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Upgrading of phosphate ores - a review

Article in Powder Handling and Processing · May 2007

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UPGRADING OF PHOSPHATE ORES – A REVIEW
Abdel-Zaher M. Abouzeid
Cairo University, Faculty of Engineering, Department of Mining, Giza, Egypt.

ABSTRACT: The world production of marketable phosphate rock exceeded 145 million ton in 2006. about 95
percent of this production is utilized in fertilizer industry. The marketable phosphate is usually 30 percent P2O5 or
higher. The run-of-mine material is mostly of lower grade which needs processing or upgrading. The processing
techniques depend on the type of phosphate minerals existing in the ore as well as the associated gangue minerals.
Some times, simple, inexpensive techniques are enough to produce the required grade. For example, Crushing
and screening is used to get rid of the coarse hard siliceous material, and attrition scrubbing and desliming is used
to remove the clayey fine fraction. If silica is the main gangue material, single stage or double stage flotation is the
conventional mineral processing technique used in this case. If the ore is igneous carbonatitic alkaline or ultra
basic phosphate deposit, crushing, grinding, scrubbing, and flotation associated with other steps such as magnetic
and or gravity separation is proved to be successful in upgrading this type of ore. The sedimentary phosphate
ores having carbonate-apatite (francolite) as the main phosphate mineral and containing carbonates ( Calcite
and/or dolomite) and / or considerable amount of organic matter represent a challenge in the field of phosphate
concentration due to similarity in the physico–chemical properties of surfaces of the constituents of the ore.
Calcination is one solution to upgrade such type of ores, but it is indicted with some drawbacks. This overview
discusses and summarizes the State-of-the Art and the existing efforts to overcome these problems and to
produce a high grade phosphate product suitable for fertilizers and other phosphate chemical industries.

Keywords: Phosphate ores, processing technology

1. INTRODUCTION

Phosphorus is an element which is very essential in

the agricultural sector in the form of fertilizers and
animal feed stocks. Approximately 95% of the world
phosphate rock production is consumed in fertilizer
manufacturing. Most of the balance is processed, in
electric furnaces, into elemental phosphorus which is
the main raw material for making industrial
phosphates [1,2]. Economic recovery of phosphates
is limited to naturally concentrated phosphate
mineral deposits. Occasionally natural concentrations
are enough to be used as mined; generally, however,
the ore is low grade and must be concentrated for
economic utilization. Physical as well as thermal Figure 1. World phosphate production rate since 1850
treatment techniques are used for concentrating the [2, 19]
run of the mine phosphates. More than 40 countries
produce phosphate rock around the world. In 2005, 1.1. Types of Phosphate Rocks
the world phosphate production reached 148 Mt, out
of which 143 Mt were produced by sixteen major There are five major types of phosphate resources in
phosphate producing countries (countries whose the world [3]:
production exceeds 1 million tons per year)[2,8].
These countries, arranged according to their • Marine phosphate deposits.
production capacities from high to low, are: USA, • Igneous phosphate deposits.
Morocco, China, Russia, Tunisia, Jordon, Brazil, • Metamorphic deposits.
Israel, Syria, South Africa, Egypt, Australia, Senegal,
• Biogenic deposits.
India, Togo, and Canada. Only 5 Mt are produced by
all other countries. Figure 1 shows the growth curve • Phosphate deposits as a result of weathering.
of the world annual phosphate production since the
year 1850, when the first world phosphate The world phosphate resources are distributed,
production was recorded [2]. according to their type, approximately as follows:
75% sedimentary marine deposits, 15-20 % from
igneous, metamorphic and weathered deposits, and
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 11

2-3% from biogenic resources (bird and bat guano Figure 2 shows the location of major phosphate rock
accumulations). producers as well as some of the known phosphate
deposits not yet in production [1].

Figure 2. Location of the major phosphate rock-producing areas of the world and some of the known deposits not
now in operation [1]

1.2. Mineralogical, Chemical and Textural may be replaced in part by uranium, lanthanide rare
Characteristics of Phosphate Minerals earths or certain other trace metals such as cadmium,
zinc, magnesium, strontium and barium. In some
Phosphate minerals occurring in the primary cases chlorine occurs in place of part of the fluorine.
environment include[3]: The extent to which substitution occurs and what the
substitutes are, depend on the prevailing conditions
• Flour-apatite (Ca10(PO4)6F2), found mainly in when the apatite was formed and on the influence of
igneous and metamorphic environments, for subsequent events, such as weathering. In
example, in carbonatites, and mica-pyroxenites, sedimentary deposits of marine origin, the phosphate
• Hydroxy-apatite (Ca10(PO4)6(OH)2), found in material occurs in admixtures with detritus materials
igneous, metamorphic environments but also in such as quartz, mica and clay, often with limestone
biogenic deposits, e.g. in bone deposits. and occasionally with dolomite. Igneous apatites may
contain other impurities, not commonly found in
• Carbonate-hydroxy-apatite
sedimentary deposits, originating from other
(Ca10(PO4,CO3)6(OH)2), found mainly on islands
constituents of the magma from which the apatite
and in caves, as part of bird and bat excrements,
crystallized [4].
guano.
• Francolite (Ca10-x-yNaxMgy(PO4)6-z(CO2)z 1.3. Techniques and Measurements Used to
F0.4zF2),This complex carbonate-substituted
Identify Phosphate Minerals
apatite is found only in marine environments,
and to a much smaller extent, also in weathering
The most important techniques used for identifying
environments, for instance over carbonatites.
phosphate minerals are [3]:
The ability of anions to substitute for phosphate in
• X-ray diffraction (XRD) for mineralogical
apatite is not restricted to F-, CO3-2 and OH-, found
analysis.
in the differing variants of apatite. Silicate, vanadate,
aluminate, titanate and arsenate may also occur in • X-ray Fluorescent (XRF) for elemental
place of part of the phosphate. Likewise, calcium analysis.
12 Volume 9 - Issue 17

• Scanning Electron Microscope (SEM) for available at costs comparable to those 20 or 30 years
grain interaction and spot analysis. ago. It has been widely suggested that, in general,
• Infra Red methods (IR) for detection of there have been a continuous decrease in world
surface-layer structure. phosphate rock quality as reserves of high-quality
• Micro-probe analysis for elemental rock are being depleted. As the high-grade phosphate
distribution in the matrix. deposits are becoming depleted, the quality of
phosphate rock that is utilized on a worldwide basis
• Microscopic identification for mineralogy
is decreasing. High P2O5 content equates to low
and grain interrelation.
impurity content, high yields per ton of material
• Analytical chemical methods. shipped, handled and processed, increased reaction
• Measurement of refractive indices. efficiencies, fewer processing problems and less
• Porosity and pore size distribution waste. An industry assessment suggests that the
measurements. phosphate content of pre-beneficiated ore is already
• Surface area measurements. decreasing by around 1% per decade [4].
• Thermal Analysis (DTA), (TGA).
• Unit-Cell dimensions (a-value), and crystal Estimates of world phosphate reserves and
size. availability of exploitable deposits vary greatly and
assessments of how long it will take until these
1.4. The Main Parameters of Phosphate reserves are exhausted also vary considerably.
Furthermore, it is commonly recognized that the
Characterization
high quality reserves are being depleted expeditiously
and that the prevailing management of phosphate, a
There are several parameters that are used in
finite non-renewable source, is not fully in accord
characterizing phosphate rocks. Among these
with the principles of sustainability. A 50% world
parameters are[3].
population increase over the next 50 years would
point towards an increase in global food needs by at
• Unite-cell a-dimension (a-value), a
least a proportionate figure, assuming roughly
crystallographic expression of the
constant per capita cereal consumption. As demand
composition of the apatite composition. The
for food increases, this may result in bringing into
a-cell dimension is expressed in Angstrom (1
agricultural use more land, but certainly will bring a
A=10-10 m).
requirement for increased yields, thus increasing
• Refractive index. fertilizer demand. Hence, agricultural phosphate use
• Solubility data based on chemical extraction may increase faster than world population [5].
methods, e.g. neutral ammonium citrate
solubility (NAC). Depletion of current economically exploitable
• PO4/CO3 ratio as a measure of carbonate reserves are estimated at somewhere from 60 to130
substitution in phosphate minerals. years. Using the median reserves estimates and under
• Surface area (expressed in m2 g-1), and pore reasonable predictions, it appears that phosphate
size distribution indicating potential reserves would last for at least 100+ years. Increasing
reactivity [11]. demand and increasing prices will make more
reserves economically exploitable [5-7]. Based on the
The calcium phosphate content of phosphate rock is present rate of production, about 150 Mt/a, and the
expressed in different world areas by one of the available extractable reserves, 18 billion ton, the life
following terms [1]: time of these known reserves is about 120 years [2].

BPL (bone phosphate of lime) 2. BENEFICIATION OF PHOSPHATE

TPL (triphosphate of lime) ORES
P2O5 (phosphorus pentoxide)
P (phosphorus – not commonly used) Because of the increasing demand on phosphate rock
for fertilizers, it is becoming more and more
An illustration of relationship between the above common to mine and process low grades of
terms is: phosphate deposits. The majority of these low grade
80 % BPL == 80% TPL == 36.6% P2O5 == 16% P. deposits are of sedimentary phosphates and the rest
are of different origins. These deposits occur in the
High-grade phosphate rock is available from several form of ore bodies in one thick bed or several
sources, such as Togo, Senegal and Morocco. successive beds intercalated with non-phosphatic
However, premium rocks from these sources are not materials.
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 13

Phosphate ores show a wide diversity in the solubility and reactivity. Further more, as a result
composition of their gangue materials but generally of the low calcination temperature; the reduction
fall into one of the following categories, based on the of calcium sulphate, present in the ore, to
major associated gangue materials [8]: corrosive calcium sulfide by the organic matter is
minimized. During burning the organic matter,
1. Siliceous ores: These contain quartz, chalcedony the following two conditions must be satisfied:
or different forms of silica. Such ores could be organic carbon must be decreased to less than
upgraded economically by such techniques as 0.3% to minimize gassing in the wet phosphoric
flotation or gravity separation methods. acid processing, and apatite CO2 must be
maintained at a level close to 2% to allow good
2. Clayey ores: these mainly contain clays and reactivity to the calcined product [12-14].
hydrous iron and aluminum silicates or oxides as
gangue materials. These impurities could be 5. Phosphate ores containing more than one type
removed by simple beneficiation techniques such of the gangue minerals: many of the sedimentary
as scrubbing and washing. In some cases, phosphate deposits contain mixtures of
dispersing agents would be necessary. undesired constituents. These ores require series
of upgrading operations in their flow sheets
3. Calcareous ores of sedimentary origin: these depending on the type of gangue minerals
contain calcite and dolomite as the major existing in each ore. This may include, after size
impurities with small amounts of silica. It is reduction, combination of attrition scrubbing,
usually difficult to remove the carbonate desliming, flotation, gravity separation, and/or
minerals efficiently from such ores by such calcination. Each flow sheet is to be designed
techniques as flotation [9, 10], or by physical after thorough characterization of and testing on
separation methods. This is because the physical a representative sample of the ore under
properties of carbonates and phosphates are very exploitation.
similar. Separation by physical means even
becomes impossible when the carbonate 6. Igneous and metamorphic phosphate ores: the
minerals are finely disseminated into the main gangue materials in these ores are sulfides,
phosphate particles. Recent experimental results magnetite, carbonates.(calcite, dolomite, siderste,
11 showed that the flotation techniques applied and ankerite), nepheline syenite, pyroxenite,
on a calcareous ore may be effective only if the foskorite, etc. Processing of these ores may
phosphate can be liberated from the gangue include after crushing and grinding, washing,
materials. In the case of the unaltered ores, desliming, magnetic separation, and flotation
complete liberation is achieved only with depending on the types of gangue minerals
extremely fine grinding. Consequently, partially present. However, flotation is a common step in
liberated flotation feed must be used to avoid all of them [1].
loss of selectivity resulting from fine grinding.
Under such conditions high concentration ratios About 20% of the world’s phosphate rock now
cannot be reached. For upgrading such type of comes from the mining and beneficiation of igneous
ores, crushing and screening may be used if there deposits, but this percentage will drop as production
are differential friability differences between from sedimentary deposits increases. Igneous apatite
phosphates and carbonates. However, recovery in relatively small quantities has been recovered from
in this case may be unreasonably low. An veins and from magnetite ore bodies where it occurs
alternative technique for upgrading these ores is in minor amounts. The important igneous apatite
calcination. Calcination is the process of heating deposits of commercial interest are found in certain
the ore to a high temperature ranging from 800o intrusive complexes of alkalic rocks. Commonly near
to 1000oC to decompose the CaCO3 to CaO and the center are veins and larger bodies rich in
gaseous CO2. The CaO formed is then removed carbonates (calcite, dolomite, siderite, and ankerite)
as calcium hydroxide by quenching and washing. emplaced either in a molten condition or by
metasomatic processes. The calcareous deposits of
4. Phosphate ores with organic matter, some times the igneous phosphate rocks are called carbonatites.
called "black phosphates"[12]: Ores of this type
are generally upgraded by heating the ore up to World production of apatite (igneous) concentrates
about 800oC. This type of calcination burns the in 1980 was about 25 Mt. Table 1 lists most of the
organic material and the residual organic carbon operating apatite mines in the world in 1985. Brazil is
without significantly affecting the superior actively developing new apatite mines; in 1985 its
qualities of the sedimentary phosphates such as production of phosphate rock, largely igneous
14 Volume 9 - Issue 17

apatite, was estimated to be 5.8 Mt, compared to 1.7 all other apatite mines in the world, are surface
Mt in 1980. The Russians developed new operations operations. Foskor, in South Africa, developed
in the Kola area and have new mines operating on additional large mine-beneficiation operations on the
apatite in the Lake Baikal region in Siberia. Some of Phalaborwa carbonatite complex. Carbonatites have
the Russians apatite mines in the Kola Peninsula are been found in Australia in 1968, New Zealand in
underground, but the majority of its mines, as well as 1970, and early in 1980s in Paraguay [1].

Table 1. World Apatite Mines in 1985 [1]

No.
Concentrate, Grade,
Country No. Mines Beneficiation Type Deposit
1000 t/a % P2O5
Plants
Nepheline syenite
USSR (Kola) 6 2 20 17
(unweathered)
South Africa Pyroxenite and foskorite
2 1 3.5 7
(Phalaborwa) (unweathered)
1 carbonatite (unweathered)
Barzil 5 3 5.8 13.5-15 4 carbonatite weathered
residuals.
Zimbabwe
1 1 1 7 Alkalic complex.
(Dorowa)

by desliming and / or classification. Such

3. TECHNIQUES FOR UPGRADING technique is successfully used to upgrade
PHOSPHATE ORES the Red Sea Coast phosphate rock in Egypt.

There are several beneficiation techniques for b) It is also used when the associated gangue
upgrading phosphate ores. The choice of one of minerals are mainly coarse silica or chert
these techniques depends on the type of ore as well chips. In this case, phosphorites are
as the associated gangue minerals. Among these collected from under the screens in a wet
techniques are: process. This may also be practiced to
separate a coarse phosphate-rich fraction
1. Size reduction and screening: this technique ahead of a flotation section such as in
utilizes the differences in differential friability Florida plants [1-15].
between phosphate minerals and associated
gangue and cementing matrix (carbonates, silica, 3. Electrostatic separation: In combination with
and silicates). In most cases, phosphate minerals attrition, desliming, and gravity separation, the
are friable while gangue minerals are hard. Here, electrostatic separation was successful in
high percentage of P2O5 is lost in the coarse upgrading phosphate ores by removing silica and
fraction. Air elutriation may be practiced to get /or carbonates, mostly on laboratory scales.
rid of the very fine fraction that is rich in clays. However, the low capacity of the electrostatic
An example of using this technique is the separators limits their use for large scale
beneficiation plant of the Nile Valley phosphate production. This technique is used to
rock at East Sibaeya area, Egypt. There the main concentrate phosphate ores of different types.
beneficiation facilities are crushing and screening The following are examples of the ores
to recover the phosphate product in the fine responded to the electrostatic separation:
fraction.
a) A calcareous ore (from North Africa) was
2. Attrition scrubbing and classification. Some of upgraded using electrostatic separation to
the operations using this technique are listed produce a concentrate assaying: 32.9 % P2O5
below: at 80 % P2O5 recovery from a feed assaying
24.1 % P2O5 [16].
a) This technique is used when the main
gangue minerals are clays. Clays are b) Abu-Tartour ore, Eastern Desert, Egypt
characterized by their fine size, loosely (containing quartz, ankerite, gypsum and
bound grains with the phosphorite pellets. pyrite) produced a concentrate assaying 33%
Attrition in water liberates and disperses the P2O5 at recovery of 71.5% from a feed
clay particles in water and they are removed assaying 27.5 % P2O5 [17]..
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 15

c) A siliceous ore (from Qusseir, Red Sea P2O5 and the phosphate concentrate assays
Coast, Egypt) produced a concentrate 29–30 % P2O5 at a recovery of 70 % [24].
assaying 33.8 % P2O5 at 70.3% recovery
from a feed assaying 16.5% P2O5 [18] . 5. Flotation: More than 60% of the marketable
phosphate in the world is produced by flotation
d) A siliceous ore (from Hamadat mine, Red [25].
Sea Coast, Egypt) produced a concentrate
assaying 30 % P2O5 at a recovery of 76.3 % a) Siliceous ores: The common technique for
from a feed assaying 18.2 % P2O5 [19]. processing siliceous phosphate ores is the
anionic-cationic flotation technique. If there
e) One of the few plants that used electrostatic is any carbonate minerals, it will report to
separators on an industrial scale, was the the phosphate concentrate [26-28].
Pierce plant in Florida, USA. The plant used
to upgrade phosphate flotation-concentrate b) Carbonaceous ores: phosphate minerals and
using electrostatic separators. The feed carbonate minerals ( Calcite and dolomite)
assayed 32.9 % P2 O5 and 11.3 % insoluble, exhibit very similar surface chemical
and the final concentrate assay was 35.3 % properties. Sedimentary phosphates are
P2 O5 and 5.6 % insoluble [20]. more sensitive to the similarity in surface
chemical properties of these minerals. This
4. Magnetic separation: when one of the major makes their separation by flotation a
gangue constituents is magnetic, magnetic challenging problem [29-32].
separators are used as one of the steps in the
flow-sheet to remove the magnetic constituents. Much research has been carried out to try to reduce
This is mostly used in the beneficiation of the calcium carbonate content of phosphate rocks by
igneous phosphate rocks. However, it has also flotation and/or calcination [33]. Hignett et al. [34]
been used for upgrading some sedimentary claimed that flotation seems to work best on ores
phosphate ores. The following are examples of containing well-crystallized carbonates. When the
plants using magnetic separation in their flow- ore contains soft or chalky carbonates the flotation
sheets: results were less satisfactory. This was the case of
East Mediterranean and North Africa ores where the
a) The complex igneous phosphate deposit at carbonate crystals are intergrown so that the
phalaborwa ( South Africa) is upgraded in phosphate is not liberated by comminution until the
three stages [21]: rock is too fine for flotation [35, 36].

1. copper flotation However, as discussed previously, it is obvious that

2. magnetic separation the problem of separating carbonates from
3. The non-magnetic fraction is subjected to phosphates in the sedimentary rocks is seriously
flotation to float apatite The Run-Of-Mine, complicated, and a brief survey on the latest efforts
ROM, to this plant assayed 7 % P2O5 , and for solving this problem is due. The currently used
the phosphate concentrate assay was more commercial process of double flotation is not
than 36 % P2O5 at a recovery of 75-80 % adequate for reducing the dolomitic impurity level to
P2O5 . less than 1.0 % by weight MgO in the concentrate,
as stipulated by the phosphate industry. During the
b) In the Brazil's long established apatite ( past decade, studies conducted by investigators in the
igneous) beneficiation plants, magnetic Florida phosphate industry [38-41] and the
separation followed by desliming and Tennessee valley Authority [42] have resulted in the
flotation are included in the phosphate development of a number of processes. However, all
concentration plants. Ores assaying 7-15% these studies originated on a bench scale and the
P2O5 are upgraded to produce concentrates fundamentals involved in the separation scheme have
assaying 36 to 38% P2O5 [22, 23]. not been established. This leads to serious
limitations for optimization of these processes and
c) The dolomitic–pyritic sedimentary also their use for beneficiating ores of different origin
phosphate ore of Abu-Tartour phosphate and composition.
deposit in Egypt is subjected to high
intensity magnetic separation, after Recently, Moudgil and Chanchani [43, 44] and Ince
desliming, to separate the feebly magnetic [45] have conducted some fundamental studies which
ankerite. The feed assays about 22-26 % resulted in the development of two processes for the
16 Volume 9 - Issue 17

removal of dolomite from apatite. Extension of these particles probably as a replacement of dissolved
fundamental studies to beneficiate the natural ores gypsum, and
on a bench scale was also reported [46]. Also, Shong
et al. [47] have attempted a systematic optimization b) The mild attack on calcite particles
of some variables using a three stage flotation accompanied by the evolution of tiny CO2
scheme with various reagents. bubbles on the surface.

To help understand the collector adsorption Johnston and Leja [60] continued the effort to
mechanisms in the phosphate- carbonate systems, understand the complex nature of the phosphate-
more extensive investigations were conducted to carbonate systems. Flotation behavior of two apatite
clarify the effect of the addition of organic and samples and a dolomite sample were investigated in
inorganic salts on the surface charge of the two presence of oleic acid and soluble phosphate
species, apatites and carbonates[48-53]. These studies solutions. They concluded that:
established firmly that phosphate ions function as
potential determining ions for apatites, while Ca++ a) Flotation of apatite is prevented by the
ions act as either potential- determining ions [56] or depressing action of soluble phosphate ions in
specifically adsorbed ions [57-59] for apatites. In the acid solutions, whereas dolomite floats readily
case of calcite, both Ca++ and carbonate ions have in presence of such ions.
been shown to be potential-determining ions for the
mineral [51-54]. Flotation behavior of apatites and b) If gypsum is present in the flotation feed,
carbonates was conducted under various excessive quantities of phosphate ions are
experimental conditions [56-60]. needed for the depression of apatite because
of a fast metathesis reaction between gypsum
Smani et al. [52] provided a comprehensive review of and orthophosphate ions. This reaction can
electrophoretic studies of phosphates and associated be completely suppressed by the addition of
calcareous gangue minerals, together with flotation suitable quantities of sulfate ions, which is
results of selective separation of phosphate oolites exactly opposite to the findings of Mitzmager
and calcite. In their investigation, it was shown that and co-workers [61].
H+, OH-, Ca++, and HPO4-2 function as potential–
determining ions for apatites. They also c) Following the findings reported by Bertolucci
demonstrated that adsorption of sodium and co-workers [62, it was suggested that the
dodecylsulfonate and dodecylamine chloride on depressing action of phosphate ions on apatite
phosphate surface is due to electrostatic attraction is due to the formation of a more strongly
while adsorption of oleate at pH greater than 6 is due hydrogen-bonded phosphate-water layer
to a chemical binding energy between oleate ions and around apatite particles than around dolomite
surface sites of the phosphate particles. Between particles. Evolution of CO2 from dolomite or
about pH 5.5 and 6.5 , the phosphated-surfce calcite, in acidic solutions, disturbs the
particles were sharply depressed , whereas their hydrogen bonding around these particles. This
flotation recovery increased at pH 4. Depression of allows an immediate adsorption of collector
such particles between pH 5.5 and 6.5 was explained and results in dolomite or calcite flotation.
to be due to the lack of adsorption of the collector,
whatever the concentration may be. The flotation at Moudgil and Chanchani [44] used two-stage
pH 4 was suggested to be due to adsorption of conditioning process for the flotation of dolomite
neutral molecules in the vicinity of the isoelectric from apatite. The mixture of minerals (dolomite +
point, IEP. Mitzmager and Co-workers [61] dealt apatite) was first conditioned at pH 10 in presence of
with the effect of soluble alkali phosphate salts on a fatty acid collector. The system was then
oleate flotation of calcite from phosphate slimes. reconditioned below pH 4.5 where dolomite was
They tested the selective depressing action of soluble floated. Soto and Iwasaki [63] showed that in a
alkali phosphate salts on phosphate minerals. The mixture of francolite and dolomite, the primary
authors concluded that the mechanisms of the amines were uniquely selective towards the
depression of phosphate and activation of calcite by phosphate mineral. In a phosphate ore, primary
soluble alkali phosphate is due, at least, to two amines were adsorbed mainly on the phosphate
parallel effects: indicating that stronger interaction existed between
the amine and francolite than between the amine and
a) The adsorption of molecular dicalcium dolomite. The US Bureau of Mines developed a
phosphate (CaHPO4) on the phosphate process to separate carbonate (calcite) from
phosphate minerals occurring in the unaltered
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 17

phosphate ores of Phosphate Formation [64]. The c) The phase boundary line between hydroxyl-
process uses fluosilicic acid to depress the phosphate apatite and CaHPO4(S) occurring at pH 4.6 is
while floating the calcite with fatty acid emulsion. shifted towards more acidic pH values when
Another US Bureau of Mines report of investigation dissolved Ca++ is added to the system, and
dealt with the beneficiation of high-magnesium towards less acidic pH values when soluble
phosphate from Southern Florida [65]. Several phosphate salts are added to the system.
depressants such as starch, fluosilicic acid, sodium This may explain why it is relatively easy to
borate, lactic acid, sodium biphosphate, phosphoric depress apatites in acid media in absence of
acid, and acetic acid failed to depress phosphate carbonates, while the same thing cannot be
minerals. A technique of sizing, grinding, desliming, achieved when natural ores are treated.
scrubbing, redesliming, and flotation was then
devised to treat three southern Florida high-MgO These theoretical analyses were proceeded a step
phosphate ores. Moudgil, et al. [66] described further [31] in order to assess the most important
flotation process based on the depression of apatite conditions for separation of carbonates from
with sodium chloride in acid medium and flotation of phosphates. The final conclusion of this study was
dolomite with fatty acids. When this process was that: “Concentration of calcium - phosphate
applied to a natural phosphate ore, it was possible to complexes, in the solution, in equilibrium with all
float dolomite from apatite at pH=4. Hanna and apatites increases with the decrease of pH and with
Anazia 28 described a flotation process developed by the increase of added soluble phosphate, oxalate, and
Alabama Mineral Resources Institute (MRI) for sulfate salts; but sharply decreases by adding or
selective fatty acid flotation of carbonates from dissolving calcium salts”. To sum up this theoretical
sedimentary apatites in the pH range of 4-6 without discussion, two conditions seem essential to be
conditioning of the pulp prior to flotation. The fulfilled in order to achieve selective flotation of
success of the process is based on the fact that fatty carbonates from apatites in acid media (pH 5.5-6.0).
acids adsorb more rapidly onto carbonate surfaces These are: minimizing Ca++ and /or increasing
than onto phosphate surfaces. Carbonates are floated HPO4-2 in the carbonate/apatite/water system.
in slightly acidic circuit immediately upon the
addition of the collector and frother, then the pulp is The following are examples for separating carbonates
conditioned briefly, and the phosphates are floated from phosphates, on the laboratory scale, by
from the siliceous constituents with no further flotation:
addition of collector in most instances.
a) The USBM treated a sedimentary ore
Important as they are, these studies have not (carbonate-apatite in addition to pyrite, Ca &
provided an understanding of the mutual effects of Mg carbonates and silica). Three-stage
phosphate and carbonate minerals on each other. flotation operation was adopted starting with
This shows the need for a thorough thermodynamic flotation of pyrite using xanthates. They
analysis of the phosphate-carbonate systems in added H2SiF6 as depressant for phosphate
aqueous solutions. minerals, and used anionic collector to float
the carbonates followed by cationic flotation
Simultaneously, in 1978/1979, two studies were to remove silica. The phosphate concentrate
published by Johnston and Leja [66] and Elgillani assayed 29 % P2O5 at 69 % recovery from a
[29] on the analytical aspects of the feed assaying 19.9 % P2O5 (see Fig.3) [69].
calcite/apatite/water system. These analyses showed
that the control of dissolved Ca++ in the system b) A thermodynamic analysis of the apatite-
seems to be the key to achieve selective flotation of calcite system was carried out at Cairo
carbonates, especially calcite, from apatite. Based on University 32. It showed that at pH = 5.8, it
thermodynamic analysis of the apatite /calcite / is possible to float carbonates from
water system that was carried out in these studies, it calcareous sedimentary phosphate ores. A
was concluded that: flotation scheme was designed such that the
pH value was kept constant around 5.8
a) Depression of apatite is probably related to during conditioning and flotation of a
its instability in acid media. deslimed sample. Flotation continued until
barren froth was observed. Both the
b) Concentrations of aqueous calcium carbonate float and phosphate concentrate
phosphate complexes such as CaHPO4 and were filtered, washed, dried, weighed, and
CaH2PO4+ increases with the decrease in pH analyzed. Using this scheme, the following
of the system. results were obtained for samples from two
18 Volume 9 - Issue 17

mines from the Red Sea Coast phosphate phosphate ores, are tremendous. Most of these
rock, Egypt (see Tables 2 and 3). efforts are documented by the Florida Institute of
Phosphate Research, FIPR [70]. This extremely
As a matter of fact, the efforts spent in solving the important publication is a collection of abstracts of
problems of separating carbonates from phosphate most of the published material on phosphate
ores, particularly in the case of sedimentary concentration all over the world since 1930.

Table 2. El-Hegab El-Shemali Phosphate Sample (the feed assayed 23% P2O5) (ref.32). The feed particle size
range was -125 + 25 microns, and pH was in the range of 5.7-5.9.
Product P2O5 , % Insoluble, % LOI, % P2O5Rec., % Modifying Reagents +
Carbonate Float 16.9 2.71 27.34
2.4 kg/t H2 SO4 *
Phosphate Conc. 28.7 3.12 12.42 65.1
Carbonate Float 16.92 2.61 27.39
2.8 kg/t H2 C2 O4 *
Phosphate Conc. 30.85 2.87 10.63 62.37
Carbonate Float 14.57 2.53 28.96
2.1 kg/t H3 PO4 *
Phosphate Conc. 31.51 3.10 10.51 67.75
Carbonate Float 15.1 2.96 28.6
6.4 kg/t KH2 PO4 **
Phosphate Conc. 32.99 3.22 9.42 67.18
Carbonate Float 16.2 2.84 27.52 1.6 kg/t KH2 PO4 **
Phosphate Conc. 30.1 2.95 10.93 64.00 1.6 kg/t H2 SO4
Carbonate Float 15.0 2.72 28.87 1.6 kg/t KH2 PO4 **
Phosphate Conc. 33.4 2.93 9.2 64.7 2.4 kg/t H2 C2 O4
Carbonate Float 18.0 2.94 22.62 5.1 kg/t H3 PO4 ***
Phosphate Conc. 30.66 1.48 8.71 61.9 1.7 kg/t H2 SO4
Carbonate Float 17.39 2.22 23.66 5.7 kg/t H3 PO4 ***
64.9
Phosphate Conc. 31.26 1.1 8.5 1.9 kg/t H2 C2 O4
+Phosphate depression and pH controller, collector was 0.6 kg/t in all experiments.
*Reagent was added during conditioning and flotation.
**KH2PO4 was added before conditioning and pH was adjusted by H2SO4 and/or H2C2O4.
***Reagents were added as mixed solutions during conditioning and flotation.

Table 3. Hamrawain Phosphate Sample (the feed assayed 19.0% P2 O5) (ref. 32). The feed particle size range was -
125 + 25 microns, and pH was in the range of 5.7-5.9.

Product P2O5 , % Insoluble, % LOI, % P2O5Rec., % Modifying Reagents +

Carbonate Float 10.51 6.0 31.25

2.2 kg/t H2 SO4 *
Phosphate Conc. 27.62 3.38 11.55 68.51
Carbonate Float 8.49 5.47 33.47
4.0 kg/t H2 C2 O4 *
Phosphate Conc. 30.0 3.22 9.8 77.96
Carbonate Float 7.11 5.94 34.6
2.96 kg/t H3 PO4 *
Phosphate Conc. 31.65 3.17 7.8 79.91
Carbonate Float 7.44 5.5 35.5
9.6 kg/t KH2 PO4**
Phosphate Conc. 31.84 2.45 7.54 79.7
Carbonate Float 7.63 6.41 34.06 3.2 kg/t KH2 PO4**
Phosphate Conc. 30.81 2.77 8.21 77.62 1.5 kg/t H2 SO4
Carbonate Float 7.45 5.87 34.3 2.4 kg/t KH2 PO4 **
Phosphate Conc. 31.91 2.8 7.45 78.13 2.0 kg/t H2 C2 O4
+Phosphate depression and pH controller, collector is 0.8 kg/t in all experiments.
*Reagent was added during conditioning and flotation.
** KH2PO4 was added before conditioning and pH was adjusted by H2SO4 and/or H2C2O4

4. THERMAL TREATMENT OF with specific properties. The main objectives behind

PHOSPHATE ORES heating up the ore are:

More than 10% of the world marketable phosphates i) Removing water

are produced by calcinateion. Traditionally, heat 120-150º C Drying
treatment of phosphate ores is defined as heating up
the ore to a certain temperature to obtain a product ii) Removing organic matter
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 19

650-750º C Calcination iv) Removing fluorine

iii) Dissociation of carbonates up to 1350oC Defluorination
850-1000oC Calcination

Figure 3. Beneficiation of partially altered sedimentary phosphate rock containing carbonates, silica, and pyrite as
the main gangue material [69]

Drying, which is a common step in the wet a) Almost all these heat treatment operations are
processing of phosphates, is categorized under preceded with ore preparation such as:
thermal treatment, but it is not included under the crushing, grinding, sizing and / or classification,
term calcination. and possibly flotation, to get rid of some of the
liberated impurities at one or more of these
stages.
20 Volume 9 - Issue 17

b) Calcination of phosphate ores is necessary for an animal feed supplement. The product is
obtaining a phosphate product suitable for the essentially a solid solution of calcium
production of light green phosphoric acid, phosphates as well as calcium silicate. The
which is in turn suitable for the production of principle reaction is shown below. No attempt
pure super phosphoric acid. This last product is has been made to balance the equation, which
used in the preparation of pure chemical comprises of a far more complex set of
reagents, soft drinks, and other pharmaceutical chemical reactions [74]:
preparations. There are two types of calcination
operations. 3[Ca3(PO4)].CaF2(s) + SiO2(s) + NaOH (aq) +
H3PO4(aq) Æ 3Ca3(PO4)2.Na3PO4.Ca2SiO4(s) +
One is associated with organic matter. In this 2HF(g)
operation, the ore is heated up to 650-750oC to
burn the organic matter and to oxidize the Figure 4 shows a schematic flow sheet for the
residual carbon. In this case, exothermic defluorination process of the phosphate rock [73].
reactions (as a result of burning organic matter
and oxidizing residual carbon) take place at this
level of temperature. The organic matter in the
ore contributes appreciable amounts of the heat
requirement for calcination [71].

The other type of calcination of phosphate ores

is carried out for the dissociation of carbonates.
The calcination temperature in this case ranges
from 850-1000oC [71]. The dissociation of
carbonates is highly an endothermic reaction
which requires large fuel consumption. The
suggested dissociation reaction goes as follows
[72]:

CaCO3 + Heat Æ CaO + CO2 +42.9 kcal/mole

c) Defluorination is the process of obtaining
fluorine-free highly purified forms of
Figure 4. Delfuorination process of phosphate rocks
phosphorus-containing products to be used as [73]
supplements in livestock and poultry feeds,
with phosphorus in water soluble forms. These 4.1. Energy Consumption in Thermal
products are essential for the health of the Treatment of Phosphate Ores
animals. Since fluorine is toxic to animals, it
has to be removed almost completely by The amount of energy for mining and physical
defluorinating the phosphate ores. beneficiation of phosphate ores to produce one ton
of commercial rock phosphate (32% P2O5) is
Defluorinated phosphates are produced by approximately 0.9 GJ/tonne of rock phosphate
adding defluorinating agents, such as
(about 2.9 GJ/tonne P2O5). However, if the rock is
phosphoric acid and soda compounds, in calcined, the total energy requirement is doubled [75].
controlled amounts to phosphate rock and Considering all the major factors consuming heat in
calcining the mix at temperatures ranging from the calcination process, the heat required to produce
about 1370 oC to 1510 oC – conditions that
one kg of calcined phosphate from a raw feed
drive off the fluorine and converts the containing about 50 % calcium carbonate and 10 %
unavailable phosphate to the biologically moisture was found to be in the range of 800 kcal/kg
available form. The process transforms of calcined product. This amount of heat is
phosphate mineral to the defluorinated
equivalent to about 0.15 kg of coal of calorific value
phosphate with a P/F ratio of more than 100. in the range of 7000 kcal/kg of coal. This amounts
Calcined product is cooled and screened to to 3.6 GJ/ton of calcined product [76].
defluorinated phosphate rock (DFP) or tri-
calcium phosphate (TCP) [73]. Because it has a It was reported by Bandyopadhyay 71 that the
low enough fluoride to phosphorus ratio, and calcination process involves drying of beneficiated
the phosphorus is bio-available, it is suitable as phosphate rock ( from 10-15 % moisture down to 1-
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 21

3 % moisture) followed by calcination at temperature d) Eliminating the foaming phenomenon

of about 800oC. The data provided by during acid attack of the calcined phosphate
Bandyopadhyay was basically for the treatment of the products. These solves technical problems,
North Carolina phosphate ores. This type of ore caused by the presence of organic matter
contains organic matter as the main impurity in the and/or carbonate minerals, and saves the
ore. For this reason the cost for the calcination costs of the defoaming reagents.
process was considerably low. He reported US$ 1.68
/ short ton for drying and US$ 3.49/short tone for e) The capital costs of the calcination plants are
drying and calcination at 800oC based on the 1999 comparable with the drying units which are
cost level. In this case, the energy consumption for commonly included in the wet beneficiation
calcination was very low due to the presence of flow-sheets.
organic matter which supplied most of the
calcination heat during burning. The energy cost for f) The special products obtained by high
the defluorination of phosphates at 1350o C was in temperature treatment (super phosphoric
the range of US$ 36.2/short tone of product [71]. It acid and defluorinated phosphates) are
is thought that the feed to the defluorination plant highly demanded and highly priced.
was also a North Carolina phosphate rock, which
means that for defluorination of a calcareous ore, Any way, the final decision for obtaining the required
with little or no organic matter, the energy required phosphate product will be taken based on thorough
will be higher. analysis of the economic and technical assessment of
the process and on the available type of ore that will
4.2. Limitations and Benefits of High be used as the initial feed.
Temperature Treatment of Phosphate Ores
4.3. Types of Thermal Treatment Units
There are several factors that are traditionally known
as drawbacks for the calcination of phosphate ores There are various types of units for calcination of
[19, 67,77]. Among these factors are: phosphate ores. These include:

a) High capital cost of calcination plants. a) Vertical shafts [1, 80, 81].

b) Energy extensive operation. b) Fluidized bed reactors [72, 78, 79].

c) Low reactivity products. c) Rotary kilns [1,80].

d) It usually affects gypsum filtration rate, d) Traveling grate kilns [81].

adversely [73].
e) Traveling grate-rotary kiln systems 1,81.
On the other hand, there are factors that are in favor
of phosphate calcination. Among these factors are: f) Flash calciner [1, 12-14, 80, 82, 83].

a) Upgrading of the ore, reduces the tonnages Readers may be referred to the cited references for
to be treated for the same P2O5 units, and , detailed designs, and operating techniques, and
hence reduces costs for transportation and advantages of each of the above units.
fertilizer and/or phosphoric acid production.
4.4. Industrial Calcination Plants
b) Reduces the amount of sulfuric acid required
for acidulation of the ore in the subsequent Worldwide phosphate calcining capacity in
chemical processing. 1981 was about 14 Mt/a. About 75 % of world
calcination is treated in Dorr-Oliver FlouSolids
c) In most cases, the drawback of low reactivity systems. Allowing 85% equipment availability,
of the calcined product could be avoided by
the yearly design capacity was 8.9 Mt/a.
controlling calcinations temperature below
800oC when the main impurities are organic Actual production is probably 120 % of design
matters. In this type of phosphate ore, with capacity, or 14.3 Mt/a for all calcining
high organic matter content, burning of installations. These installations are designed
organic matter is exothermic (evolves heat) to reduce the organic content of phosphate
which saves energy. rock. However, in Algeria, the calciners, which
22 Volume 9 - Issue 17

are operated at higher temperatures, are used to calcination plants for the removal of organic
drive off CO2 from carbonates. Table 4 gives matter as well as calcite [1].
the most important world phosphate
Table 4. World Phosphate Calcining Capacity, 1981 (ref. 1)
Installation Location Calcination Units Design Capacity, t/d
Djebel Onk Algeria 3 3000
OCP Morocco 2 3700
Beker Idaho 4 5830
Simplot Idaho 4 5000
Stauffer Wyoming 3 2000
Texas Gulf North Carolina 6 9000
Total 22 28530

4.5. Effect of Substituting Carbonates on the Maslennikov and Kavitskaya [89] and Alden and
Characteristics of Carbonate-Apatite Lindqvist 90 recognized that the a-axis in apatite
containing both fluoride and carbonate ions would
The apatite in phosphorites and rock phosphates be short (9.32 to 9.35 Å ) compared to the a-axis of
usually are poorly crystallized [33, 37]. Their igneous and metamorphic apatite (9.38 to 9.40 Å)
compostions differ considerably from those of pure that contain fluoride ions with almost no carbonate
fluorapatite or hydroxy-apatite. Their X-ray ions. Such variations in the a-dimension indicate that
diffraction patterns are typically apatite with slight the excess CaF2 or CaCO3 cannot be simply
shifts that show changes in the cell parameters [77]. adsorbed on the surface of the apatite crystals, but it
As already mentioned, most sedimentary may correspond to some regular type of overgrowth
phosphorites contain considerable amounts of that leads to a series compounds with end-members
carbonate [85], up to 6.3 % of the phosphate general formulae of [84]:
mineral, and are often considered to be carbonate-
apatite or francolites [84]. Gruner and McConnell Ca10(PO4)6F2...Ca10-a-bNaaMgb(PO4)6x(CO3)xF2 . Fy
[98] found small distinct changes in the intensities of
certain francolite reflexions from those of apatite Electroneutrality of the above equation is preserved
reflexions. However , Hendricks and Hill [86] when a= x–y. Experimentally it was found that
reported that X-ray goniometer photographs of y=0,4x where x varies from near zero to 1.5 and b =
francolite crystals are indistinguishable from those of 0.4a. These end-members correspond to the
apatite crystals, although theoretically they should. chemical composition shown in Table 5. The
Altschuler et al. [87] presented X-ray evidence for maximum degree of substitution was found for
carbonate flourapatite as a distinct variety of apatite carbonate-francolite type apatite when x/(6–x ) ≈
rather than a mixture of a carbonate phase and 0.3. The most significant feature revealed is that the
flourapatite, Silverman et al. [88] investigated the relative increase in amounts of F, Mg, Na, and CO2 is
differences in X-ray patterns of carbonate- accompanied by a decrease in P2O5 content and
fluorapatite, hydroxy-apatite, and fluorapatie. They nearly constant CaO content [85].
detected the presence of carbonate in the structure of
carbonate-apatite and differentiated it from that of
fluorapatite.

Table 5. Comparison between the chemical constituents of fluorapatite and francolite (ref. 77).
Constituent, % Fluorapatite (x = 0) Francolite (x/(6-x) ≈ 0.3)
CaO 55.6 55.1
P2O5 42.2 34.0
CO2 0.0 6.3
F 3.77 5.04
Na2O 0.0 1.4
MgO 0.0 0.7

Apatite prepared with increasing contents of the a-axis. As no phase other than apatite is
carbonate and decreasing content of phosphate detectable from the X-ray patterns, it was concluded
exhibit proportional changes in the dimensions of that the carbonate is a substitute for the phosphate
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 23

within the structure. Smith and Lehr22 indicated that This means that the release of CO2 from carbonate-
there is a reasonable correlation between the total apatite is easier than from calcite probably due to
fluorine content and the carbonate content and the internal stresses inside the carbonate-apatite
length of the a-axis. The increase in carbonate structure. It should be noted that the two samples are
content in the lattice structure would cause a of the same ore sample with the calcite-free sample
decrease in the a-axis of the unit cell. Lehr [92] prepared by dissolution of calcite using Silverman
confirmed the findings of McClellan and Lehr [84] solution (Tri-ammonium citrate solution) [100].
and showed that there is a progressive change in the
unit cell dimension as (CO3+F) replaces (PO4) and
that the minimum length of the a-axis corresponds to
a high substitution of carbonate.

The increase in carbonate and fluorine substitution

will lead to a decrease in crystallite size . Crystallite
sizes range from microscopically coarse crystals for
igneous and metamorphic apatite to submicroscopic
crystallites, only a few hundred Angstrom units, in
the most highly substituted sedimentary apatite.
LeGeros et al. [93] concluded that the presence of
carbonate causes diminution in size and a change in
the shape of apatite crystallites. Carbonate-free
apatite are thin, elongated crystallites while the
apatite rich in carbonate are more spheroidal
Figure 5. Weight loss as a function of calcination
crystallites with a length–to–thickness ratio temperature for the two Jordanian calcareous
approaching unity. They also concluded that the phosphate samples (an orginal sample and a calcite-
changes in size and shape possibly were due to the free sample) [77, 98]
formation of weak bonds by carbonates, and that the
growth of a crystal is less in the general direction of Phosphate ores of high carbonate content could be
the formation of weak bonds than in the general beneficiated by heating the rock to temperatures
direction of the formation of strong bonds. between 600 and 950 oC. This removes free and
combined moisture and most of the carbon dioxide
Cuthbert and Rowland [94] studied the differential [101, 102]. Clay, iron and aluminum oxides, if
thermal analysis of ten different carbonate minerals present in the phosphate ores, are very harmful
and found that they dissociated at different impurities in the calcination process. If the ore is not
temperatures. All the carbonates showed washed, the clay will be hardened by dehydration,
endothermic reactions caused by dissociation, but and sometimes it may form silicates with magnesium
siderite showed an exothermic reaction caused by the and calcium oxides that are responsible for some
decomposition of FeCO3, which gives FeO which is technical troubles and clinker formation in the kiln
immediately oxidized to Fe2 O3 [94, 95]. The especially at calcination temperatures about 1100oC
differential thermal curve of calcite showed an 101,103. Washing the ore before calcination, therefore,
intense broad endothermic reaction starting at about is very important. The calcination temperature plays
625oC and ending at about 893oC with a peak at 840 a decisive role in determining the time required for
oC. The aragonite curve also showed a broad hydrating the lime. Petrographic studies showed that
endothermic reaction starting at about 600 oC. In the phosphate samples heated at 1200oC contained free
same direction, Faust 96 made several studies using CaO, some undecomposed CaCO3, slaked CaO,
differential thermal analysis to differentiate between clinker material in a glass phase, and, in some cased,
magnesite and dolomite and between calcite and gypsum. The undecomposed CaCO3 was found in
aragonite 97. Silverman et al.88 were able to detect the single grains or mixed with aggregates of CaO [101,
carbonate associated as calcite from bound carbonate 104].
in carbonate-bearing apatite by means of DTA
analyses. Confirmation of these findings was 4.5.1. Characteristics of Calcined Phosphate
observed by El-Jallad [98] and Abouzeid et al. [77] Product
for two francolite phosphate samples; one includes
associated calcite and the other is calcite-free sample. The thermograph of the material to be calcined as a
Figure 5 shows that the rate of dissociation of function of temperature is different from one type of
carbonate-apatite (the Calcite-free sample) is higher phosphate ore to the other depending whether the
than that of the sample containing associated calcite. ore contains organic matter, carbonate minerals , or
24 Volume 9 - Issue 17

both of them as the main gangue material. If organic thermograph for a phosphate ore containing
matter is dominating, the reaction will be exothermic, carbonates and organic matter as the main gangue
and less energy is required to initiate the reaction constituents [98]. In this figure, there is a series of
(Figure 6) [12]. It should be noted that there is an weak endothermic reactions as a result of moisture
exothermic reaction between 625 ºC and 800 ºC evaporation and removal of water of crystallization
probably due to recrystallization of the carbonate- with a possibility of overlapping an exothermic effect
apatite constituents. With carbonates, e.g. about 50 with a peak at 470º C due to burning of organic
% calcite, as gangue minerals, with little or no matter. There is also a strong exothermic reaction
organic matter, the reactions will be endothermic with a peak at 750º C, probably due to
needing around 400 kcal/kg of heat energy for recrystallization of the carbonate-apatite, followed by
dissociation of carbonates [76], Figure 7. a strong endothermic reaction caused by the
dissociation of calcite [98]. Differential thermal
analyses were also done on different phosphate
samples from different localities in Jordan by Rosh
and Saadi [107]. They noticed that there was an
endothermic moisture peak between 100 to 200oC,
two strong exothermic peaks at temperatures from
300 to 400oC and 730 to 770oC, and strong
endothermic carbonate doublet peaks between 795
to 815oC and 830 to 890oC.

Figure 6. Differential thermal analysis for a Moraccan

phosphate ore, rich in organic matter [12]

Figure 8. Differential thermal analysis for a Jordanian

phosphate ore containing organic matter and
calcareous gangue material [98]

4.5.2. Effect of Calcination on Physical

Properties of the Phosphate Rock.

4.5.2.1. Unit Cell Dimensions and Crystal Size:

Figure 7. Differential thermal analysis for the Chemical analysis of calcined phosphate showed
dissocation of calcite [98] higher P2O5 grade in the phosphate product after
calcination [101-111]. Stolovitskaya [113] pointed
This is a large amount of heat energy to be supplied out that the degree of recrystallization of CaO
to the system for calcination. When both organic depends mainly on the calcinations temperature.
matter and carbonate minerals exist, the thermograph Decomposition of the adsorbed and combined
reflects exothermic peaks, endothermic peaks and water, burning of organic matter and most of the
interference regions where both exothermic and combined carbon dioxide increase the phosphate
endothermic reactions overlap [98]. In this case the grade in the calcined product.
amount of heat energy needed for calcination will
depend on the relative existence of the two Freeman et al. [114] Ando and Matsono [115] found
constituents, organic material and carbonate that the a-axis of the unit cell started increasing when
minerals. Figure 8 shows the differential the carbonate-apatite was heated above 500oC.
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 25

When heated above 900 oC, it reached the value of

the a-axis of fluorapatite. The X-ray diffraction peaks
of fluorapatite became more distinct and stronger by
calcination above 700 oC. They attributed this
behavior to crystal growth of apatite through the
combination of fine crystals of the initial phosphate
forming larger crystals, which upon calcination at
about 950 oC, resembled Kola apatite. Smith and
Lehr [116] found that the major effect of calcining
carbonate apatite above 800 oC was the evolution of
carbon dioxide with a consequent increase in crystal
size and the recrystallization of stoichiometric
fluorapatite and the segregation of isotropic CaO and
CaF2. They also found that the loss of carbon
dioxide of the carbonate apatite, by calcination, Figure 9. The unit cell dimension (a-axis) as a
caused an increase in the unit cell a-axis. Abouzeid et function of calcination temperature for two Jordanian
al. [77] obtained similar results concerning the phosphate samples (an original sample a calsite-free
increase in the a-axis and the growth of crystal size as sample) [77, 98]
the calcination temperature increases. The value of
the a-axis of the unit cell increased from 3.335Å at
room temperature to 3.364Å after calcinations at 950
oC (Figure 9). The crystal size of the phosphate

mineral was increased from 500Å at room

temperature to 2200Å after calcination at 950 oC
(Figure 10). It can be noted that the presence of
calcite and/or calcium oxide does not affect the
values of a-axis or the crystal size at all calcination
temperatures. Masslenikov and Kavitskaya [89]
noticed an increase in the length of the unit cell a-
axis of the carbonate-apatite after calcination. This
increase was due to the loss of carbon dioxide in the
carbonate-apatite. Lately, Blazy and Bouhaouss [12]
reported that the value of the a-axis of the unit cell
continuously increased with temperature until it Figure 10. The mean crsytal size of phosphate
reach 9.357Å at 950 oC when calcination was carried minerals as a function of calcination temperature
out for four stages in a flash calcination system. [77]

4.5.2.2. Surface Area, Porosity, and Material Density: Porosity: The porosity of the phosphate rock
sometimes increases with increasing temperature up
Surface area: Freeman et al.[114] reported that the to about 700 oC and then decreased from this level
specific surface area of the calcined product of on as in the case of the Utah phosphate rock 114. In
phosphate rock decreased with increasing calcination some other phosphates, such as the Morocco
temperature. They carried out their tests on two phosphate, the porosity gradually decreases with
different phosphate samples from Morocco and increasing temperature and then suddenly falls to
Utah. There was a sharp decrease in specific surface minimum at about 700 oC [114]. The porosity trends
area with increasing temperature in both samples suggest the destruction of the pore systems in both
between 500 oC and 800 oC, with the Morocco samples for both the macro pres and Micro pores,
sample more pronounced in the density decrease. but particularly the fine pores. For the Morocco
They attributed this remarkable change in surface sample the destruction of pores was quiet severe
area to the aggregation of elementary fine grains in which may be reflected on the reactivity of the
this temperature range suggesting that consolidation calcined product. It is worthy to mention that in the
of these very small grains occurs at these case of the Utah sample, the gradual incrase of
temperatures. It may also be possible that the porosity in the lower range of temperature ( below
destruction of the pore structure of the rock in this 500 oC) may be explained on the basis of
temperature range contributes to the drastic decrease volatilization of organic matter [114].
in specific surface area of the sample as will be
discussed later.
26 Volume 9 - Issue 17

Density: It was observed that there is little change in in a mixture of sulfuric and phosphoric acid showed
particle density below 750 oC. Above this a remarkable decrease in their chemical reactivity.
temperature, some changes in density occur, where Lehr [92] and Smith and Lehr [116] studied the
the density slightly increases with increasing solubility behavior (chemical reactivity) of 17
calcination temperature. The particle density roughly phosphate rocks before and after calcination by using
reflects the internal collapse of the particle porosity neutral ammonium citrate solution for the reactivity
between temperatures, of 650 oC to 750 oC. The true measurements. They found that the chemical
density is almost not affected by the calcination reactivity decreased slightly above 600 oC owing to
temperature except at relatively high temperatures the annealing of phosphate crystals. However, there
where crystal transition may take place and cause the was a sharp drop in the chemical reactivity of the
density to be lower [114]. phosphate rock after calcination avobe 750 oC caused
by recrystalization. It reached its lowest value when
4.5.3. Effect of Calcination on Chemical calcined at about 950 oC owing to extensive crystal
Reactivity of the Calcined Product growth. Henger and Pacl [105] found that the
chemical reactivity of calcined phosphates decreased
The chemical reactivity was found to be a reasonable as the calcination temperature increased and reached
measure of the suitability of the the phosphate rock. its lowest value at 900 oC. They used in their studies
The solubility behavior of phosphorus in mild 2 percent citric acid, 0.25 N nitric acid , 0.25 N
solvents such as citric acid, neutral ammonium sulphuric acid, and 0.25 N phosphoric acid. They
citrate, and alkaline citrate provides a very good attributed the drop in chemical reactivity of the
indication of relative reactivity. The amount of calcined phosphate, at about 900 oC to an alteration
soluble phosphate extracted from a certain quantity of carbonate-apatite to fluorapatie and to a decrease
of phosphate rock in a certain volume of solvent in the specific surface area. El-Jallad [98] found that
under specific conditions is called the relative this decrease in chemical reactivity could be caused
solubility or reactivity of the rock. Diluted mineral by changes in crystal structure, crystal size, and the
acids may also be used for measuring the relative presence of CaCO3 and CaO in the product.
reactivity of the phosphate rock.

The reactivity of a phosphate rock is an inherent

property of the mineral that influences its rate of
reaction with acids 114. It seems also that the
occurrence of the phosphate minerals as well as their
associated constituents and the extent of the physical
and chemical changes as a function of calcination
temperature are highly effective factors on the rate of
dissolution of the phosphorus in various acid
references. The phosphate rock reactivity is a strong
function of the unit cell dimension, a-value. Figure
11 shows the trend of the chemical reactivity of some
phosphate samples as a function of the unit cell
dimension [3, 77]. This figure demonstrates that the
reactivity of phosphate rocks decreases with
increasing the a-value of the unit cell. Figure 11. The solubility index as a function of the
unit cell dimension a-value of the phosphate minerals
[3, 77]
The chemical reactivity of the phosphate rock with a
solution of 2 percent citric acid decreased slightly
It has been reported that rocks from different
upon calcination at 500 oC because of the decrease in
geographic deposits respond differently, from the
porosity. It also decreased sharply when the
physical and chemical aspects, to calcinations.
phosphate rock was calcined above 900 oC as a result
Changes in some cases are negligible, and in some
of changes in unit cell dimensions, crystal growth,
other cases are highly remarkable. Table 6 gives
decrease in porosity and surface area as mentioned
some examples of the change in reactivity indices of
before. Treatment of the phosphate rock in an 0.25
some phosphate samples from different geographic
N hydrochloric acid showed a slight decrease in
locations [71, 77, 114]. It is obvious from Table 6
reactivity after calcination. This decrease, however,
that the reactivity index is different for different
was not significant compared to the original
phosphate deposits differing in geographic locations.
uncalcined phosphate rock. The rate of
It also shows that the drop in reactivity index of the
decomposition of phosphates calcined above 900 oC
A.M. Abouzeid/The Journal of ORE DRESSING ® 2007 27

calcined product can be as high as 88% of the amount of calcium carbonate and calcium oxide
uncalcined rock and as low as 5%. Also, due to the affect the reactivity index to a noticeable extent.
limited amount of dissolving acid, the relative

Table 6. Percent relative reactivity of some phosphate rocks of different geographic locations,
using neutral ammonium citrate solutions (ref. 77,114).
Reactivity
Geographic Percent of
index of Calcinations
location of the reactivity index of Remarks
uncalcined temperature, C
o
deposit uncalcined rock
phosphate rock
Jordanian CO2(total) = 19.1%
24 950 12.5
phosphate CO2(apatite)=6.1%
Jordanian Calcite-free
43 950 41.9
phosphate CO2(apatite)=6.1%
Morocco CO2(total) =5.2%
87 910 53.4
phosphate CO2(apatite)=4.8%
CO2(total) =2.7%
Utah phosphate 60 775 89.7
CO2(apatite)=1.6%
CO2(total) =4.6%
Peru phosphate 75 900 93.8
CO2(apatite)=4.2%
Florida CO2(total) =2.4%
52 815 95.0
phosphate CO2(apatite)=2.2%

SUMMARY minerals are removed by magnetic separation, and

clays and fine impurities are removed by attrition
Techniques for beneficiation of phosphate rocks scrubbing and desliming.
depend on the type of the phosphate deposit, the
phosphate minerals existing in the ore as well as the Phosphate ores containing high content of organic
associated non-phosphatic material. Simple material as the main ingredients are processed by
beneficiation techniques such as crushing and calcination at about 500 to 750 oC to burn out the
screening or scrubbing and desliming are successfully organic material. Sometimes, calcination temperature
used when the main gangue material is hard siliceous is higher than this range, which may be as high as 800
oC to burn the residual carbon. At this low range of
material, silicates and/or clayey material.
temperature, physical and chemical properties of the
Ores containing quartz, chalcedony or different phosphate minerals are not significantly affected and
forms of silica, may be upgraded using gravity hence, the reactivity index of the phosphate is not
and/or electrostatic techniques. However, the use of remarkably affected. The reactions taking place as a
these techniques for large scale production is limited result of raising temperature are exothermic reactions
due to their limited capacities. The main which does not need large additional amount of
conventional concentrating technique for such ore is energy. The calcined product in this case is suitable
flotation. Flotation in this case is carried out either in for the manufacture of clear green phosphoric acid
one stage or two-stage operation. The one stage which is used as a source for producing super
technique is mainly to float the phosphate minerals phosphoric acid and other high grade chemical
using oleic acid or sodium oleate with the addition of reagents.
fuel oil (kerosene) as collectors at pH=8. the two-
stage process includes, in addition to the previous The calcareous sedimentary phosphate ores form the
step, decreasing the value of pH to 4, skimming the main challenging problem in phosphate processing.
desorbed oleic acid, and adding cationic collector to Electrostatic and gravity separation are not yet up to
float the trapped silica. This technique produces a the large scale production techniques. Extensive
clean high grade phosphate product. efforts have been spent to use flotation, which is the
most widely technique used in processing most of
Igneous phosphate rocks are concentrated mainly by the ores with different modifications and
anionic flotation of phosphates. The flow-sheet for developments, for upgrading the calcareous
upgrading this type of ore may include intermediate sedimentary phosphate ores. On the laboratory scale,
steps depending on the type of gangue minerals some of these approaches were successful, but they
associated with the phosphate minerals. If sulfides are not tested in pilot or industrial scales. The rest of
exist, they are removed by flotation. Magnetic these efforts were neither practical nor successful. To
28 Volume 9 - Issue 17

utilize these natural phosphate deposits, some of [1] Emich, G. D., 1984, Phosphate Rock
them are being calcined and/or defluorinated. "Industrial Minerals and Rocks, vol. 2, pp.
Although these products are of inferior quality with 1017-1047.
respect to the chemical reactivity and extensive
amounts of energy are used, they are almost pure [2] Jasinski, S. M., 2007 "Phosphate Rock," USGS,
products suitable for producing high grade chemical pp. 120-121
reagents and/or defluorinated phosphates for animal
feed stocks. These calcines are of high quality and [3] Straaten, P. V., 2002, " Rocks for Crops , Agro
are sold as expensive commodities for special minerals of sub-Sahara Africa, " pp. 7-24
purposes. In the case of using these products for
producing phosphoric acids defrothing reagents are [4] USGS survey , Mineral Commodity Summaries,
not needed, and filtration of residual solids are made Jan 2003, Global Reserves and Availability.
easier.
[5] Haarr, A., 2005, " The Reuse of Phosphorus,"
Researches for economic and technical utilization of Eureau Position paper EU2-04-SL09,pp. 1-2
the huge calcareous phosphate deposits around the
world are urgently needed. Thorough understanding [6] Steen, I., 1998, Kemira Agro, in Phosphorus
of the thermodynamics of the and Potassium, Issue no. 217, Proceedings
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that are more selective to phosphate or carbonate
minerals is another incentive to apply flotation in [7] Evans, T. D., and Johnston, A. E., 2004,
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carbonates for better particle/collector interaction Yearbook, Vol.56, pp. 1-10.
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concentrating phosphates on industrial scale may Bangkok, Thailand, Minerals Resources
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ACKNOWLEDGEMENT
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The author would like to thank Dr. Bhaskar and Metallurgical Processing vol. 22, no. 2,pp.
Bandyonadhyay, consultant, Professor Peter van 107-115.
Straaten from the University of Guelph, Canada,
Miss Karen Stewart, Librarian at Florida Institute of [13] Henin, J. P. and Lectard, A., 1983, Engineering
Phosphate Research, and the phosphate Staff at the and Mining Journal, vol. 10,pp. 77-84.
United States Geological Survey for their close
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author, generously, with the necessary information Minerals, Mines and Carrieres, Les
regarding the subject. The author's appreciation is Technologues, pp. 249-252.
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patience in typing the draft of the paper and [15] Phosphate Rock Processing, Mineral Products
reproducing the attached Figures. Industry, Emission Factors, 1993, Section 11.
21, pp. 1-10. [www.epa.gov]
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