minerals

Article
Thermal Beneficiation of Sra Ouertane (Tunisia)
Low-Grade Phosphate Rock
Noureddine Abbes 1, * , Essaid Bilal 2 , Ludwig Hermann 3 , Gerald Steiner 4 and
Nils Haneklaus 4, *
1 Groupe Chimique Tunisien, Gabes 6000, Tunisia
2 École Nationale Supérieure des Mines de Saint Etienne, 42023 Saint-Etienne, France; bilalessaid@gmail.com
3 Proman Management GmbH, Weingartenstrasse 92, 2214 Auersthal, Austria; l.hermann@proman.pro
4 Td Lab Sustainable Mineral Resources, Danube University Krems, Dr.-Karl-Dorrek-Straße 30, 3500 Krems,
Austria; gerald.steiner@donau-uni.ac.at
* Correspondence: abbes.nour85@gmail.com (N.A.); nils.haneklaus@donau-uni.ac.at (N.H.)




Received: 7 August 2020; Accepted: 13 October 2020; Published: 22 October 2020


Abstract: Low-grade phosphate rock from Sra Ouertane (Tunisia) was beneficiated using a
thermal treatment consisting of calcination, quenching, and disliming. Untreated phosphate rock
samples (group 1), calcined phosphate rock samples (group 2), as well as calcined, quenched,
and dislimed (group 3) phosphate rock samples, were investigated using inductively-coupled plasma
atomic emission spectroscopy (ICP-AES), inductively-coupled plasma mass spectrometry (ICP-MS),
thermogravimetric analysis (TGA), and X-ray powder diffraction (XRD). Besides, the particle size
distribution of the aforementioned three groups was determined. The proposed thermal treatment
successfully increased the P2 O5 content of the untreated phosphate rock from 20.01 wt% (group 1) to
24.24 wt% (group 2) after calcination and, finally, 27.24 wt% (group 3) after calcination, quenching,
and disliming. It was further found that the concentration of relevant accompanying rare earth
elements (Ce, La, Nd, Pr, Sm, and Y) was increased and that the concentration of Cd could be
significantly reduced from 30 mg/kg to 14 mg/kg with the proposed treatment. The resulting phosphate
concentrate showed relatively high concentrations in metal oxides: Σ MgO, Fe2 O3 , Al2 O3 = 3.63 wt%
and silica (9.81 wt%) so that it did not meet the merchant grade specifications of a minimum P2 O5
content of 30 wt% yet. Removal of these elements could be achieved using additional appropriate
separation techniques.

Keywords: thermal beneficiation; calcination; low-grade phosphate rock; Sra Ouertane; Tunisia

1. Introduction
Phosphate rock plays a critical economic role in Tunisia and other countries worldwide.
The increasing demand for phosphate rock for fertilizer production and its importance in animal
feedstocks, as well as food-grade phosphates and other industrial uses, further solidifies the importance
of the phosphate industry in these countries. The demand for phosphate rock is typically fulfilled
through phosphate rock mining. The phosphate industry mined nearly 250 million tons of phosphate
rock in 2018 [1]. In Tunisia, the phosphate rock industry is of considerable importance to the country’s
economy. Since the discovery of Tunisian phosphate deposits in the 19th century, phosphate production
is controlled and operated by the Gafsa Phosphate Company (CPG, Compagnie des Phosphates de
Gafsa, Gafsa, Tunisia). Tunisia has three major phosphate rock deposits: the Northern Basin, the Eastern
Basin, and the Gafsa Basin. Figure 1 provides a brief overview of the major phosphate rock deposits
in Tunisia.

Minerals 2020, 10, 937; doi:10.3390/min10110937 www.mdpi.com/journal/minerals

Minerals 2020, 10, 937 2 of 13
Minerals 2020, 10 2 of 13

Figure
Figure 1. Major
Major phosphate
phosphate rock
rock deposits
deposits in
in Tunisia.
Tunisia.

Currently, more than 90% of the phosphate rock produced in Tunisia is mined from the Gafsa
Basin. Tunisia
Tunisiapossesses
possessesother
otherlarge
largephosphate
phosphate rock deposits
rock withwith
deposits reserves matching
reserves thosethose
matching of theof
Gafsa
the
Basin in quantity but not in quality with regards to the phosphorous (P) content
Gafsa Basin in quantity but not in quality with regards to the phosphorous (P) content [2]. These [2]. These deposits
are in Sraare
deposits Ouertane, which iswhich
in Sra Ouertane, part ofis the
partNorthern Basin. Basin.
of the Northern Up to date,
Up tothese
date, reserves have not
these reserves havebeen
not
exploited
been [3]. With
exploited [3]. the increased
With interestinterest
the increased in mining of phosphate
in mining rock androck
of phosphate other monetarily
and valuable
other monetarily
accompanying
valuable elements,elements,
accompanying such as raresuchearth elements
as rare earth(REEs)
elements and(REEs)
uranium and[4–11], presently
uranium [4–11],considered
presently
low P-gradelow
considered deposits aredeposits
P-grade becoming areincreasingly relevant. relevant.
becoming increasingly
Table 11provides
providesananoverview
overview of of
thethe
typical P2 OP52,OREEs,
typical andand
5, REEs, uranium concentrations
uranium of some
concentrations mine
of some
sites in
mine theinNorthern-,
sites Eastern-,
the Northern-, and Gafsa
Eastern-, BasinBasin
and Gafsa for which detailed
for which data data
detailed was was
made available
made for this
available for
study.study.
this The SraTheOuertane low-grade
Sra Ouertane phosphatephosphate
low-grade rock deposit in northern
rock deposit Tunisia can be Tunisia
in northern characterized
can beas
a deposit withas
characterized relatively
a deposithigh uranium
with relativelyandhigh
REEuranium
content compared to othercompared
and REE content deposits in
toTunisia [12–18].
other deposits
in Tunisia [12–18].
Table 1. Potential P2 O5 , Uranium, and Rare Earth Element (REE) Concentrations in Some Tunisian
Phosphate
Table Rock Deposits
1. Potential [19,20]. and Rare Earth Element (REE) Concentrations in Some Tunisian
P2O5, Uranium,
Phosphate Rock Deposits [19,20]. P O (wt%) Uranium (mg/kg)
P
REE (mg/kg)
Deposit 2 5
Basin
Min. Max. Avg. Min. Max. Avg. Min. Max. Avg.
P2O5 (wt%) Uranium (mg/kg) ∑ REE (mg/kg)
Basin Deposit 19.7
Sekerna 23.8Max. 21.8 36.2 55.1 45.6 750 Max.800 Avg.775
Northern Basin Min. Avg. Min. Max. Avg. Min.
Sra Ourtane 21.9 26.1 24.0 73.9 112.2 93.6 401 690 546
Sekerna 19.7 23.8 21.8 36.2 55.1 45.6 750 800 775
Northern
Eastern BasinBasin Jebel Jebs 27.9 29.5 28.7 40.8 46.7 44.1 935 1020 974
Sra Ourtane 21.9 26.1 24.0 73.9 112.2 93.6 401 690 546
Eastern Basin Jellabia
Jebel Jebs 16.4 27.9 30.329.5 26.028.7 19.9
40.8 53.7
46.7 32.7
44.1 155
935 617
1020 974432
Kef Eddour 25.4 28.8 26.5 23.9 41.1 31.9 171 478 320
Gafsa Basin Jellabia 24.1 16.4 28.330.3 26.426.0 20.9
19.9 36.2
53.7 32.7 155 617
Metlaoui 29.9 175 550 432326
Kef Eddour23.9 25.4 29 28.8 27.226.5 25.4
Naguess 23.9 44.2
41.1 31.9
33.6 171
204 478
508 320345
Gafsa Basin
Metlaoui 24.1 28.3 26.4 20.9 36.2 29.9 175 550 326
The relatively largeNaguess
amount of 23.9
impurities29 found
27.2 in the
25.4Sra 44.2
Ouertane
33.6deposit
204 make
508 beneficiation
345
using flotation technically challenging [21–23]. Calcination is, therefore, considered here for P2 O5
The relatively
concentration. large amount
Calcination of impurities
can largely found in the
remove carbonates andSra Ouertane
organic deposit
matter make
from the beneficiation
phosphate rocks.
using
Organicflotation
matter technically challenging
can lead to increased use[21–23]. Calcination
of sulfuric is, therefore,
acid for the considered
digestion process that here for P2O5
consequently
concentration.
increases overallCalcination
productioncancosts
largely remove
[24–26]. In carbonates and organic
this basic technical matter
study, from the phosphate
the economics of such a
rocks. Organic
calcination matter
system werecan
not lead to increased
considered yet. Theuse of sulfuric
location acidprovides
in Tunisia for the excellent
digestionconditions
process that
for
consequently increases
concentrated solar overall
power, and production
we hope that costs [24–26].rock
phosphate In this
frombasic
Sratechnical
Ouertanestudy,
couldthe economics
ultimately be
of such a calcination system were not considered yet. The location in Tunisia provides excellent
conditions for concentrated solar power, and we hope that phosphate rock from Sra Ouertane could
ultimately be heat treated using solar-powered calcination systems. Reliable cost estimations of the
Minerals 2020, 10, 937 3 of 13
Minerals 2020, 10 3 of 13

heat
total treated using
treatment solar-powered
costs with such calcination
solar-poweredsystems.
systemsReliable
can becostprovided
estimations at of the totaltechnology
a higher treatment
costs withlevel.
readiness such solar-powered systems can be provided at a higher technology readiness level.
Currently, approximately 10% of the phosphate rock processed processed worldwide
worldwide is is calcined
calcined [27].
[27].
Further depletion of higher grade phosphate rock resources, as well as technical innovations, such as
solar-driven calcination of phosphate rocks [28,29], may increase the percentage of phosphate rocks
that will be calcined
calcined in the
the future.
future. Previously thermal beneficiation of Tunisian phosphate rock with
aluminum silicates [30] and ammonium
aluminum silicates ammonium sulfate
sulfate [31]
[31] has
has been
been studied.
studied. Furthermore,
Furthermore, calcination
calcination of
Gafsa-Metloui: Jebel Oum El Khacheb deposit [32] and Ras-Dhara deposit [33], as well as M’dhilla [34]
phosphate
phosphate rock,
rock,has been
has investigated,
been and and
investigated, Jaballi et al. [35]
Jaballi analyzed
et al. the thermal
[35] analyzed the behavior
thermal of phosphate
behavior of
rocks from rocks
phosphate the Ypresian
from thephosphate
Ypresiandeposit.
phosphateBesides, Daik
deposit. et al. [36]
Besides, and
Daik et Dabbebi et al.
al. [36] and [37] looked
Dabbebi et al. into
[37]
the calcination
looked into theof phosphate
calcinationwashing waste from
of phosphate the Gafsa-Metloui
washing waste from deposit. The objectivedeposit.
the Gafsa-Metloui of this work
The
was to examine
objective of this the
work technical feasibility
was to examine oftechnical
the a thermalfeasibility
beneficiation path forbeneficiation
of a thermal Sra Ouertanepath low-grade
for Sra
phosphate rock usingphosphate
Ouertane low-grade calcination, quenching,
rock and disliming.
using calcination, quenching, and disliming.

2. Materials and
2. Materials and Methods
Methods
The
The Sra
Sra Ouertane
Ouertane depositdeposit consists
consists of
of three
three phosphate
phosphate rock
rock layers
layers (A1,
(A1, A2,
A2, and
and C).
C). Stratigraphic
Stratigraphic
information
information ofof the
the Sra
Sra Ouertane
Ouertane deposit
deposit is
is provided
provided in in Figure
Figure 2. Samples from
2. Samples from layers
layers A1,
A1, A2,
A2, and
and C
C
were made available for this study. The usual P O concentration of the different layers
were made available for this study. The usual P2O5 concentration of the different layers is as follows:
2 5 is as follows:
A1
A1 (15–21
(15–21 wt%
wt% P O55),), A2
P22O A2 (8–13
(8–13 wt%
wt% PP22O
O55),),and
andCC(10–13
(10–13wt%
wt%PP2O
2O 5 ).
5).

Lithology Log Layer Thickness (m) P2O5 content (wt%)

Ostreas shales, coquinas F 3

Nummulitic limestone E 40 1.6

Alternance marly and limestone D 15 4

Coarse phosphate grain C 10 13

Maris B 1 4

Fine calcareous phosphate A2 12 10

Fine-grained phosphate A1 21 18

Maris (El Haria formation) M 100

White limestone (Abiod formation) Ab3 120

Figure
Figure 2.
2. Stratigraphic
Stratigraphic information
information of
of the
the Sra
Sra Ouertane
Ouertane deposit
deposit in
in Northern
Northern Tunisia [16].
Tunisia [16].

Samples from layers A1, A2, and C of the Sra Ouertane phosphate rock deposit were used for
the thermogravimetric analysis (TGA). Later,
Later, a detailed sample analysis was performed with samples
from the layer A1. The samples were provided by the National Office of Mines (ONM) of Tunisia and
homogenized following the French regulation for the preparation of soil samples (NF X31-101) [38].
Minerals 2020, 10, 937 4 of 13

from the
Minerals layer
2020, 10 A1. The samples were provided by the National Office of Mines (ONM) of Tunisia4 of and
13
homogenized following the French regulation for the preparation of soil samples (NF X31-101) [38].
The received samples were washed washed with with water, dried at 110 ◦°C C overnight, and sieved
sieved to give a size
fraction less than 250 μm µm using ASTM (American Society for Testing Testing andand Materials)
Materials) sieves.
sieves.
Elemental analysis
analysisofofthethe samples
samples fromfrom
layerlayer
A1 was A1 conducted
was conducted using inductively-coupled
using inductively-coupled plasma
plasma mass spectrometry
mass spectrometry (ICP-MS,(ICP-MS, PerkinWoodbridge,
Perkin Elmer, Elmer, Woodbridge,ON, Canada) ON Canada) to determine
to determine the uranium, the
uranium,
thorium, andthorium, and REE
REE content and content and inductively-coupled
inductively-coupled plasma atomic plasma atomicspectroscopy
emission emission spectroscopy
(ICP-AES,
(ICP-AES,
HORIBA Jobin HORIBAYvon,Jobin
France)Yvon, France)
for all for all otherAll
other constituents. constituents. All chemical
chemical analyses analyses were
were conducted with
conducted
experimental with experimental
errors below 5%.errors below 5%.
The particle sizeThe particle size
distribution wasdistribution
determinedwas usingdetermined using
laser diffraction
laser diffraction
techniques on a techniques
Malvern Masteron a Malvern Master Sizer
Sizer S (Spectris S (Spectris
plc, Egham, UK)plc,
in Egham,
the wet UK)mode.in the wetpowder
X-ray mode.
X-ray powder diffraction (XRD) analysis was performed using a “Philips
diffraction (XRD) analysis was performed using a “Philips MPD1880-PW1710” diffractometer (Philipps, MPD1880-PW1710”
diffractometer
Eindhoven, The(Philipps, Eindhoven,
Netherlands) that usesNL)CuKα thatradiation
uses CuKα (λ =radiation
0.15418 nm) (λ =in0.15418 ◦ interval
the 2–80nm) in the with
2–80°a
interval of 0.02a◦ and
step size with stepcounting
size of time
0.02°ofand counting
20 s/step at room time of 20 s/step
temperature. Theatidentification
room temperature.
of the phasesThe
identification
was determined of the
usingphases was determined
the ICDD-PDF2004 using the
standard ICDD-PDF2004
database [39]. standard database [39].
Of particular
particular relevance
relevancefor forthis
thisstudy
study waswas thethe required
required calcination
calcination temperature
temperature and and residence
residence time
time of the phosphate rock that should be processed so that the suitability
of the phosphate rock that should be processed so that the suitability of solar-driven systems can be of solar-driven systems
can be determined.
determined. Depending Depending on thephosphate
on the given given phosphate rock, calcination
rock, calcination temperatures
temperatures can varycan vary
from asfrom
high
900 ◦as
as high C to900as°Clow low ◦as
to as 500 C 500 °C [40,41].
[40,41]. In thisIn thisattempt,
first first attempt, the thermal
the thermal analysis
analysis of theof the samples
samples from
from
layer layer A1 mg
A1 (9.66 (9.66 mg sample
sample weight), weight),
layer A2layer A2 mg
(16.75 (16.75 mg sample
sample weight),weight),
and layerandC layer
(12.35Cmg (12.35
samplemg
sample
weight)weight)
(particle(particle distribution:
distribution: 1 mm, 1500 mm, µm500 andμm, 250and
µm) 250 μm)
was was conducted.
conducted. The characteristic
The characteristic TGA
TGA curves for layers A1, A2, and C of the Sra Ouertane phosphate rock
curves for layers A1, A2, and C of the Sra Ouertane phosphate rock are shown in Figure 3. Experiments are shown in Figure 3.
Experiments
were conducted were at conducted
a temperature at a of
temperature
up to 800 C. ◦ of up to 800 °C.

Figure 3. The characteristic thermogravimetric analysis (TGA) curves of the samples from layers A1,
Figure
A2, and3.CThe characteristic
from Sra Ouertane thermogravimetric
phosphate rock. analysis (TGA) curves of the samples from layers A1,
A2, and C from Sra Ouertane phosphate rock.
Three peaks, typical of the calcination of phosphate rock, could be identified. The first mass loss
Three peaks, 80
at approximately typical of the calcination
◦ C corresponded to theofremoval
phosphate rock, could
of adsorbed be identified.
water. A secondThe weakfirstpeak
mass loss
could
at approximately 80 °C corresponded ◦ to the removal of adsorbed water. A second
be identified at approximately 550 C. Elgharbi et al. [33] attributed this peak to the simultaneous weak peak could
be identifiedofat
elimination approximately
chemical water in 550 °C. Elgharbi
the rock structureetandal.oxidation
[33] attributed this matter.
of organic peak toAsthe simultaneous
most phosphate
elimination of chemical water in the rock structure and oxidation of organic
rocks contain organic matter rich in sulfur, sulfur gas was released. The most pronounced peak matter. As most
was
phosphate rocks contain
found at 650–750 ◦ C, whereorganic matterdissociated,
carbonate rich in sulfur,
andsulfur gas was
CO2 was released.
released. Theonmost
Based pronounced
the TGA results,
peak was foundtemperature
the calcination at 650–750 °C, waswhere
set tocarbonate
720 ◦ C. Thedissociated,
weight lossandatCO
7202 ◦was released.
C was 11.88%Based
(layeron the9.72%
A1), TGA
results, the calcination temperature was set to 720 °C. The weight loss at 720 °C was
(layer A2), and 7.90% (layer C), respectively. Best practice experience with conventional kilns in Tunisia 11.88% (layer
A1), 9.72% (layer
recommends A2), and time
a calcination 7.90%of(layer C), respectively.
3 h. Thus, calcination Best practice experience
experiments with conventional
were performed at 720 ◦ C for
kilns
3 h. ItinisTunisia recommends
worth noting a calcination
that the time of 3 h.ofThus,
thermal dissociation calcination
carbonates is an experiments
endothermicwere performed
reaction with a
at 720 °C for 3 h. It is
significant energy requirement:worth noting that the thermal dissociation of carbonates is an endothermic
reaction with a significant energy requirement:
CaCO3 + Heat → CaO + CO2 ∆H = 965 kcal/kg CO2 or 42.9 kcal/mol CO2 (1)
CaCO + Heat → CaO + CO ΔH = 965 kcal/kg CO2 or 42.9 kcal/mol CO2 (1)
The calcine was further quenched in 5% ammonium nitrate solution with 25% solid content. The
calcine was kept in the ammonium nitrate solution for 2 h. In a subsequent disliming process,
particles of less than 60 μm were removed using a hydro-cyclone. The preliminary flow sheet of the
alternative beneficiation process for Sra Ouertane phosphate rock is provided in Figure 4.
Minerals 2020, 10, 937 5 of 13

The calcine was further quenched in 5% ammonium nitrate solution with 25% solid content.
The calcine was kept in the ammonium nitrate solution for 2 h. In a subsequent disliming process,
particles of less than 60 µm were removed using a hydro-cyclone. The preliminary flow sheet of the
alternative
Minerals 2020, beneficiation
10 process for Sra Ouertane phosphate rock is provided in Figure 4. 5 of 13

Figure 4.
Figure Simplifiedprocess
4. Simplified process flow
flow diagram,
diagram, describing
describing thermal
thermal beneficiation
beneficiation of Sra
of the theOuertane
Sra Ouertane
low-
low-grade
grade phosphate
phosphate rock rock by calcination,
by calcination, quenching,
quenching, and and disliming.
disliming.

3. Results and Discussion

3. Results and Discussion
The elemental components relevant for further fertilizer processing of samples from layer A1 are
The elemental components relevant for further fertilizer processing of samples from layer A1
provided in Table 2. The P2 O5 content of the untreated phosphate rock was successfully increased
are provided in Table 2. The P2O5 content of the untreated phosphate rock was successfully increased
from 20.01 wt% to 24.24 wt% after calcination. Further treatment consisting of quenching and
from 20.01 wt% to 24.24 wt% after calcination. Further treatment consisting of quenching and
disliming increased the P2 O5 content to 27.24 wt%. Merchant grade phosphate rock should show
disliming increased the P2O 5 content to 27.24 wt%. Merchant grade phosphate rock should show P2O5
P2 O5 concentrations of at least 30 wt%. Besides, it is important to mention that the atomic ratio
concentrations of at least 30 wt%. Besides, it is important to mention that the atomic ratio CaO/P2O5
CaO/P2 O5 = 1.94 of the untreated phosphate rock was still higher than the stoichiometric value of
= 1.94 of the untreated phosphate rock was still higher than the stoichiometric value of francolite with
francolite with very low carbonate substitution (CaO/P2 O5 = 1.65). Besides, the metal element ratio
very low carbonate substitution (CaO/P2O5 = 1.65). Besides, the metal element ratio (MER) of 0.18 =
(MER) of 0.18 = (MgO + Fe2 O3 + Al2 O3 )/P2 O5 was just slightly below the maximum acceptable
(MgO + Fe2O3 + Al2O3)/P2O5 was just slightly below the maximum acceptable value of 0.2.
value of 0.2.
The calcined and treated phosphate rock, on the other hand, could be associated with the
fluorapatite
Table 2. phase. TheAnalysis
Elemental CaO/P2O = 1.68 was Calcined,
of5 Untreated, now veryasclose
Well to
as that of francolite.
Calcined Besides,
and Treated the MER of
Sra Ouertane
0.13 was
(Layer well
A1)below the acceptable
Phosphate Rock. value of 0.2.
A loss of 39 wt% Al2O3 and 30 wt% MgO from untreated phosphate rock to calcined and treated
Calcined and Treated
phosphate
Component rock Untreated
can be observed
Phosphatein Table
Rock 2. This
(wt%) loss could
Calcined be associated
Phosphate Rock (wt%) with clays that were in a
Phosphate Rock (wt%)
fraction of fewer than 60 microns. It is known that Mg is correlated with CO32− apatite, and it could
P2 O5 20.01 24.24 27.24
thus be CaO estimated that a portion
42.93 of MgO was associated 47.01with the departure of45.65 CO32− during
calcination.
SO 3 SO3 increased by 18% in the calcined and treated sample (Table 2). Francolite, the
1.88 2.03 2.25
MgO
phosphoric mineral of almost1.29
all sedimentary phosphorites,1.18 0.92
has a variable chemical composition that
Fe2 O3 1.52 1.26 1.16
can beAlrepresented
2 O3
by (Ca, Mg,2.56Sr, Na)10 (PO4, SO4, CO3)6 F2–32.14
. We hypothesized that a part 1.55 of the CO3
2−

SiO2 was substituted3.08

of francolite by SO4 during calcination in 12.4
2− addition to the conventional 9.81substitution
CO2
between PO43− and CO32−. 14.78 1.95 1.95
F 2.50 2.45 2.20

Table 2. Elemental Analysis of Untreated, Calcined, as Well as Calcined and Treated Sra Ouertane
The calcined and treated phosphate rock, on the other hand, could be associated with the
(Layer A1) Phosphate Rock.
fluorapatite phase. The CaO/P2 O5 = 1.68 was now very close to that of francolite. Besides, the MER of
0.13 was well below the acceptable
Untreated Phosphate value of Calcined
0.2. Phosphate Calcined and Treated Phosphate
Component
A loss of 39 wt%Rock
Al2 O(wt%)
3 and 30 wt% MgO from Rockuntreated
(wt%) phosphate rock toRock (wt%) and treated
calcined
P2O5 rock can be observed
phosphate 20.01 24.24could be associated with clays
in Table 2. This loss 27.24 that were in a
CaOof fewer than 6042.93
fraction microns. It is known that 47.01 45.65 and it could
Mg is correlated with CO3 2− apatite,
thus be estimated that a portion of MgO was associated with the departure of CO3 2.25
SO3 1.88 2.03 2− during calcination.
MgO 1.29 1.18 0.92
SO3 increased by 18% in the calcined and treated sample (Table 2). Francolite, the phosphoric mineral
Fe2O3 1.52 1.26 1.16
of almost
Al2O3
all sedimentary 2.56
phosphorites, has a variable2.14chemical composition that can be represented by
1.55
(Ca, Mg, Sr, Na) (PO , SO , CO ) F . We hypothesized that a part of the CO 2− of francolite was
SiO2 10 4 3.08 4 3 6 2–3 12.4 3 9.81
CO2 14.78 1.95 1.95
F 2.50 2.45 2.20

Relevant trace element concentrations are provided in Table 3. During the beneficiation process,
the cadmium content was significantly reduced from 30 mg/kg to 14 mg/kg. Many countries have legal
limits for the cadmium content in fertilizers [42,43] so that reducing the cadmium content early on in
Minerals 2020, 10, 937 6 of 13

substituted by SO4 2− during calcination in addition to the conventional substitution between PO4 3−
and CO3 2− .
Relevant trace element concentrations are provided in Table 3. During the beneficiation process,
the cadmium content was significantly reduced from 30 mg/kg to 14 mg/kg. Many countries have
legal limits for the cadmium content in fertilizers [42,43] so that reducing the cadmium content early
on in the process is a positive side effect of heat treatment of phosphate rock and can be pursued
deliberately by controlling the treatment temperature and the oxygen content within the reactor [10].
At temperatures >750 ◦ C, cadmium can be transferred to the gaseous phase and removed through the
air pollution control system. Depending on the process parameters and the targeted cadmium removal
rate, up to 95% cadmium can be removed from most sedimentary phosphate rock types. Electrostatic
precipitation, wet scrubbing, and/or baghouse filters are usually installed for gas cleaning.

Table 3. Relevant Trace Elements in Untreated, Calcined, as Well as Calcined and Treated Sra Ouertane
(Layer A1) Phosphate Rock.

Element Untreated Phosphate Rock (mg/kg) Calcined Phosphate Rock (mg/kg) Calcined and Treated Phosphate Rock (mg/kg)
Cd 30 26 14
Cr 160 93 74
Mn 67 48 42
V 66 45 43
Zn 214 207 142
U 60 68 79
Th 25 29 34

The uranium and thorium contents were increased since volatile constituents in the phosphate
rock were driven off. The uranium content at Sra Ouertane reported in the literature (see Table 1)
could reach higher concentrations than the uranium concentration that was ultimately measured in
the samples here. The uranium concentration measured here would most likely be too low to enable
commercially viable uranium recovery [44–47].
Relevant REE concentrations of the Sra Ouertane low-grade phosphate rock are provided in Table 4.
The Sra Ouertane phosphate rock deposit showed relatively high REE concentrations by Tunisian [48]
and international [9,49] standards, and recovering REEs might be attractive when developing the
ore [8,50,51]. During the beneficiation process, all REEs were concentrated as volatile constituents
were driven off.

Table 4. Relevant Rare Earth Elements (REEs) in Untreated, Calcined, as Well as Calcined and Treated
Sra Ouertane (Layer A1) Phosphate Rock.

Untreated Phosphate Rock Calcined Phosphate Rock Calcined and Treated Crustal Abundance
Element
(mg/kg) (mg/kg) Phosphate Rock (mg/kg) (mg/kg) [52]
Ce 220 240 285 67
La 161 175 192 39
Nd 67 76 89 42
Pr 29 37 49 9
Sm 28 34 47 7
Y 66 76 88 33

The particle size distribution was another important parameter for phosphate rock calcination.
The particle size of the Sra Ouertane (layer A1) phosphate rock is provided in Figure 5 after sieving
with 250 µm ASTM sieves. The particle size distribution of the untreated (Figure 5), calcined (Figure 6),
as well as the calcined and treated (Figure 7) phosphate rock, was provided. Calcination slightly
increased particle diameters. After calcination, less than 25 vol% of the phosphate rock particles
had an equivalent particle diameter below 10 µm. The characteristic peak of particles at 100 µm
was present in all stages. It is important to emphasize that the lab-scale experiments conducted here
might result in very different particle size distributions than the ones obtained from industrial (rotary
kiln) calcination that might, for instance, impose larger friction on the material during processing.
The effect of disliming or removal of particles with an equivalent diameter of 60 µm in a hydro-cyclone
could best be observed by the difference in particle distribution after calcination and after disliming.
Minerals 2020, 10, 937 7 of 13

The disliming step conducted on the lab-scale here successfully removed the largest share of small
Minerals 2020,
particles that10 7 of 13
Minerals 2020, 10were unwanted in further wet acid processing. 7 of 13

Figure 5. Particle size distribution in vol% of untreated Sra Ouertane (layer A1) phosphate rock.
Figure 5. Particle size distribution in vol% of untreated Sra Ouertane (layer A1) phosphate rock.

Figure 6. Particle size distribution in vol% of the calcined Sra Ouertane (layer A1) phosphate rock.
rock.
Figure 6. Particle size distribution in vol% of the calcined Sra Ouertane (layer A1) phosphate rock.
Minerals 2020, 10, 937 8 of 13
Minerals 2020, 10 8 of 13

Minerals 2020, 10 8 of 13

Particle size
Figure 7. Particle size distribution
distribution in
in vol%
vol% of
of the
the calcined
calcined and
and treated
treated Sra
Sra Ouertane
Ouertane (layer
(layer A1)
A1)
Figure 7. Particle size distribution in vol% of the calcined and treated Sra Ouertane (layer A1)
phosphate rock.
phosphate rock.
XRD analysis
XRD analysis was
was conducted
conducted to to better
better understand
understand the the effect
effect of
of the
the concentration procedure on
concentration procedure on
XRD analysis was conducted to better understand the effect of the concentration procedure on
the phosphate
the phosphate rock.
rock. The
The diffractogram
diffractogram of of the
the XRD
XRD analysis
analysis was was characterized
characterized by by aa number
number of of typical
typical
the phosphate rock. The diffractogram of the XRD analysis was characterized by a number of typical
peaks
peaks found
found in
inother
other natural sedimentary phosphate rocks (see forfor
instance [32,33,53]) andand
revealed the
peaks found in othernatural
naturalsedimentary
sedimentaryphosphate rocks
phosphate rocks (see
(see instance
for instance [32,33,53])
[32,33,53]) revealed
and revealed
presence
thethe of the
presence following
ofof
the phases: Fluorapatite
following (Ca (PO 4 )6 F42)),
6Fquartz (SiO 2 ), and carbonates, which are
presence the followingphases:
phases:Fluorapatite
Fluorapatite10Ca Ca10 (PO 2), quartz (SiO 2), and carbonates,
10(PO4)6F2), quartz (SiO2), and carbonates, which
which
mostly
areare present
mostly
mostly
in
present the form
presentininthe
of
theform
calcite (CaCO
formofofcalcite
calcite(CaCO
). Figure
(CaCO33).
3 8
). Figure
shows
Figure 88 shows
the
showsthe XRD
theXRD pattern
XRDpattern of the
patternofoftheuntreated
the Sra
untreated
untreated
Ouertane
SraSra phosphate
Ouertane
Ouertane phosphaterock.rock.
phosphate rock.

Figure
Figure XRD
8. 8. pattern
XRD patternofofthe
theuntreated Ouertane(layer
untreated Sra Ouertane (layerA1)
A1)phosphate
phosphate rock.
rock.
Figure 8. XRD pattern of the untreated Sra Ouertane (layer A1) phosphate rock.
Calcination
Calcinationreduced
reducedthe
theCO CO22 content
content of the Sra Ouertane
Ouertane oreoresignificantly.
significantly.Figure
Figure 9 shows
9 shows thethe
Calcination
diffractogram
diffractogram reduced
of of
the XRD
the the
XRDanalysisCO2ofcontent
analysis ofthe Sraof
theSra the Sra phosphate
Ouertane
Ouertane Ouertane rock
phosphate ore
rocksignificantly. Figure
aftercalcination
after calcination and
and 9without
shows
without thethe
diffractogram
characteristic ofcalcite
characteristic the XRD
calcite (CaCOanalysis
(CaCO3 )
3 ) peak
peak of the
that
that Sra
can
can Ouertane
be
be phosphate
observed
observed in
in Figure
Figurerock
8.
8. after
Besides, calcination
Besides, the CaO
the CaO and
peaks
peakswithout
resulting the
resulting
from
from carbonate
characteristic
carbonate decomposition
calcite (CaCO3) peak
decomposition could
could well-identified
thatbecan be observedinin
well-identified inthe calcined
Figure
the phosphate
8. Besides,
calcined therock
phosphate CaO (Figure
rockpeaks 9).
resulting
(Figure 9).
from carbonate decomposition could be well-identified in the calcined phosphate rock (Figure 9).
Minerals
Minerals 2020,
2020, 10
10, 937 99 of
of 13
13
Minerals 2020, 10 9 of 13

Figure 9.
9.9.XRD
Figure
Figure XRDpattern
XRD patternof
pattern ofthe
of thecalcined
calcinedSra
calcined Ouertane
SraOuertane (layer
Ouertane(layer A1)
(layerA1) phosphate
A1)phosphate
phosphate rock.
rock.
rock.

During
During
During disliming,
disliming,
disliming, smaller
smaller
smaller particles
particles<60
particles <60
<60 were
µmμm removed
were
were using
removed
removed a hydro
using
using cyclone.
aahydro
hydro The XRD
cyclone.
cyclone. The
The pattern
XRD
XRD
of pattern
pattern of of
thethe
the calcined calcined
and
calcined andSra
treated
and treated SraOuertane
Ouertane
treated Sra Ouertane phosphate
phosphate rock
rockisisprovided
rock is provided
phosphate inin10.
in Figure
provided Figure
The10.
Figure The
absence
10. absence
The of peaks
absence
of of peaks
related
peaks related
torelated
CaCO toCaCO
and
3 to CaCO
CaO3 3wasandnoticeable.
and CaO was
CaO was noticeable.
noticeable. The
The only
only remaining
The only remaining mineral
remaining mineral
species species
were
mineral were
fluorapatite,
species were
fluorapatite, quartz,
quartz, and silicates.
fluorapatite, and silicates.
quartz, and silicates.

Figure 10. XRD pattern of the calcined and treated Sra Ouertane (layer A1) phosphate rock.
Figure 10.
Figure XRDpattern
10. XRD patternof
ofthe
thecalcined
calcinedand
andtreated
treatedSra
SraOuertane
Ouertane (layer
(layer A1)
A1) phosphate
phosphate rock.
rock.
All three XRD patterns are depicted together in Figure 11. Shown is the diffractogram of the
All three
three
untreated
All XRD patterns
phosphate
XRD patterns are depicted
depicted
rock (SRT-DP),
are together
the calcined
together in Figure
Figurerock
phosphate
in 11. (SRT-CAL),
11. Shown isis the
Shown the diffractogram
as well of the
as the calcined
diffractogram of the
and treated
untreated
untreated (SRT-CALT)
phosphate
phosphate rock Sra Ouertane
rock (SRT-DP),
(SRT-DP), the phosphate
the calcined
calcined rock (bottom
phosphate
phosphate to top). Theas
rock (SRT-CAL),
rock (SRT-CAL), ascomparison
well as
well the of
as the the
calcined
calcined
different
and treated XRD patterns
(SRT-CALT) showed
Sra a significant
Ouertane reduction
phosphate rock of calcite
(bottom to(CaCO
top). 3) again
The
and treated (SRT-CALT) Sra Ouertane phosphate rock (bottom to top). The comparison of the and thus
comparison proved
of the that
different
thepatterns
XRD process, showed
on a laboratory scale, reduction
a significant significantly increased
of calcite the 3P)2O
(CaCO 5 content.
again and thus proved that the process,
different XRD patterns showed a significant reduction of calcite (CaCO3) again and thus proved that
on aprocess,
the laboratory
on ascale, significantly
laboratory increased theincreased
scale, significantly P2 O5 content.
the P2O5 content.
Minerals 2020, 10, 937 10 of 13
Minerals 2020, 10 10 of 13

Figure 11. XRD

Figure 11. XRD patterns
patterns of
of the
the calcined
calcined and
and treated
treated (SRT-CALT),
(SRT-CALT), calcined
calcined (SRT-CAL),
(SRT-CAL), as
as well
well as
as
untreated (SRT-DP) Sra Ouertane (layer A1) phosphate rock.
untreated (SRT-DP) Sra Ouertane (layer A1) phosphate rock.

4. Conclusions
4. Conclusions
In total, the P2 O5 content could be increased from some 20.01 wt% (untreated ore) to 27.24 wt%
In total, the P2O5 content could be increased from some 20.01 wt% (untreated ore) to 27.24 wt%
(calcined and treated ore). To reach merchant grade P2 O5 concentrations of at least 30 wt%, further
(calcined and treated ore). To reach merchant grade P2O5 concentrations of at least 30 wt%, further
processing steps would be required. If, for instance, the relatively high silica content of 9.81 wt% could
processing steps would be required. If, for instance, the relatively high silica content of 9.81 wt%
be reduced to some 2.5 wt%, phosphate concentrate with 30.2 wt% P2 O5 would result as a final product.
could be reduced to some 2.5 wt%, phosphate concentrate with 30.2 wt% P2O5 would result as a final
It is important to emphasize that even though additional processing steps for further ore concentration
product. It is important to emphasize that even though additional processing steps for further ore
are required, the first steps described here are valuable and may help promote the use of Sra Ouertane
concentration are required, the first steps described here are valuable and may help promote the use
low-grade phosphate rock ore in a sustainable manner.
of Sra Ouertane low-grade phosphate rock ore in a sustainable manner.
Author Contributions: Conceptualization, N.A. and N.H.; methodology, N.A.; writing—original draft preparation,
Author
N.H. andContributions: Conceptualization,
N.A.; writing—review and editing, N.A. and N.H.;
all authors. methodology,
All authors have readN.A.; writing—original
and agreed draft
to the published
version of theN.H.
preparation, manuscript.
and N.A.; writing—review and editing, all authors. All authors have read and agreed to the
publishedThis
Funding: version of the
project manuscript.
received funding from the IAEA in Vienna as part of CRP: T11006 [54].
Funding: This projectThe
Acknowledgments: received funding
authors from the
are grateful IAEA
for in Vienna
funding from as
thepart of CRP:
IAEA that T11006 [54].research possible.
made this
The views expressed may have not been endorsed by the sponsoring agency. Any remaining errors, omissions,
Acknowledgments:
or inconsistencies areThe authors are
the authors’ grateful for funding from the IAEA that made this research possible. The
alone.
views expressed may have not been endorsed by the sponsoring agency. Any remaining errors, omissions, or
Conflicts of Interest: The authors declare no conflict of interest.
inconsistencies are the authors’ alone.

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

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