the flotation of sedimentary phosphate ores, as they provide
80% of the world’s phosphate production.
Minerals 2020, 10, 1109 4 of 22

Table 1. Leading phosphate producers [13].

Reserves
Top Phosphate 2019 Production
Deposit Types Phosphate Minerals Gangue Minerals (Million
Mine Producers (Million Tons)
Tons)
Sedimentary (marine, weathered), Igneous Collophane, fluorapatite, francolite,
China Dolomite, quartz, clay, calcite, goethite, chlorite, zircon 110 3200
(carbonatite/alkalic), Metamorphic, Guano monazite
Morocco Marine sedimentary Apatite Quartz, dolomite, calcite, aluminum silicate minerals 36 50,000
Sedimentary (marine, weathered), Igneous
Francolite, monazite, wavellite, Quartz, dolomite, calcite, magnetite, aluminum silicate minerals, goethite,
United States (carbonatite/alkalic), Metamorphic 23 1000
crandallite ankerite
(metasedimentary), Guano
Fluorapatite, hydroxylapatite, Magnetite, ilmenite, titanium magnetite, baddeleyite, forsterite, calcite,
Russia Marine sedimentary, Igneous (carbonatite/alkalic) 14 600
francolite, monazite phlogopite, mica, titanium-augite, pyrite
Jordan Marine sedimentary N.A. N.A. 8 1000
Saudi Arabia Marine sedimentary N.A. N.A. 6.2 1400
Sedimentary (marine, weathered) Metamorphic
Vietnam Apatite N.A. 5.5 30
(metasedimentary), Guano
Fluorapatite, francolite, collophane,
Calcite, magnetite, quartz, aluminum silicate minerals, pyrite, ankerite,
Brazil Igneous (carbonatite/alkalic), Guano dahllite, monazite-(Ce), phoscorite, 5.3 1700
fluorite, barite, quartz, carbonate
metavariscite, strengite, variscite
Collophane, francolite, dahllite, Pyrite, quartz, calcite, dolomite, goethite, chlorite, zircon,
Egypt Marine sedimentary 5 1300
wavellite, manganapatite montmorillonite, gypsum, glauconite
Peru Marine sedimentary Fluorapatite Carbonates (calcite, dolomite), diatomite 3.7 210
Israel Marine sedimentary N.A. N.A. 3.5 62
Tunisia Marine sedimentary N.A. N.A. 3 100
Fluorapatite, collophane, monazite,
Sedimentary (Marine, weathered), Metamorphic
wavellite, dufrenite, millisite, Calcite, dolomite, quartz, hematite, goethite, quartz, Aluminum silicate
Australia (metasedimentary), Igneous (carbonatite/alkalic), 2.7 1200
churchite, xenotime, florencite, minerals
Guano
goyazite
Syria Sedimentary (marine, weathered) N.A. N.A. 2 1800
Calcite, magnetite, quartz, aluminium silicate minerals, pyrite, ankerite,
Fluorapatite, francolite, collophane,
fluorite, barite, quartz, carbonate, anatase, Au, Mn, aegirine, amphibole,
South Africa Igneous (carbonatite/alkalic), Marine sedimentary dahllite, monazite-(Ce), phoscorite, 1.9 1400
pyroxene, arfvedsonite, vermiculite, serpentine, carbonatite minerals
metavariscite, strengite, variscite
enriched in copper and iron
N.A.: Not available.
Minerals 2020, 10, 1109 5 of 22

Table 2. Abundant phosphate minerals and their occurrence.

Name Types Formula Occurrence

Chlorapatite Ca5(PO4)3 Cl Ig, Mt.
Hydroxylapatite Ca5(PO4)3 OH Ig, Mt, Sd.
Dahllite or Carbonate- Ca5(PO4,CO3)3
Sd, Mt.
Apatite hydroxylapatite (OH,O)
Fluorapatite Ca5(PO4)3 F Ig, Mt, Sd.
Francolite or Carbonate-
Ca5(PO4,CO3)3 (F,O) Sd, Mt.
fluorapatite
Monazite Monazite-(Ce) CePO4 Ig, Mt, Sd. (Phosphate minerals containing REE).
Xenotime Xenotime-(Y) YPO4 Ig, Mt. (Phosphate minerals containing REE).
Ig, Mt, Sd. Occurs in organically rich sedimentary deposits (clays and sandstones), hydrothermal
Vivianite Fe3(PO4)2 8(H2O)
replacement deposits, and in phosphate-rich granite pegmatites.
Variscite AlPO₄ 2(H₂O) Sd, Mt. Occurs as a secondary mineral in hydrothermal replacement deposits and brecciated sandstones.
Al3(PO4)2(OH,F)3 Sd, Mt. Occurs as a secondary mineral in the oxidized low-grade metamorphic rocks, epithermal veins,
Wavellite
5(H2O) and in phosphate-rich sedimentary deposits.
Ig, Sd. Occurs as coatings and cements in guano rocks and as coatings on phosphate minerals in granite
Monetite CaHPO4
pegmatite.
Whitlockite Ca9Mg (PO4)6(HPO4) Sd, Mt. Occurs in granite pegmatites; may be formed in caves from leached guano.
Brushite Ca(HPO4) 2H2O Sd. Occurs in cave guano deposits.
Struvite (NH4)Mg(PO4) 6H2O Sd. Occurs in guano deposits; peat beds; organically rich sediments.
Variscite Al(PO4) 2H2O Sd, Mt. Occurs in guano beds and metamorphosed sedimentary rocks.
Ig: Igneous rocks; Sd: Sedimentary rocks; Mt: Metamorphic rocks.
Minerals 2020, 10, 1109 6 of 22

Table 3. Potential effects of phosphate impurities and their acceptable levels.

Impurity Potential Sources Acceptable Level Desirable Properties Undesirable Properties
Low Al2O3 content improves the filtration rate by High Al2O3 content impairs filtration, increases acid
Aluminum silicate minerals, wavellite, metavariscite, crandallite,
Al2O3 Up to 3% [7,14] promoting the growth of gypsum crystals [15]. viscosity [14], decreases plant capacity, and P2O5
variscite.
Reduces corrosion caused by fluoride ion [14]. recovery [7].
High Fe2O3 content causes excessive sludge
Fe2O3 Goethite, magnetite, hematite, strengite. Up to 2% [14] Recoverable in case of excessive presence [14]. formation, decreases the filtration rate, and
influences the acid viscosity [14].
Increases the sulfuric acid consumption and impairs
MgO Dolomite, ankerite, phoscorite. Less than 1% [7] May have a nutrient value [14].
gypsum filtration [7].
Causes corrosion, mud, slurry formation, and might
Fluorine Fluorite, fluorapatite, francolite. Up to 4% [14] Can be recovered as a by-product [14].
impair gypsum filtration [15].
High SiO2 content causes wear and erosion of
Reactive silica forms with fluoride SiF4 and
SiO2 Quartz, Aluminum silicate minerals. Around 2% [7] equipment and can impair the filtration of gypsum
fluosilicates rather than the harmful H2SiF6 [7,14].
[7,15].
Less than 0.03%
Chlorine Chlorapatite. (stainless steel None. Increases equipment erosion [7].
equipment)
CaO:P2O5 ratio less Increases the consumption of sulfuric acid and causes
CaO Calcite, dolomite, ankerite, fluorite, gypsum, crandallite, apatite. Improves the reactivity of the phosphate ore [15].
than 1.6 [7] foam formation during the acid attack [15].
Up to 60 mg/kg P2O5 Does not pose notable problems in the production of
Carbonate apatite (Cd substitutes Ca and/or is trapped in the structure
Cadmium (European union) None. phosphoric acid [7]. Toxic in specific end products
during its formation by the sedimentation of phosphate rock) [16].
[17] (animal feed and fertilizers) [15].
Following the sedimentation of the phosphate ore, U might substitute Ca
Typically, 4 Bq U per
Uranium in the apatite crystal and/or is adsorbed into it or forms uranium Can be recovered as a by-product [14]. Hazardous to human health [7].
g P2 O5 .
phosphate minerals such as phosphuranylite [18].
Minerals 2020, 10, 1109 7 of 22

2. Parameters Affecting Phosphate Flotation

2.1. Phosphate and Gangue Minerals’ Surface Properties

Mineral surface properties are critical for flotation control as they represent the fundamental
concepts behind the technological process. They allow to, both, predict and describe the physical and
chemical superficial interactions of the mineral-reagent, mineral-medium, and mineral-mineral
interactions.

2.1.1. Phosphate Minerals’ Solubility and Surface Charge

The surface charge of phosphate minerals and their impurities (i.e., gangue minerals) is affected
by many variables, e.g., pH and RPO values (reduction/oxidation potential). Respectively, the
mechanisms governing the surface charge are complex rendering separation by froth flotation
challenging in some cases. Minerals from the apatite group are the most abundant. It has been
suggested that their active surface sites are formed by calcium hydroxyl (≡CaOH) and phosphorus
hydroxyl (≡POH) groups [19]. It is considered that ≡Ca─OH2+ and ≡P─O− are dominant surface
groups [19]. The ions H+ and OH− are specifically adsorbed on the surface. Basically, depending on
the pH, two different surface groups (both metal ions and ligands) can be adsorbed on the
hydroxylated apatite surface. Hence, the adsorption of the flotation modifying agents on mineral
surfaces is usually expressed in relation to pH being a critical parameter. The apatite’s surface charge
depends not only on pH but also on the concentration of various chemical species as well as on
pretreatments. In this context, hydrogen, hydroxyl, calcium, fluoride, and phosphate are the apatite’s
potential determining ions [20]:
 H+ and OH− ions are critical as they control the solution pH and eventually the mineral’s surface
charge [19];
 Phosphate (PO43–) decreases the mineral’s surface charge under all pH conditions [20];
 Calcium makes the mineral more positively charged under all pH conditions [20];
 Fluoride is found to increase the surface charge in acidic medium and slightly decreases it in
basic solutions following the possible formation of fluorite (CaF2) and fluorapatite (Ca5(PO4)3F),
respectively [20].
The zeta potential expresses the electrical potential difference between the ion layer adsorbed
onto the particle’s surface and the bulk solution [21]. It enables prediction as to whether or not a
reagent will bind to the particle’s surface. The isoelectric point (IEP) is the pH value corresponding
to a zero zeta potential. IEP values of hydroxyapatite, fluorapatite, francolite, and collophane in
different operating conditions are listed in Table 4. Parameters such as mineral purity, particles size,
solid content, electrolyte, and measurement technique influence the IEP value.

2.1.2. Gangue Minerals’ Solubility and Surface Charge

The most common impurities found in the sedimentary phosphate ores are carbonates (calcite
and dolomite) and quartz.
 Calcite solubility and surface charge
Calcite solubility in aqueous medium leads to the release or deposition of Ca2+ and CO32− on
mineral surfaces depending on the solution pH. This latter and concentrations of Ca2+, CO32−, and
HCO3 might fluctuate under the influence of dissolved atmospheric CO2. Moreover, the hydrated
calcite surface can have both protonated anion sites (>CO3H) and hydroxylated cation sites (>CaOH).
Hence, in a froth flotation system, the solution pH controls the calcite surface charge. Nevertheless,
it has been demonstrated experimentally that, when the calcium ions concentration was kept
constant, the calcite surface charge was independent of pH [22]. The adsorption of Ca2+ and CO32−
onto the mineral surface (Figure 1) is represented through the following surface complexation
Reactions (with or without the presence of CO2) [22].
Minerals 2020, 10, 1109 8 of 22

>CO3H + Ca2+  >CO3Ca+ + H+ (1)

>CaOH + CO2  >CaCO3− + H+ (2)
>CaOH + CO2  >CaHCO3 (3)

To summarize, calcite surface determining ions (PDI) are the lattice ions Ca2+ and CO32−. Mg2+
can also be considered as a PDI. The pH affects the zeta potential by moderating the equilibrium pCa
for a given CO2 partial pressure (pCO2), therefore, it does not directly control the zeta potential [22].
Table 5 presents calcite IEP values and their measurement operating conditions.
Minerals 2020, 10, 1109 9 of 22

Table 4. The isoelectric point (IEP) values of phosphate minerals and their measurement operating conditions.

Size
Mineral Source IEP Purity Wt% Electrolyte pH Adjustment Ref
(µm)
Geological museum of Yunnan
3 >99% 0.1 <5 10−3 M NaCl N.A. [23]
province, China.
Africa. 4 High purity 0.02 <5 10−2 M KNO3 HCl and NaOH [24]
Ontario, Canada. 5.5 39.18% P2O5 0.01 <43 10−3 M KNO3 HCl and NaOH [25]
Ward’s Natural Science 0.1 M HCl and 0.1
Fluorapatite 3.9 37.8% P2O5 N.A. <5 N.A. [26]
Establishment, Canada. M NaOH
10% HCl and 10%
Madagascar in South Africa. 3.4 Pure 0.05 <38 N.A. [27]
NaOH
Ward’s Natural Science
2.75 Mainly fluorapatite 0.01–0.1 <20 10−2 M KCl HCl and NaOH [28]
Establishment, Canada.
Fort Dauphin, Tuléar province,
2–3 N.A. 0.01 <5 10−3 M KCL NaOH and HCl [29]
Madagasca.
Carbonate-
4.8 ± 31.78% P2O5 prior 0.5, 0.1, and 0.01 M
fluorapatite Oulad Abdoun, Morocco. 1 <50 HNO3 and KOH [30]
0.2 to sieving KNO3
(Francolite)
Sinai Manganese Company Quseir
6.8 >99% 0.1 <45 10−2 M NaCl N.A. [31]
(Red Sea, Egypt).
Ward’s Natural Science
Hydroxy- 4 High purity 2 ≤20 10−3 M KCL HCl and NaOH [32]
Establishment, Canada.
apatite
The Lisina deposit, Bosilegrad, Serbia. <5 98.45% 0.1 <5 NaNO3 HCl and NaOH [33]
Dayukou phosphate mine in Hubei
6.5 92.05% 0.01 <2 10−3 M KCl HCl and NaOH [34]
Province, China.
Collophane
Shanxi Province, China. 6.4 High purity 0.005–0.01 <20 10−3 M KCl HCl and NaOH [35]
Guizhou province, China. 2–3 94.51% 0.1 ≤5 10−3 M KNO3 HCl and NaOH [36]
Gregory, Bottley and Lloyd Ltd.,
3.9 Pure 0.05 ≤5 10−2 M NaCl HCl and NaOH [37]
United Kingdom.
Luiz Menezes Comércio e Exportacao
Apatite 6.5 99% 2 <38 10−3 M KCl HCl and NaOH [38]
de minerais (Brazil).
Ward’s Natural Science
4.2 46.06% P2O5 0.01–0.1 <20 10−3 M KCl HCl and NaOH [39]
Establishment, Canada.
Minerals 2020, 10, 1109 10 of 22

Figure 1. Illustration of the electrical double layer of calcite surface in water with NaCl as the
electrolyte. IHP and OHP stand for the inner and outer Helmholtz planes, respectively [22].

Table 5. IEP calcite values and their measurement operating conditions.

pH
Source IEP Purity Wt (%) Size (µm) Electrolyte Ref
Adjustment
Rongan mine in
99.21% HCl and
Guangxi province, 9.2 0.1 <5 10−3 M KCl [40]
CaO NaOH
China.
Guangxi province
10−2 M HCl and
and Hunan province, 9.5 98.91% 0.1 <2 [41]
KNO3 NaOH
China.
Yunna province of HCl and
9.5 98% 0.01 <5 10−3 M KCl [42]
China. NaOH
Shizhuyuan mine, HCl and
10.3 >98% 0.05 <2 10−2 M KCl [43]
Chenzhou, China. NaOH

 Dolomite solubility and surface charge

The surface of dolomite resembles that of calcite. Dolomite is soluble in aqueous medium and
the lattice ions Ca2+, Mg2+, and CO32− are susceptible, depending on the solution pH, to either dissolve
in the solution or precipitate on mineral surfaces. Moreover, the solution pH and concentrations of
Ca2+, Mg2+, CO32−, and HCO3 might fluctuate under the influence of dissolved atmospheric CO2. The
species existing on the dolomite surface were investigated by some researchers. Figure 2 presents the
calculated speciation at the dolomite–solution interface [44]. Based on these calculations, at a pH
below 4, carbonate sites are protonated with predominantly >CO3H species. In higher pH conditions,
>CO3− dominates as deprotonation occurs. pH as well as the dissolved carbonate concentration
influence the speciation at the dolomite metal sites. At a pH below 8, >MeOH2+ species are dominant,
however, once the pH exceeds 8 > MeCO3− dominates. The study confirms the similarities between
calcite and dolomite interfaces in aqueous solutions. It also indicates that the PDI for the dolomite
surface are its lattice ions (as for calcite) being Ca2+, Mg2+, and CO32− [44]. Table 6 presents IEP values
of dolomite and their measurement conditions.
Minerals 2020, 10, 1109 11 of 22

Figure 2. Calculated surface speciation of dolomite (0.01 mol/L NaCl, 10−3 M Ca2+, and Mg2+ solution
in equilibrium with pCO2 = 10−3.5 atm). (a) Carbonate sites, and (b) metal sites [44].

Table 6. IEP values of dolomite and their measurement conditions.

Wt Size pH
Source IEP Purity Electrolyte Ref
(%) (µm) Adjustment
Wulongquan Mine in HCl and
4.4 90.62% 0.01 <2 10−3 M KCl [34]
Hubei Province, China. NaOH
Sterling Hill Mine, New relatively 10–3 M HCl and
4.8 0.01 D50 < 2.3 [45]
Jersey, USA. pure NaCl KOH
Ward’s Natural Science mainly 0.01– HCl and
3.37 <20 10−2 M KCl [28]
Establishment, Canada. dolomite 0.1 KOH
36.06%
Ward’s Natural Science 0.01– HCl and
6.2 MgO, <20 10−3 M KCl [39]
Establishment, Canada. 0.1 NaOH
60.27% CaO
20.62%
10−3 M HCl and
Selasvann, Norway. 7 MgO, 0.01 <43 [25]
KNO3 NaOH
31.36% CaO
Sinai Manganese
10−2 M
Company Quseir, Red 8.5 >99% 0.1 <45 N.A. [31]
NaCl
Sea, Egypt.

 Quartz solubility and surface charge

Quartz can be found as an impurity in most phosphate ores. Its superficial properties in aqueous
solution resembles the properties of amorphous silica. Therefore, the two materials carry similar
functional surface groups, and consequently, have the same reaction mechanism [46]. In the quartz-
fatty acid flotation system, and in the absence of metal ions, the predicted Reactions are:
>SiOH  SiO− + H+, (4)
and RCOOH  RCOO− + H+. (5)
According to the reactions above, the adsorption of fatty acids on the quartz surface is nearly
impossible. Though, in the presence of metal ions, quartz hydrophobicity can be achieved by surface
reactions such as the ones presented below (Reaction 6, 7, and 8) [46]. Table 7 presents the IEP values
of quartz and its measurement operating conditions.
>SiOH + Me2+  SiOMe+ + H+, (6)
>SiOH + Me + RCOO− + H2O  SiOMeOHRCOO− + 2H+,
2+ (7)
Or, + Me3+ + RCOO− +H2O  MeOHRCOO− + 3H+. (8)
Minerals 2020, 10, 1109 12 of 22

Table 7. IEP values of quartz and measurement conditions.

Size pH
Source IEP Purity Wt (%) Electrolyte Ref
(µm) Adjustment
Ward’s Natural
Science Negativ 0.01– HCl and
96.02% <20 10−3 M KCl [39]
Establishment, e 0.1 NaOH
Canada.
SAC Co., South 99.2% 0.1M HCl and
2.1 N.A. <5 N.A. [26]
Korea. SiO2 0.1M NaOH
Hubei province, Relatively 10% HCl and
2 0.05 <38 N.A. [27]
China. pure 10% NaOH
Luanping county,
HCl and
Hebei province, 2 99% 0.05 <5 N.A. [47]
NaOH
China.

2.1.3. Wettability (Contact Angle)

Mineral wettability is critical to the establishment of an efficient froth flotation process. It
conveys the mineral’s floatability with or without the addition of collectors. The wettability is
expressed by an empirical angle. It can be experimentally measured by various methods. For
instance, a liquid drop is laid on a solid surface. The intersection of the liquid-solid and liquid-vapor
interfaces forms the angle termed “contact angle”. A hydrophobic surface retains a contact angle
larger than 90°. A hydrophilic surface has a smaller contact angle [48]. The contact angle was first
introduced by Tomas Young (1805) and can be calculated through its equation:
γlv cos θY = γsv − γsl, (9)
where γlv, γsv, and γsl represent the liquid-vapor, solid-vapor, and solid-liquid interfacial tensions,
respectively, and θY is the Young’s contact angle.
However, the contact angles calculated through young’s equation are usually different from the
measured ones. The calculated θY can be experimentally confirmed only in ideal conditions where
the solid surface is physically and chemically homogenous, and the experiment is conducted under
extremely controlled conditions. In reality, most measurements are done on heterogenous imperfect
solid surfaces (especially for minerals). The advancing and the receding contact angles are other
variations of θ. They are measured by expanding and contracting the liquid, respectively and the
difference between these two is called the hysteresis (H), a very interesting and informative
parameter:
H = θa – θr. (10)
Table 8 presents phosphate minerals, calcite, dolomite, and quartz contact angles with water
using different experimental methods. As already mentioned, the contact angle’s precision depends
on the sample preparation as its interface needs to be smooth and homogeneous and the
measurement must be conducted in controlled conditions to avoid vibrations.
Minerals 2020, 10, 1109 13 of 22

Table 8. Contact angle values of phosphate minerals, calcite, dolomite, quartz, and their measurement conditions.

The Contact Angle Contact Angle Value

Mineral Source Method Ref
Type In °
Ontario, Canada. - The captive bubble 36 [49]
(001) 45.1
Anemzy, Imilchil, High Atlas Mts, (100) 58.9
Single crystal Static The sessile drop [50]
Morocco. (101) 63.6
Fluorapatite (111) 72.8
Yunnan and Hunan Province, China. Static The sessile drop 54.6 [51]
−425 + 150 µm 52.7
Capillary penetration
Mineral powder Gregory, Bottley and Lloyd, London. - −150 + 38 µm 8.35 [52]
(Washburn method)
−38 µm 55.3
White pebbles 0
Carbonate
Tan pebbles Central Florida, USA. Advancing The sessile drop 10 [53]
fluorapatite
Black pebbles 10
Phosphate mine in Guizhou province, Capillary penetration (Washburn
Collophane Mineral powder - About 20° [36]
China. method)
Calcite crystals (Iceland Ward’s Natural Science Establishment,
Advancing The sessile drop 21 [54]
Calcite Spar) USA.
Single crystal Yunnan and Hunan Province, China. Static The sessile drop 45.6 [51]
Selasvann, Norway. - The captive bubble technique 50.5 [49]
Dolomite Haicheng of Liaoning Province, China. - - 11.67 [55]
Konya-Argit region, in Turkey. - The captive bubble technique Between 5.68 and 7.68 [56]
Xinjiang Keketuohai Rare Metal Mine,
Advancing The sessile drop Between 1.5 and 5 [57]
China.
Hand-picked
Anqian iron mine, Liaoning Province,
Quatrz Static Sessile drop method Between 22 and 25 [58]
China.
Phosphate mine in Guizhou province, Capillary penetration (Washburn
Mineral powder - About 20° [36]
China. method)
Minerals 2020, 10, 1109 14 of 22

2.2. Flotation Reagents

Flotation reagents, especially regulators (activators, depressants, and pH regulators) and

collectors, impact the selective separation of phosphate minerals from impurities, which are usually
carbonates (calcite and dolomite) and silicates (quartz). During the phosphate direct flotation process,
gangue minerals are depressed and the phosphate mineral retaining a hydrophobic surface is floated.
The opposite occurs during reverse flotation. Table 9 summarizes the reagents used in the phosphate
reverse and direct flotation.

2.2.1. Gangue Minerals Reagents

 Calcite and Dolomite Reagents
Generally, anionic collectors are used for carbonates flotation. In the past decades and still in
some cases today, anionic collectors’ production depended on tall oil and oxidized petroleum as raw
materials. However, these come with multiple downsides. Rather, vegetable oils such as rice bran,
hydrogenated soybean, cottonseed, and jojoba oils represent a promising inexpensive source for fatty
acids [59]. There are some cases when amphoteric collectors (e.g., aminopripionic acid [60,61],
carboxyethyl imidazoline [62]) are used for floating carbonates. Moreover, nonionic collectors are
generally used to improve the performance of ionic surfactants. They reduce the electrostatic
repulsions between ionic head groups, generate hydrophobic chain interactions, and consequently,
the adsorption of the ionic collector on mineral surfaces [29]. Table 10 presents the conditions and
results where anionic and amphoteric collectors are used for the flotation of calcite and dolomite.
According to research conducted on different organic reagents used as dolomite depressants,
carboxymethyl cellulose, citric acid, and naphtyl anthyl sulfonates are effective [63]. The β-naphthyl
sulfonate formaldehyde condensate (NSFC) was used as a dolomite depressant during the anionic
flotation of collophane at pH value of 9 [34]. NSFC was chemically adsorbed on the dolomite surface
and barely adsorbed to collophane. However, NSFC’s chemical toxicity is a severe limitation [34].
Additionally, Bacillus subtilis and Mycobacterium phlei have been tested as depressants of apatite and
dolomite [64]. Results indicated the adsorption of both bacteria species on the minerals surfaces. They
functioned as depressants for dolomite, as well as for apatite. Although these bacteria do not ensure
apatite dolomite selectivity, a simulation of the flotation environment can provide a better choice of
bacteria for this purpose.
 Quartz Reagents
Usually, the elimination of silicates minerals, such as quartz, is conducted using cationic
collectors. Table 11 presents different reagents mentioned as silica collectors in the literature. Sodium
silicate is reported as a performing quartz depressant. Silva et al. [65] investigated the mechanism of
quartz depression using sodium silicate. They have found that at a pH value of 7, monomeric Si(OH)4
and polymeric species, resulting of sodium silicate hydrolysis, were adsorbed on the quartz surface.
For a sample containing 97.2% SiO2, the quartz depression was observed at a dosage of 1000 g/t
Na₂SiO₃. Optimum floatability was obtained in the pH range from 5 to 8 using a dosage of 1500 g/t
Na₂SiO₃ in the presence of 150 g/t amine. Under these conditions, quartz floatability was less than
10%. At a pH value of 11, floatability is high, suggesting that sodium silicate is not adsorbed onto the
quartz surface. Morever, starch exhibits a depressive effect on quartz flotation. Its flocculation
property enables it to adsorb onto the quartz surface engendering its depression [66]. Nevertheless,
starch is not an efficient depressant for quartz due to its low selectivity. It is still used in a number of
concentrators as it is cheap in comparison to other effective reagents [67].
Minerals 2020, 10, 1109 15 of 22

Table 9. Families of reagents used in phosphate flotation.

Selective Phosphate Flotation

Apatite Calcite and Dolomite Quartz
Collectors Depressants Collectors Depressants Collectors Depressants
Anionic Cationic
• Natural polysaccharides
Anionic • Fluosilicic acid, • Fatty acids, • Amine collectors (Primary, • Cationically modified
(Starch, quebracho),
• Fatty acids, • Sulfuric acid, • Saponified Secondary, Tertiary amines), polysaccharides,
• Synthetic polymers,
• Hydroxamates • Phosphoric acid and its derivatives, vegetable oils, • Amine salts, • Inorganic soluble salts
• Inorganic soluble salts,
• Natural polysaccharides (Starch), • Ester, • Quaternary ammonium salts. (Sodium silicate),
• Citric acid,
Amphoteric, • Synthetic polymers. Amphoteric, Amphoteric, •Hydrofluoric acid.
• Hydrofluoric acid.
Cationic. Nonionic. Nonionic.

Table 10. Collectors used for the selective flotation of carbonates (calcite and dolomite).

Type Name Supplier Source pH Dosage IRR (%) P2O5 Increase (%) Recovery (%) Ref
Gafsa-Metlaoui Basin;
V2711 Flotinor 5 0.2 kg/t 69.61 MgO 11.6 92.4 P2O5 [68]
Clariant South of Tunisia.
Flotinor 7466 North Africa phosphate ore. N.A. 0.6 kg/t 91.13 MgO 7.76 75.1 P2O5 [69]
Zhuzhou Chemical Pure calcite and fluorite minerals
Anionic Sulfoleic acid (SOA) Industry Research obtained from Xinyuan Mine, 9 6 mg/L 80.34 CaO 7.23 85.2 CaO [70]
Institute Chenzhou, Hunan, China.
Sodium dodecyl sulfate (SDS) N.A. Yichang, Hubei Province, China. N.A. 0.4 kg/t 60.20 MgO 6.38 71.86 [71]
The sedimentary phosphate
saponified jojoba oil Ferquima 6.5 200 mg/L N.A. N.A. N.A. [72]
deposit of Itataia, Brazil.
Lianyungang Subbituminous coal obtained from
N.A. 0.4 kg/t 95.10 8.10 88
Amphoteric dodecyl-N-carboxyethyl-N- Chemicals Plant, Peabody Energy in the USA.
[31]
Collectors hydroxyethyl-imidazoline Jiangsu Province, Phosphate (francolite) from Quseir
N.A. 0.4 kg/t 94.24 MgO 7.70 82 P2O5
China. (RedSea, Egypt).
IRR: Impurities-removal-ratio.
Minerals 2020, 10, 1109 16 of 22

Table 11. Cationic collectors used for the selective flotation of silica (quartz).

P2O5
Dosage IRR Recovery
Name Supplier Source pH Increase Ref
(kg/t) (%) (%)
(%)
Alkyl amine salt
66.01 5.50 85 P2O5
(DAH)
Ether-amine salt The Abyad
48.31 4.75 80.11 P2O5
(GE−619) N.A. area in 5 1 [73]
Quaternary Jordan.
ammonium salt 15.54 2.67 95.45 P2O5
(CTAB)
Flotigam EDA Minas Gerais 9 0.06 N.A. N.A. 100 SiO2
[74]
Flotigan 2835–2L state, Brazil. 9 0.06 N.A. N.A. 87 SiO2
Clariant,
North Africa
Switzerland.
Flotigam 7470 phosphate N.A. 0.42 37.14 7.76 75.1 P2O5 [69]
ore.
AkzoNobel 86.75
Lilaflot D817M 71.32 N.A.
Surface combustible
Chemistry, 87.26
Lilaflot 811 Peabody 65.32 N.A.
USA. combustible
Energy in the Natural 3 [70]
Dodecyl USA.
trimethyl Sigma-Aldrich, 90
49.96 N.A.
ammonium USA. combustible
bromide (DTAB)
IRR: Impurities-removal-ratio.

2.2.2. Apatite Minerals Reagents

Apatite minerals are usually depressed in acidic medium. Studies showed that at a pH value
below 4.5, apatite floatability is weak due to the dominance of Ca2+, CaH2PO4+, and H2PO4−. The
H2PO4− species in the suspension occupies apatite’s active sites and leads to a poor recovery.
Therefore, inorganic acids are considered effective depressants with phosphoric acid being the most
used as it does not cause any complication during the enrichment process. Phosphate salts can
depress apatite, as well.
Always in acidic medium, using sulfate or oxalate salts is reported to further depress apatite.
These reagents incite the precipitation of the dissolved Ca2+, leading to apatite dissolution and a
greater presence of phosphate ions in the suspension [75,76].
Additionally, a synthetic polymeric depressant “ACCO-PHOS 950” was developed by Cytec.
The aim is to limit apatite loss during silicates flotation using amine collectors. The reagent proved
to be effective when used on North Africa’s high-grade phosphate ores [77]. Zhang and Snow (2014)
[78] investigated sodium tripolyphosphate, fluosilicic acid, diphosphonic acid, starch and sodium
silicate as apatite depressants candidates. The phosphate ore used contains 19.82% P2O5 and 40.28%
Insol. Sodium tripolyphosphate gave promising results. Using it as apatite depressant yielded a final
phosphate concentrate assaying approximately 31% P2O5 and up to 7% Insol with over 94% P2O5
recovery. During reverse flotation of silica from a fine-grained feed, starch effectively depressed the
apatite.

2.3. Influence of Particle Size

Particle size is a main parameter in the flotation process. Particles of various sizes behave
differently in the flotation system, directly affecting the recovery, selectivity, and overall
performance. Usually, fine particles’ flotation is less preferred compared to coarse mineral particles.
Fine-grained minerals have a higher surface energy, leading to a nonselective reagent consumption,
entrainment or entrapment of particles and an instability of bubble-particle aggregates. A study of
the relationship between the phosphate particles size and flotation recovery was carried out by
Gaudin et al. (1931). The results revealed that under similar operating conditions, particles of various
sizes exhibit different flotation kinetics. The maximum phosphate minerals recovery was obtained
Minerals 2020, 10, 1109 17 of 22

when treating size fractions between 60 and 200 µm. Mineral liberation, which is related to the
particle size, is also a parameter in the froth flotation of phosphate ores. Fine grinding is critical to
attain greater liberation but will unfavorably affect the separation efficiency. Therefore, there is
generally a compromise when choosing the particle size. A preforming flotation system requires an
effective liberation of desired minerals without overgrinding the ore.

2.4. Influence of the Froth Stability

2.4.1. Froth Stability

The attachment of hydrophobic mineral particles to gas bubbles leads to the genesis of a
concentrated mineral lather. The froth’s stability is critical and is generally maintained using foaming
agents (frothers). The froth must sustain the particle’s weight, while resisting excessive coalescence
and bursting. On the other hand, the proper functioning of the flotation process requires a
manageable and easily suppressed froth for a practical recovery [79]. Froth stability is affected by the
parameters such as gas flow rate, stirring rate, solid content, particle size, mineralogy, reagents type
and dosage, and water’s ionic strength. Farrokhpay et al. [80] noted that froth stability can be assessed
through parameters such as froth half-life time, froth maximum height at equilibrium, dynamic froth
stability factor, bubble growth across the froth phase, air recovery, and solid loading on bubbles on
top of the froth surface, froth velocity, and froth rise velocity, etc.
Particle size and solid content: Liu et al. [79] investigated, in their recent study, the effect of
particle size and solid content on fluorapatite, calcite, dolomite, and quartz froths stability. Using a
setup inspired from Lunkenheimer’s report [81], they assessed the dynamic froth stability factor (Ʃ)
for different particle sizes and solid contents. This factor is calculated using:

× (11)
Σ= =

Vf is the froth volume (cm3), Q is the gas flowrate (cm3/s), S is the cross-sectional area of the column
(cm2), and Hmax is the maximum froth equilibrium height (cm).
Liu et al. [79] found that for fluorapatite, calcite, dolomite, and quartz the fine particles
contribute to froth stability as a result of capillary mechanisms, whilst larger particles lead to froth
rapture and instability. Additionally, they observed that increasing the solid content to a certain
extent stabilizes the froth (Figure 3).

(a) (b)

Figure 3. Effect of (a) particle size (b) solid content of fluorapatite, quartz, calcite, and dolomite on the
dynamic froth stability factor [79].

Water’s ionic strength/mineralogy: According to Liu et al.’s study [79], dolomite and especially
the calcite froths stability were found to be superior than those of fluorapatite and quartz. It was
demonstrated that Ca2+ and Mg2+ ions resulting from calcite and dolomite dissolution stabilize the
Minerals 2020, 10, 1109 18 of 22

froth. Moreover, the froth half-life time increased dramatically with the addition of Ca2+ ions up to
5.10−4 mol/ L Ca2+ but decreased rapidly thereafter.
Reagent type: The reverse flotation process widely used for upgrading siliceous phosphate ores
are considered challenging, especially regarding froth stability. In most cases, cationic collectors are
used to float the siliceous gangue. However, they produce an expanding overly stable froth that
might entrain other minerals, causing lack of selectivity [59,79,82].

2.4.2. Bubble’s Size

Hoang et al. [83] studied the effect of flotation time and froth height on the bubble’s size. They
found that the bubble’s size increased with flotation time, contributing to the reagent’s consumption
and the decrease in the solid content leading to bubble coarsening. They also stated that the bubble’s
size increased with the froth height due to water film rupture resulting from low reagents
concentration and hydrophobic particles existing in the water film.

3. Conclusions
Based on common scientific data, it can be deduced that the phosphate ores’ enrichment was not
as complicated as the enrichment of other minerals, namely, metal sulfides and oxides. The deposits
already exploited have been high in P2O5 content, contained less impurities, and there were not as
many strict quality regulations as there is today. With the depletion of these deposits, upgrading
complex phosphate ores, while respecting rigorous criteria, is more and more challenging. Phosphate
processing regulations are not only about the concentrate’s quality. They also cover environmental
issues, such as CO2 emission, polluting and toxic reagents, water and waste management.
• Huge carbon dioxide emissions are the main downside of thermal beneficiation techniques such
as calcination. Hence, froth flotation was developed to replace it in many cases.
• Water recycling is already applied in most phosphate concentrator plants.
• Phosphate waste valorization is an interesting recent topic with numerous industrial
opportunities. Hakkou et al. [84] mentioned multiple methods of phosphate wastes valorization.
One way is the use of alkaline phosphate wastes (APW) to inhibit the acid mine drainage (AMD).
Regarding its high calcite content, 15% APW was used to neutralize the acidity produced by
pyrrhotite tailings’ oxidation [85]. The APW were also assessed in the passive AMD water
treatment [84]. Additionally, phosphate wastes with a size less than 1 mm, were tested in store-
and-release (SR) covers to reclaim industrial mine sites [86].
• Flotation reagents can be environmentally harmful and highly toxic. For instance, different
apatite depressants (organic and inorganic) are used in the reverse flotation of sedimentary
phosphate ores. The most common ones are phosphoric and sulfuric acid and their derivatives.
Using these inorganic depressants can entail, however, potential threats to the environment [87]
(e.g., calcium phosphate scale formation and water eutrophication [88]). Organic depressants
have been developed for apatite/carbonate separation, as well. Nevertheless, they are usually
extremely toxic which limits their use [87].
Author Contributions: Conceptualization, M.D. and YT; methodology, M.D. and Y.T.; validation, Y.T., M.B. and
R.H.; writing—original draft preparation, M.D.; writing—review and editing, M.D. and Y.T.; supervision, Y.T,
R.H. and M.B.; project administration, Y.T.; funding acquisition, Y.T, R.H. and M.B. All authors have read and
agreed to the published version of the manuscript.

Funding: This research was financially supported through the research program between OCP S.A under the
specific agreement OCP/UM6P AS34.

Conflicts of Interest: The authors declare no conflict of interest.

Minerals 2020, 10, 1109 19 of 22

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