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 physicochemical 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 treatment techniques are used for concentrating the run of the mine phosphates. More than 40 countries produce phosphate rock around the world. In 2005, the world phosphate production reached 148 Mt, out of which 143 Mt were produced by sixteen major phosphate producing countries (countries whose production exceeds 1 million tons per year)[2,8]. These countries, arranged according to their production capacities from high to low, are: USA, Morocco, China, Russia, Tunisia, Jordon, Brazil, Israel, Syria, South Africa, Egypt, Australia, Senegal, India, Togo, and Canada. Only 5 Mt are produced by all other countries. Figure 1 shows the growth curve of the world annual phosphate production since the year 1850, when the first world phosphate production was recorded [2].

Figure 1. World phosphate production rate since 1850 [2, 19]

1.1. Types of Phosphate Rocks

There are five major types of phosphate resources in the world [3]: Marine phosphate deposits. Igneous phosphate deposits. Metamorphic deposits. Biogenic deposits. Phosphate deposits as a result of weathering.

The world phosphate resources are distributed, 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
Figure 2 shows the location of major phosphate rock producers as well as some of the known phosphate deposits not yet in production [1].

2-3% from biogenic resources (bird and bat guano accumulations).

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 Characteristics of Phosphate Minerals

Phosphate minerals occurring in the primary environment include[3]: Flour-apatite (Ca10(PO4)6F2), found mainly in igneous and metamorphic environments, for example, in carbonatites, and mica-pyroxenites, Hydroxy-apatite (Ca10(PO4)6(OH)2), found in igneous, metamorphic environments but also in biogenic deposits, e.g. in bone deposits. Carbonate-hydroxy-apatite (Ca10(PO4,CO3)6(OH)2), found mainly on islands and in caves, as part of bird and bat excrements, guano. Francolite (Ca10-x-yNaxMgy(PO4)6-z(CO2)z F0.4zF2),This complex carbonate-substituted apatite is found only in marine environments, and to a much smaller extent, also in weathering environments, for instance over carbonatites.

may be replaced in part by uranium, lanthanide rare earths or certain other trace metals such as cadmium, zinc, magnesium, strontium and barium. In some cases chlorine occurs in place of part of the fluorine. The extent to which substitution occurs and what the substitutes are, depend on the prevailing conditions when the apatite was formed and on the influence of subsequent events, such as weathering. In sedimentary deposits of marine origin, the phosphate material occurs in admixtures with detritus materials such as quartz, mica and clay, often with limestone and occasionally with dolomite. Igneous apatites may contain other impurities, not commonly found in sedimentary deposits, originating from other constituents of the magma from which the apatite crystallized [4].

1.3. Techniques and Measurements Used to Identify Phosphate Minerals

The most important techniques used for identifying phosphate minerals are [3]: X-ray diffraction (XRD) for mineralogical analysis. X-ray Fluorescent (XRF) for elemental analysis.

The ability of anions to substitute for phosphate in apatite is not restricted to F-, CO3-2 and OH-, found in the differing variants of apatite. Silicate, vanadate, aluminate, titanate and arsenate may also occur in place of part of the phosphate. Likewise, calcium

12
Scanning Electron Microscope (SEM) for grain interaction and spot analysis. Infra Red methods (IR) for detection of surface-layer structure. Micro-probe analysis for elemental distribution in the matrix. Microscopic identification for mineralogy and grain interrelation. Analytical chemical methods. Measurement of refractive indices. Porosity and pore size distribution measurements. Surface area measurements. Thermal Analysis (DTA), (TGA). Unit-Cell dimensions (a-value), and crystal size.

Volume 9 - Issue 17

available at costs comparable to those 20 or 30 years ago. It has been widely suggested that, in general, there have been a continuous decrease in world phosphate rock quality as reserves of high-quality rock are being depleted. As the high-grade phosphate deposits are becoming depleted, the quality of phosphate rock that is utilized on a worldwide basis is decreasing. High P2O5 content equates to low impurity content, high yields per ton of material shipped, handled and processed, increased reaction efficiencies, fewer processing problems and less waste. An industry assessment suggests that the phosphate content of pre-beneficiated ore is already decreasing by around 1% per decade [4]. Estimates of world phosphate reserves and availability of exploitable deposits vary greatly and assessments of how long it will take until these reserves are exhausted also vary considerably. Furthermore, it is commonly recognized that the high quality reserves are being depleted expeditiously and that the prevailing management of phosphate, a finite non-renewable source, is not fully in accord with the principles of sustainability. A 50% world population increase over the next 50 years would point towards an increase in global food needs by at least a proportionate figure, assuming roughly constant per capita cereal consumption. As demand for food increases, this may result in bringing into agricultural use more land, but certainly will bring a requirement for increased yields, thus increasing fertilizer demand. Hence, agricultural phosphate use may increase faster than world population [5]. Depletion of current economically exploitable reserves are estimated at somewhere from 60 to130 years. Using the median reserves estimates and under reasonable predictions, it appears that phosphate reserves would last for at least 100+ years. Increasing demand and increasing prices will make more reserves economically exploitable [5-7]. Based on the present rate of production, about 150 Mt/a, and the available extractable reserves, 18 billion ton, the life time of these known reserves is about 120 years [2].

1.4. The Main Parameters of Phosphate Characterization

There are several parameters that are used in characterizing phosphate rocks. Among these parameters are[3]. Unite-cell a-dimension (a-value), a crystallographic expression of the composition of the apatite composition. The a-cell dimension is expressed in Angstrom (1 A=10-10 m). Refractive index. Solubility data based on chemical extraction methods, e.g. neutral ammonium citrate solubility (NAC). PO4/CO3 ratio as a measure of carbonate substitution in phosphate minerals. Surface area (expressed in m2 g-1), and pore size distribution indicating potential reactivity [11].

The calcium phosphate content of phosphate rock is expressed in different world areas by one of the following terms [1]: BPL (bone phosphate of lime) TPL (triphosphate of lime) P2O5 (phosphorus pentoxide) P (phosphorus not commonly used) An illustration of relationship between the above terms is: 80 % BPL == 80% TPL == 36.6% P2O5 == 16% P. High-grade phosphate rock is available from several sources, such as Togo, Senegal and Morocco. However, premium rocks from these sources are not

2. BENEFICIATION OF PHOSPHATE ORES

Because of the increasing demand on phosphate rock for fertilizers, it is becoming more and more common to mine and process low grades of phosphate deposits. The majority of these low grade deposits are of sedimentary phosphates and the rest are of different origins. These deposits occur in the form of ore bodies in one thick bed or several successive beds intercalated with non-phosphatic materials.

A.M. Abouzeid/The Journal of ORE DRESSING 2007

13
solubility and reactivity. Further more, as a result of the low calcination temperature; the reduction of calcium sulphate, present in the ore, to corrosive calcium sulfide by the organic matter is minimized. During burning the organic matter, the following two conditions must be satisfied: organic carbon must be decreased to less than 0.3% to minimize gassing in the wet phosphoric acid processing, and apatite CO2 must be maintained at a level close to 2% to allow good reactivity to the calcined product [12-14]. 5. Phosphate ores containing more than one type of the gangue minerals: many of the sedimentary phosphate deposits contain mixtures of undesired constituents. These ores require series of upgrading operations in their flow sheets depending on the type of gangue minerals existing in each ore. This may include, after size reduction, combination of attrition scrubbing, desliming, flotation, gravity separation, and/or calcination. Each flow sheet is to be designed after thorough characterization of and testing on a representative sample of the ore under exploitation. 6. Igneous and metamorphic phosphate ores: the main gangue materials in these ores are sulfides, magnetite, carbonates.(calcite, dolomite, siderste, and ankerite), nepheline syenite, pyroxenite, foskorite, etc. Processing of these ores may include after crushing and grinding, washing, desliming, magnetic separation, and flotation depending on the types of gangue minerals present. However, flotation is a common step in all of them [1]. About 20% of the worlds phosphate rock now comes from the mining and beneficiation of igneous deposits, but this percentage will drop as production from sedimentary deposits increases. Igneous apatite in relatively small quantities has been recovered from veins and from magnetite ore bodies where it occurs in minor amounts. The important igneous apatite deposits of commercial interest are found in certain intrusive complexes of alkalic rocks. Commonly near the center are veins and larger bodies rich in carbonates (calcite, dolomite, siderite, and ankerite) emplaced either in a molten condition or by metasomatic processes. The calcareous deposits of the igneous phosphate rocks are called carbonatites. World production of apatite (igneous) concentrates in 1980 was about 25 Mt. Table 1 lists most of the operating apatite mines in the world in 1985. Brazil is actively developing new apatite mines; in 1985 its production of phosphate rock, largely igneous

Phosphate ores show a wide diversity in the composition of their gangue materials but generally fall into one of the following categories, based on the major associated gangue materials [8]: 1. Siliceous ores: These contain quartz, chalcedony or different forms of silica. Such ores could be upgraded economically by such techniques as flotation or gravity separation methods. 2. Clayey ores: these mainly contain clays and hydrous iron and aluminum silicates or oxides as gangue materials. These impurities could be removed by simple beneficiation techniques such as scrubbing and washing. In some cases, dispersing agents would be necessary. 3. Calcareous ores of sedimentary origin: these contain calcite and dolomite as the major impurities with small amounts of silica. It is usually difficult to remove the carbonate minerals efficiently from such ores by such techniques as flotation [9, 10], or by physical separation methods. This is because the physical properties of carbonates and phosphates are very similar. Separation by physical means even becomes impossible when the carbonate minerals are finely disseminated into the phosphate particles. Recent experimental results 11 showed that the flotation techniques applied on a calcareous ore may be effective only if the phosphate can be liberated from the gangue materials. In the case of the unaltered ores, complete liberation is achieved only with extremely fine grinding. Consequently, partially liberated flotation feed must be used to avoid loss of selectivity resulting from fine grinding. Under such conditions high concentration ratios cannot be reached. For upgrading such type of ores, crushing and screening may be used if there are differential friability differences between phosphates and carbonates. However, recovery in this case may be unreasonably low. An alternative technique for upgrading these ores is calcination. Calcination is the process of heating the ore to a high temperature ranging from 800o to 1000oC to decompose the CaCO3 to CaO and gaseous CO2. The CaO formed is then removed as calcium hydroxide by quenching and washing. 4. Phosphate ores with organic matter, some times called "black phosphates"[12]: Ores of this type are generally upgraded by heating the ore up to about 800oC. This type of calcination burns the organic material and the residual organic carbon without significantly affecting the superior qualities of the sedimentary phosphates such as

14
apatite, was estimated to be 5.8 Mt, compared to 1.7 Mt in 1980. The Russians developed new operations in the Kola area and have new mines operating on apatite in the Lake Baikal region in Siberia. Some of the Russians apatite mines in the Kola Peninsula are underground, but the majority of its mines, as well as

Volume 9 - Issue 17

all other apatite mines in the world, are surface operations. Foskor, in South Africa, developed additional large mine-beneficiation operations on the Phalaborwa carbonatite complex. Carbonatites have been found in Australia in 1968, New Zealand in 1970, and early in 1980s in Paraguay [1].

Country USSR (Kola) South Africa (Phalaborwa) Barzil Zimbabwe (Dorowa)

No. Mines 6 2 5 1

Table 1. World Apatite Mines in 1985 [1] No. Concentrate, Grade, Beneficiation 1000 t/a % P2O5 Plants 2 1 3 1 20 3.5 5.8 1 17 7 13.5-15 7

Type Deposit Nepheline syenite (unweathered) Pyroxenite and foskorite (unweathered) 1 carbonatite (unweathered) 4 carbonatite weathered residuals. Alkalic complex.

3. TECHNIQUES FOR PHOSPHATE ORES

UPGRADING

by desliming and / or classification. Such technique is successfully used to upgrade the Red Sea Coast phosphate rock in Egypt. b) It is also used when the associated gangue minerals are mainly coarse silica or chert chips. In this case, phosphorites are collected from under the screens in a wet process. This may also be practiced to separate a coarse phosphate-rich fraction ahead of a flotation section such as in Florida plants [1-15]. 3. Electrostatic separation: In combination with attrition, desliming, and gravity separation, the electrostatic separation was successful in upgrading phosphate ores by removing silica and /or carbonates, mostly on laboratory scales. However, the low capacity of the electrostatic separators limits their use for large scale production. This technique is used to concentrate phosphate ores of different types. The following are examples of the ores responded to the electrostatic separation: a) A calcareous ore (from North Africa) was upgraded using electrostatic separation to produce a concentrate assaying: 32.9 % P2O5 at 80 % P2O5 recovery from a feed assaying 24.1 % P2O5 [16]. b) Abu-Tartour ore, Eastern Desert, Egypt (containing quartz, ankerite, gypsum and pyrite) produced a concentrate assaying 33% P2O5 at recovery of 71.5% from a feed assaying 27.5 % P2O5 [17]..

There are several beneficiation techniques for upgrading phosphate ores. The choice of one of these techniques depends on the type of ore as well as the associated gangue minerals. Among these techniques are: 1. Size reduction and screening: this technique utilizes the differences in differential friability between phosphate minerals and associated gangue and cementing matrix (carbonates, silica, and silicates). In most cases, phosphate minerals are friable while gangue minerals are hard. Here, high percentage of P2O5 is lost in the coarse fraction. Air elutriation may be practiced to get rid of the very fine fraction that is rich in clays. An example of using this technique is the beneficiation plant of the Nile Valley phosphate rock at East Sibaeya area, Egypt. There the main beneficiation facilities are crushing and screening to recover the phosphate product in the fine fraction. 2. Attrition scrubbing and classification. Some of the operations using this technique are listed below: a) This technique is used when the main gangue minerals are clays. Clays are characterized by their fine size, loosely bound grains with the phosphorite pellets. Attrition in water liberates and disperses the clay particles in water and they are removed

A.M. Abouzeid/The Journal of ORE DRESSING 2007

15
P2O5 and the phosphate concentrate assays 2930 % P2O5 at a recovery of 70 % [24]. 5. Flotation: More than 60% of the marketable phosphate in the world is produced by flotation [25]. a) Siliceous ores: The common technique for processing siliceous phosphate ores is the anionic-cationic flotation technique. If there is any carbonate minerals, it will report to the phosphate concentrate [26-28]. b) Carbonaceous ores: phosphate minerals and carbonate minerals ( Calcite and dolomite) exhibit very similar surface chemical properties. Sedimentary phosphates are more sensitive to the similarity in surface chemical properties of these minerals. This makes their separation by flotation a challenging problem [29-32]. Much research has been carried out to try to reduce the calcium carbonate content of phosphate rocks by flotation and/or calcination [33]. Hignett et al. [34] claimed that flotation seems to work best on ores containing well-crystallized carbonates. When the ore contains soft or chalky carbonates the flotation results were less satisfactory. This was the case of East Mediterranean and North Africa ores where the carbonate crystals are intergrown so that the phosphate is not liberated by comminution until the rock is too fine for flotation [35, 36]. However, as discussed previously, it is obvious that the problem of separating carbonates from phosphates in the sedimentary rocks is seriously complicated, and a brief survey on the latest efforts for solving this problem is due. The currently used commercial process of double flotation is not adequate for reducing the dolomitic impurity level to less than 1.0 % by weight MgO in the concentrate, as stipulated by the phosphate industry. During the past decade, studies conducted by investigators in the Florida phosphate industry [38-41] and the Tennessee valley Authority [42] have resulted in the development of a number of processes. However, all these studies originated on a bench scale and the fundamentals involved in the separation scheme have not been established. This leads to serious limitations for optimization of these processes and also their use for beneficiating ores of different origin and composition. Recently, Moudgil and Chanchani [43, 44] and Ince [45] have conducted some fundamental studies which resulted in the development of two processes for the

c) A siliceous ore (from Qusseir, Red Sea Coast, Egypt) produced a concentrate assaying 33.8 % P2O5 at 70.3% recovery from a feed assaying 16.5% P2O5 [18] . d) A siliceous ore (from Hamadat mine, Red Sea Coast, Egypt) produced a concentrate assaying 30 % P2O5 at a recovery of 76.3 % from a feed assaying 18.2 % P2O5 [19]. e) One of the few plants that used electrostatic separators on an industrial scale, was the Pierce plant in Florida, USA. The plant used to upgrade phosphate flotation-concentrate using electrostatic separators. The feed assayed 32.9 % P2 O5 and 11.3 % insoluble, and the final concentrate assay was 35.3 % P2 O5 and 5.6 % insoluble [20]. 4. Magnetic separation: when one of the major gangue constituents is magnetic, magnetic separators are used as one of the steps in the flow-sheet to remove the magnetic constituents. This is mostly used in the beneficiation of igneous phosphate rocks. However, it has also been used for upgrading some sedimentary phosphate ores. The following are examples of plants using magnetic separation in their flowsheets: a) The complex igneous phosphate deposit at phalaborwa ( South Africa) is upgraded in three stages [21]: 1. copper flotation 2. magnetic separation 3. The non-magnetic fraction is subjected to flotation to float apatite The Run-Of-Mine, ROM, to this plant assayed 7 % P2O5 , and the phosphate concentrate assay was more than 36 % P2O5 at a recovery of 75-80 % P2O5 . b) In the Brazil's long established apatite ( igneous) beneficiation plants, magnetic separation followed by desliming and flotation are included in the phosphate concentration plants. Ores assaying 7-15% P2O5 are upgraded to produce concentrates assaying 36 to 38% P2O5 [22, 23]. c) The dolomiticpyritic sedimentary phosphate ore of Abu-Tartour phosphate deposit in Egypt is subjected to high intensity magnetic separation, after desliming, to separate the feebly magnetic ankerite. The feed assays about 22-26 %

16
removal of dolomite from apatite. Extension of these fundamental studies to beneficiate the natural ores on a bench scale was also reported [46]. Also, Shong et al. [47] have attempted a systematic optimization of some variables using a three stage flotation scheme with various reagents. To help understand the collector adsorption mechanisms in the phosphate- carbonate systems, more extensive investigations were conducted to clarify the effect of the addition of organic and inorganic salts on the surface charge of the two species, apatites and carbonates[48-53]. These studies established firmly that phosphate ions function as potential determining ions for apatites, while Ca++ ions act as either potential- determining ions [56] or specifically adsorbed ions [57-59] for apatites. In the case of calcite, both Ca++ and carbonate ions have been shown to be potential-determining ions for the mineral [51-54]. Flotation behavior of apatites and carbonates was conducted under various experimental conditions [56-60]. Smani et al. [52] provided a comprehensive review of electrophoretic studies of phosphates and associated calcareous gangue minerals, together with flotation results of selective separation of phosphate oolites and calcite. In their investigation, it was shown that H+, OH-, Ca++, and HPO4-2 function as potential determining ions for apatites. They also demonstrated that adsorption of sodium dodecylsulfonate and dodecylamine chloride on phosphate surface is due to electrostatic attraction while adsorption of oleate at pH greater than 6 is due to a chemical binding energy between oleate ions and surface sites of the phosphate particles. Between about pH 5.5 and 6.5 , the phosphated-surfce particles were sharply depressed , whereas their flotation recovery increased at pH 4. Depression of such particles between pH 5.5 and 6.5 was explained to be due to the lack of adsorption of the collector, whatever the concentration may be. The flotation at pH 4 was suggested to be due to adsorption of neutral molecules in the vicinity of the isoelectric point, IEP. Mitzmager and Co-workers [61] dealt with the effect of soluble alkali phosphate salts on oleate flotation of calcite from phosphate slimes. They tested the selective depressing action of soluble alkali phosphate salts on phosphate minerals. The authors concluded that the mechanisms of the depression of phosphate and activation of calcite by soluble alkali phosphate is due, at least, to two parallel effects: a) The adsorption of molecular dicalcium phosphate (CaHPO4) on the phosphate

Volume 9 - Issue 17

particles probably as a replacement of dissolved gypsum, and b) The mild attack on calcite particles accompanied by the evolution of tiny CO2 bubbles on the surface. Johnston and Leja [60] continued the effort to understand the complex nature of the phosphatecarbonate systems. Flotation behavior of two apatite samples and a dolomite sample were investigated in presence of oleic acid and soluble phosphate solutions. They concluded that: a) Flotation of apatite is prevented by the depressing action of soluble phosphate ions in acid solutions, whereas dolomite floats readily in presence of such ions. b) If gypsum is present in the flotation feed, excessive quantities of phosphate ions are needed for the depression of apatite because of a fast metathesis reaction between gypsum and orthophosphate ions. This reaction can be completely suppressed by the addition of suitable quantities of sulfate ions, which is exactly opposite to the findings of Mitzmager and co-workers [61]. c) Following the findings reported by Bertolucci and co-workers [62, it was suggested that the depressing action of phosphate ions on apatite is due to the formation of a more strongly hydrogen-bonded phosphate-water layer around apatite particles than around dolomite particles. Evolution of CO2 from dolomite or calcite, in acidic solutions, disturbs the hydrogen bonding around these particles. This allows an immediate adsorption of collector and results in dolomite or calcite flotation. Moudgil and Chanchani [44] used two-stage conditioning process for the flotation of dolomite from apatite. The mixture of minerals (dolomite + apatite) was first conditioned at pH 10 in presence of a fatty acid collector. The system was then reconditioned below pH 4.5 where dolomite was floated. Soto and Iwasaki [63] showed that in a mixture of francolite and dolomite, the primary amines were uniquely selective towards the phosphate mineral. In a phosphate ore, primary amines were adsorbed mainly on the phosphate indicating that stronger interaction existed between the amine and francolite than between the amine and dolomite. The US Bureau of Mines developed a process to separate carbonate (calcite) from phosphate minerals occurring in the unaltered

A.M. Abouzeid/The Journal of ORE DRESSING 2007

17
c) The phase boundary line between hydroxylapatite and CaHPO4(S) occurring at pH 4.6 is shifted towards more acidic pH values when dissolved Ca++ is added to the system, and towards less acidic pH values when soluble phosphate salts are added to the system. This may explain why it is relatively easy to depress apatites in acid media in absence of carbonates, while the same thing cannot be achieved when natural ores are treated. These theoretical analyses were proceeded a step further [31] in order to assess the most important conditions for separation of carbonates from phosphates. The final conclusion of this study was that: Concentration of calcium - phosphate complexes, in the solution, in equilibrium with all apatites increases with the decrease of pH and with the increase of added soluble phosphate, oxalate, and sulfate salts; but sharply decreases by adding or dissolving calcium salts. To sum up this theoretical discussion, two conditions seem essential to be fulfilled in order to achieve selective flotation of carbonates from apatites in acid media (pH 5.5-6.0). These are: minimizing Ca++ and /or increasing HPO4-2 in the carbonate/apatite/water system. The following are examples for separating carbonates from phosphates, on the laboratory scale, by flotation: a) The USBM treated a sedimentary ore (carbonate-apatite in addition to pyrite, Ca & Mg carbonates and silica). Three-stage flotation operation was adopted starting with flotation of pyrite using xanthates. They added H2SiF6 as depressant for phosphate minerals, and used anionic collector to float the carbonates followed by cationic flotation to remove silica. The phosphate concentrate assayed 29 % P2O5 at 69 % recovery from a feed assaying 19.9 % P2O5 (see Fig.3) [69]. b) A thermodynamic analysis of the apatitecalcite system was carried out at Cairo University 32. It showed that at pH = 5.8, it is possible to float carbonates from calcareous sedimentary phosphate ores. A flotation scheme was designed such that the pH value was kept constant around 5.8 during conditioning and flotation of a deslimed sample. Flotation continued until barren froth was observed. Both the carbonate float and phosphate concentrate were filtered, washed, dried, weighed, and analyzed. Using this scheme, the following results were obtained for samples from two

phosphate ores of Phosphate Formation [64]. The process uses fluosilicic acid to depress the phosphate while floating the calcite with fatty acid emulsion. Another US Bureau of Mines report of investigation dealt with the beneficiation of high-magnesium phosphate from Southern Florida [65]. Several depressants such as starch, fluosilicic acid, sodium borate, lactic acid, sodium biphosphate, phosphoric acid, and acetic acid failed to depress phosphate minerals. A technique of sizing, grinding, desliming, scrubbing, redesliming, and flotation was then devised to treat three southern Florida high-MgO phosphate ores. Moudgil, et al. [66] described flotation process based on the depression of apatite with sodium chloride in acid medium and flotation of dolomite with fatty acids. When this process was applied to a natural phosphate ore, it was possible to float dolomite from apatite at pH=4. Hanna and Anazia 28 described a flotation process developed by Alabama Mineral Resources Institute (MRI) for selective fatty acid flotation of carbonates from sedimentary apatites in the pH range of 4-6 without conditioning of the pulp prior to flotation. The success of the process is based on the fact that fatty acids adsorb more rapidly onto carbonate surfaces than onto phosphate surfaces. Carbonates are floated in slightly acidic circuit immediately upon the addition of the collector and frother, then the pulp is conditioned briefly, and the phosphates are floated from the siliceous constituents with no further addition of collector in most instances. Important as they are, these studies have not provided an understanding of the mutual effects of phosphate and carbonate minerals on each other. This shows the need for a thorough thermodynamic analysis of the phosphate-carbonate systems in aqueous solutions. Simultaneously, in 1978/1979, two studies were published by Johnston and Leja [66] and Elgillani [29] on the analytical aspects of the calcite/apatite/water system. These analyses showed that the control of dissolved Ca++ in the system seems to be the key to achieve selective flotation of carbonates, especially calcite, from apatite. Based on thermodynamic analysis of the apatite /calcite / water system that was carried out in these studies, it was concluded that: a) Depression of apatite is probably related to its instability in acid media. b) Concentrations of aqueous calcium phosphate complexes such as CaHPO4 and CaH2PO4+ increases with the decrease in pH of the system.

18
mines from the Red Sea Coast phosphate rock, Egypt (see Tables 2 and 3). As a matter of fact, the efforts spent in solving the problems of separating carbonates from phosphate ores, particularly in the case of sedimentary

Volume 9 - Issue 17

phosphate ores, are tremendous. Most of these efforts are documented by the Florida Institute of Phosphate Research, FIPR [70]. This extremely important publication is a collection of abstracts of most of the published material on phosphate 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. Insoluble, % LOI, % P2O5Rec., % Modifying Reagents + Product P2O5 , % 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 Phosphate Conc. 17.39 31.26 2.22 1.1 23.66 8.5 64.9 5.7 kg/t H3 PO4 *** 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 Carbonate Float Phosphate Conc. Carbonate Float Phosphate Conc. Carbonate Float Phosphate Conc. Carbonate Float Phosphate Conc. Carbonate Float Phosphate Conc. Carbonate Float Phosphate Conc. P2O5 , % 10.51 27.62 8.49 30.0 7.11 31.65 7.44 31.84 7.63 30.81 7.45 31.91 Insoluble, % 6.0 3.38 5.47 3.22 5.94 3.17 5.5 2.45 6.41 2.77 5.87 2.8 LOI, % 31.25 11.55 33.47 9.8 34.6 7.8 35.5 7.54 34.06 8.21 34.3 7.45 P2O5Rec., % 68.51 77.96 79.91 79.7 77.62 78.13 Modifying Reagents + 2.2 kg/t H2 SO4 * 4.0 kg/t H2 C2 O4 * 2.96 kg/t H3 PO4 * 9.6 kg/t KH2 PO4** 3.2 kg/t KH2 PO4** 1.5 kg/t H2 SO4 2.4 kg/t KH2 PO4 ** 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 PHOSPHATE ORES

OF

with specific properties. The main objectives behind heating up the ore are: i) Removing water 120-150 C Drying ii) Removing organic matter

More than 10% of the world marketable phosphates are produced by calcinateion. Traditionally, heat treatment of phosphate ores is defined as heating up the ore to a certain temperature to obtain a product

A.M. Abouzeid/The Journal of ORE DRESSING 2007

19
iv) Removing fluorine up to 1350oC Defluorination

650-750 C 850-1000oC

Calcination Calcination

iii) Dissociation of carbonates

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 processing of phosphates, is categorized under thermal treatment, but it is not included under the term calcination.

a) Almost all these heat treatment operations are preceded with ore preparation such as: crushing, grinding, sizing and / or classification, and possibly flotation, to get rid of some of the liberated impurities at one or more of these stages.

20
b) Calcination of phosphate ores is necessary for obtaining a phosphate product suitable for the production of light green phosphoric acid, which is in turn suitable for the production of pure super phosphoric acid. This last product is used in the preparation of pure chemical reagents, soft drinks, and other pharmaceutical preparations. There are two types of calcination operations. One is associated with organic matter. In this operation, the ore is heated up to 650-750oC to burn the organic matter and to oxidize the residual carbon. In this case, exothermic 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]:

Volume 9 - Issue 17

an animal feed supplement. The product is essentially a solid solution of calcium phosphates as well as calcium silicate. The principle reaction is shown below. No attempt has been made to balance the equation, which comprises of a far more complex set of chemical reactions [74]: 3[Ca3(PO4)].CaF2(s) + SiO2(s) + NaOH (aq) + H3PO4(aq) 3Ca3(PO4)2.Na3PO4.Ca2SiO4(s) + 2HF(g) Figure 4 shows a schematic flow sheet for the defluorination process of the phosphate rock [73].

CaCO3 + Heat CaO + CO2 +42.9 kcal/mole

c) Defluorination is the process of obtaining fluorine-free highly purified forms of phosphorus-containing products to be used as supplements in livestock and poultry feeds, with phosphorus in water soluble forms. These products are essential for the health of the animals. Since fluorine is toxic to animals, it has to be removed almost completely by defluorinating the phosphate ores. Defluorinated phosphates are produced by adding defluorinating agents, such as phosphoric acid and soda compounds, in controlled amounts to phosphate rock and calcining the mix at temperatures ranging from about 1370 oC to 1510 oC conditions that drive off the fluorine and converts the unavailable phosphate to the biologically available form. The process transforms phosphate mineral to the defluorinated phosphate with a P/F ratio of more than 100. Calcined product is cooled and screened to defluorinated phosphate rock (DFP) or tricalcium phosphate (TCP) [73]. Because it has a low enough fluoride to phosphorus ratio, and the phosphorus is bio-available, it is suitable as
Figure 4. Delfuorination process of phosphate rocks [73]

4.1. Energy Consumption in Treatment of Phosphate Ores

Thermal

The amount of energy for mining and physical beneficiation of phosphate ores to produce one ton of commercial rock phosphate (32% P2O5) is approximately 0.9 GJ/tonne of rock phosphate (about 2.9 GJ/tonne P2O5). However, if the rock is calcined, the total energy requirement is doubled [75]. Considering all the major factors consuming heat in the calcination process, the heat required to produce one kg of calcined phosphate from a raw feed containing about 50 % calcium carbonate and 10 % moisture was found to be in the range of 800 kcal/kg of calcined product. This amount of heat is equivalent to about 0.15 kg of coal of calorific value in the range of 7000 kcal/kg of coal. This amounts to 3.6 GJ/ton of calcined product [76]. It was reported by Bandyopadhyay 71 that the calcination process involves drying of beneficiated phosphate rock ( from 10-15 % moisture down to 1-

A.M. Abouzeid/The Journal of ORE DRESSING 2007

21
d) Eliminating the foaming phenomenon during acid attack of the calcined phosphate products. These solves technical problems, caused by the presence of organic matter and/or carbonate minerals, and saves the costs of the defoaming reagents. e) The capital costs of the calcination plants are comparable with the drying units which are commonly included in the wet beneficiation flow-sheets. f) The special products obtained by high temperature treatment (super phosphoric acid and defluorinated phosphates) are highly demanded and highly priced.

3 % moisture) followed by calcination at temperature of about 800oC. The data provided by Bandyopadhyay was basically for the treatment of the North Carolina phosphate ores. This type of ore contains organic matter as the main impurity in the ore. For this reason the cost for the calcination process was considerably low. He reported US$ 1.68 / short ton for drying and US$ 3.49/short tone for drying and calcination at 800oC based on the 1999 cost level. In this case, the energy consumption for calcination was very low due to the presence of organic matter which supplied most of the calcination heat during burning. The energy cost for the defluorination of phosphates at 1350o C was in the range of US$ 36.2/short tone of product [71]. It is thought that the feed to the defluorination plant was also a North Carolina phosphate rock, which means that for defluorination of a calcareous ore, with little or no organic matter, the energy required will be higher.

4.2. Limitations and Benefits of High Temperature Treatment of Phosphate Ores

There are several factors that are traditionally known as drawbacks for the calcination of phosphate ores [19, 67,77]. Among these factors are: a) High capital cost of calcination plants. b) Energy extensive operation. c) Low reactivity products. d) It usually affects gypsum filtration rate, adversely [73]. On the other hand, there are factors that are in favor of phosphate calcination. Among these factors are: a) Upgrading of the ore, reduces the tonnages to be treated for the same P2O5 units, and , hence reduces costs for transportation and fertilizer and/or phosphoric acid production. b) Reduces the amount of sulfuric acid required for acidulation of the ore in the subsequent chemical processing. c) In most cases, the drawback of low reactivity of the calcined product could be avoided by controlling calcinations temperature below 800oC when the main impurities are organic matters. In this type of phosphate ore, with high organic matter content, burning of organic matter is exothermic (evolves heat) which saves energy.

Any way, the final decision for obtaining the required phosphate product will be taken based on thorough analysis of the economic and technical assessment of the process and on the available type of ore that will be used as the initial feed.

4.3. Types of Thermal Treatment Units

There are various types of units for calcination of phosphate ores. These include: a) Vertical shafts [1, 80, 81]. b) Fluidized bed reactors [72, 78, 79]. c) Rotary kilns [1,80]. d) Traveling grate kilns [81]. e) Traveling grate-rotary kiln systems 1,81. f) Flash calciner [1, 12-14, 80, 82, 83].

Readers may be referred to the cited references for detailed designs, and operating techniques, and advantages of each of the above units.

4.4. Industrial Calcination Plants Worldwide phosphate calcining capacity in 1981 was about 14 Mt/a. About 75 % of world calcination is treated in Dorr-Oliver FlouSolids systems. Allowing 85% equipment availability, the yearly design capacity was 8.9 Mt/a. Actual production is probably 120 % of design capacity, or 14.3 Mt/a for all calcining installations. These installations are designed to reduce the organic content of phosphate rock. However, in Algeria, the calciners, which

22 are operated at higher temperatures, are used to drive off CO2 from carbonates. Table 4 gives the most important world phosphate
Installation Djebel Onk OCP Beker Simplot Stauffer Texas Gulf Total

Volume 9 - Issue 17

calcination plants for the removal of organic matter as well as calcite [1].

Table 4. World Phosphate Calcining Capacity, 1981 (ref. 1) Location Calcination Units Design Capacity, t/d Algeria 3 3000 Morocco 2 3700 Idaho 4 5830 Idaho 4 5000 Wyoming 3 2000 North Carolina 6 9000 22 28530

4.5. Effect of Substituting Carbonates on the Characteristics of Carbonate-Apatite

The apatite in phosphorites and rock phosphates usually are poorly crystallized [33, 37]. Their compostions differ considerably from those of pure fluorapatite or hydroxy-apatite. Their X-ray diffraction patterns are typically apatite with slight shifts that show changes in the cell parameters [77]. As already mentioned, most sedimentary phosphorites contain considerable amounts of carbonate [85], up to 6.3 % of the phosphate mineral, and are often considered to be carbonateapatite or francolites [84]. Gruner and McConnell [98] found small distinct changes in the intensities of certain francolite reflexions from those of apatite reflexions. However , Hendricks and Hill [86] reported that X-ray goniometer photographs of francolite crystals are indistinguishable from those of apatite crystals, although theoretically they should. Altschuler et al. [87] presented X-ray evidence for carbonate flourapatite as a distinct variety of apatite rather than a mixture of a carbonate phase and flourapatite, Silverman et al. [88] investigated the differences in X-ray patterns of carbonatefluorapatite, hydroxy-apatite, and fluorapatie. They detected the presence of carbonate in the structure of carbonate-apatite and differentiated it from that of fluorapatite.

Maslennikov and Kavitskaya [89] and Alden and Lindqvist 90 recognized that the a-axis in apatite containing both fluoride and carbonate ions would be short (9.32 to 9.35 ) compared to the a-axis of igneous and metamorphic apatite (9.38 to 9.40 ) that contain fluoride ions with almost no carbonate ions. Such variations in the a-dimension indicate that the excess CaF2 or CaCO3 cannot be simply adsorbed on the surface of the apatite crystals, but it may correspond to some regular type of overgrowth that leads to a series compounds with end-members general formulae of [84]: Ca10(PO4)6F2...Ca10-a-bNaaMgb(PO4)6x(CO3)xF2 . Fy Electroneutrality of the above equation is preserved when a= xy. Experimentally it was found that y=0,4x where x varies from near zero to 1.5 and b = 0.4a. These end-members correspond to the chemical composition shown in Table 5. The maximum degree of substitution was found for carbonate-francolite type apatite when x/(6x ) 0.3. The most significant feature revealed is that the relative increase in amounts of F, Mg, Na, and CO2 is accompanied by a decrease in P2O5 content and nearly constant CaO content [85].

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 carbonate and decreasing content of phosphate exhibit proportional changes in the dimensions of

the a-axis. As no phase other than apatite is detectable from the X-ray patterns, it was concluded that the carbonate is a substitute for the phosphate

A.M. Abouzeid/The Journal of ORE DRESSING 2007

23
This means that the release of CO2 from carbonateapatite is easier than from calcite probably due to internal stresses inside the carbonate-apatite structure. It should be noted that the two samples are of the same ore sample with the calcite-free sample prepared by dissolution of calcite using Silverman solution (Tri-ammonium citrate solution) [100].

within the structure. Smith and Lehr22 indicated that there is a reasonable correlation between the total fluorine content and the carbonate content and the length of the a-axis. The increase in carbonate content in the lattice structure would cause a decrease in the a-axis of the unit cell. Lehr [92] confirmed the findings of McClellan and Lehr [84] 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 crystallites with a lengthtothickness ratio approaching unity. They also concluded that the changes in size and shape possibly were due to the formation of weak bonds by carbonates, and that the growth of a crystal is less in the general direction of the formation of weak bonds than in the general direction of the formation of strong bonds. Cuthbert and Rowland [94] studied the differential thermal analysis of ten different carbonate minerals and found that they dissociated at different temperatures. All the carbonates showed endothermic reactions caused by dissociation, but siderite showed an exothermic reaction caused by the decomposition of FeCO3, which gives FeO which is immediately oxidized to Fe2 O3 [94, 95]. The differential thermal curve of calcite showed an intense broad endothermic reaction starting at about 625oC and ending at about 893oC with a peak at 840 oC. The aragonite curve also showed a broad endothermic reaction starting at about 600 oC. In the same direction, Faust 96 made several studies using differential thermal analysis to differentiate between magnesite and dolomite and between calcite and aragonite 97. Silverman et al.88 were able to detect the carbonate associated as calcite from bound carbonate in carbonate-bearing apatite by means of DTA analyses. Confirmation of these findings was observed by El-Jallad [98] and Abouzeid et al. [77] for two francolite phosphate samples; one includes associated calcite and the other is calcite-free sample. Figure 5 shows that the rate of dissociation of carbonate-apatite (the Calcite-free sample) is higher than that of the sample containing associated calcite.

Figure 5. Weight loss as a function of calcination temperature for the two Jordanian calcareous phosphate samples (an orginal sample and a calcitefree sample) [77, 98]

Phosphate ores of high carbonate content could be beneficiated by heating the rock to temperatures between 600 and 950 oC. This removes free and combined moisture and most of the carbon dioxide [101, 102]. Clay, iron and aluminum oxides, if present in the phosphate ores, are very harmful impurities in the calcination process. If the ore is not washed, the clay will be hardened by dehydration, and sometimes it may form silicates with magnesium and calcium oxides that are responsible for some technical troubles and clinker formation in the kiln especially at calcination temperatures about 1100oC 101,103. Washing the ore before calcination, therefore, is very important. The calcination temperature plays a decisive role in determining the time required for hydrating the lime. Petrographic studies showed that phosphate samples heated at 1200oC contained free CaO, some undecomposed CaCO3, slaked CaO, clinker material in a glass phase, and, in some cased, gypsum. The undecomposed CaCO3 was found in single grains or mixed with aggregates of CaO [101, 104].

4.5.1. Characteristics of Calcined Phosphate Product

The thermograph of the material to be calcined as a function of temperature is different from one type of phosphate ore to the other depending whether the ore contains organic matter, carbonate minerals , or

24
both of them as the main gangue material. If organic matter is dominating, the reaction will be exothermic, and less energy is required to initiate the reaction (Figure 6) [12]. It should be noted that there is an exothermic reaction between 625 C and 800 C probably due to recrystallization of the carbonateapatite constituents. With carbonates, e.g. about 50 % calcite, as gangue minerals, with little or no organic matter, the reactions will be endothermic needing around 400 kcal/kg of heat energy for dissociation of carbonates [76], Figure 7.

Volume 9 - Issue 17

thermograph for a phosphate ore containing carbonates and organic matter as the main gangue constituents [98]. In this figure, there is a series of weak endothermic reactions as a result of moisture evaporation and removal of water of crystallization with a possibility of overlapping an exothermic effect with a peak at 470 C due to burning of organic matter. There is also a strong exothermic reaction with a peak at 750 C, probably due to recrystallization of the carbonate-apatite, followed by 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 dissocation of calcite [98]

This is a large amount of heat energy to be supplied to the system for calcination. When both organic matter and carbonate minerals exist, the thermograph reflects exothermic peaks, endothermic peaks and interference regions where both exothermic and endothermic reactions overlap [98]. In this case the amount of heat energy needed for calcination will depend on the relative existence of the two constituents, organic material and carbonate minerals. Figure 8 shows the differential

Chemical analysis of calcined phosphate showed higher P2O5 grade in the phosphate product after calcination [101-111]. Stolovitskaya [113] pointed out that the degree of recrystallization of CaO depends mainly on the calcinations temperature. Decomposition of the adsorbed and combined water, burning of organic matter and most of the combined carbon dioxide increase the phosphate grade in the calcined product. Freeman et al. [114] Ando and Matsono [115] found that the a-axis of the unit cell started increasing when 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, caused an increase in the unit cell a-axis. Abouzeid et al. [77] obtained similar results concerning the increase in the a-axis and the growth of crystal size as the calcination temperature increases. The value of the a-axis of the unit cell increased from 3.335 at room temperature to 3.364 after calcinations at 950 oC (Figure 9). The crystal size of the phosphate mineral was increased from 500 at room temperature to 2200 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 aaxis 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 reach 9.357 at 950 oC when calcination was carried out for four stages in a flash calcination system.

Figure 9. The unit cell dimension (a-axis) as a function of calcination temperature for two Jordanian phosphate samples (an original sample a calsite-free sample) [77, 98]

Figure 10. The mean crsytal size of phosphate minerals as a function of calcination temperature [77]

4.5.2.2. Surface Area, Porosity, and Material Density: Surface area: Freeman et al.[114] reported that the
specific surface area of the calcined product of phosphate rock decreased with increasing calcination temperature. They carried out their tests on two different phosphate samples from Morocco and Utah. There was a sharp decrease in specific surface area with increasing temperature in both samples between 500 oC and 800 oC, with the Morocco sample more pronounced in the density decrease. They attributed this remarkable change in surface area to the aggregation of elementary fine grains in this temperature range suggesting that consolidation of these very small grains occurs at these temperatures. It may also be possible that the destruction of the pore structure of the rock in this temperature range contributes to the drastic decrease in specific surface area of the sample as will be discussed later.

Porosity: The porosity of the phosphate rock

sometimes increases with increasing temperature up to about 700 oC and then decreased from this level on as in the case of the Utah phosphate rock 114. In some other phosphates, such as the Morocco phosphate, the porosity gradually decreases with increasing temperature and then suddenly falls to minimum at about 700 oC [114]. The porosity trends suggest the destruction of the pore systems in both samples for both the macro pres and Micro pores, but particularly the fine pores. For the Morocco sample the destruction of pores was quiet severe which may be reflected on the reactivity of the calcined product. It is worthy to mention that in the case of the Utah sample, the gradual incrase of porosity in the lower range of temperature ( below 500 oC) may be explained on the basis of volatilization of organic matter [114].

26 Density: It was observed that there is little change in

particle density below 750 oC. Above this temperature, some changes in density occur, where the density slightly increases with increasing calcination temperature. The particle density roughly reflects the internal collapse of the particle porosity between temperatures, of 650 oC to 750 oC. The true density is almost not affected by the calcination temperature except at relatively high temperatures where crystal transition may take place and cause the density to be lower [114].

Volume 9 - Issue 17

4.5.3. Effect of Calcination on Chemical Reactivity of the Calcined Product

The chemical reactivity was found to be a reasonable measure of the suitability of the the phosphate rock. The solubility behavior of phosphorus in mild solvents such as citric acid, neutral ammonium citrate, and alkaline citrate provides a very good indication of relative reactivity. The amount of soluble phosphate extracted from a certain quantity of phosphate rock in a certain volume of solvent under specific conditions is called the relative solubility or reactivity of the rock. Diluted mineral acids may also be used for measuring the relative 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. The chemical reactivity of the phosphate rock with a solution of 2 percent citric acid decreased slightly upon calcination at 500 oC because of the decrease in porosity. It also decreased sharply when the phosphate rock was calcined above 900 oC as a result of changes in unit cell dimensions, crystal growth, decrease in porosity and surface area as mentioned before. Treatment of the phosphate rock in an 0.25 N hydrochloric acid showed a slight decrease in reactivity after calcination. This decrease, however, was not significant compared to the original uncalcined phosphate rock. The rate of decomposition of phosphates calcined above 900 oC

in a mixture of sulfuric and phosphoric acid showed a remarkable decrease in their chemical reactivity. Lehr [92] and Smith and Lehr [116] studied the solubility behavior (chemical reactivity) of 17 phosphate rocks before and after calcination by using neutral ammonium citrate solution for the reactivity measurements. They found that the chemical reactivity decreased slightly above 600 oC owing to the annealing of phosphate crystals. However, there was a sharp drop in the chemical reactivity of the phosphate rock after calcination avobe 750 oC caused by recrystalization. It reached its lowest value when calcined at about 950 oC owing to extensive crystal growth. Henger and Pacl [105] found that the chemical reactivity of calcined phosphates decreased as the calcination temperature increased and reached its lowest value at 900 oC. They used in their studies 2 percent citric acid, 0.25 N nitric acid , 0.25 N sulphuric acid, and 0.25 N phosphoric acid. They attributed the drop in chemical reactivity of the calcined phosphate, at about 900 oC to an alteration of carbonate-apatite to fluorapatie and to a decrease in the specific surface area. El-Jallad [98] found that this decrease in chemical reactivity could be caused by changes in crystal structure, crystal size, and the presence of CaCO3 and CaO in the product.

Figure 11. The solubility index as a function of the unit cell dimension a-value of the phosphate minerals [3, 77]

It has been reported that rocks from different geographic deposits respond differently, from the physical and chemical aspects, to calcinations. Changes in some cases are negligible, and in some other cases are highly remarkable. Table 6 gives some examples of the change in reactivity indices of some phosphate samples from different geographic locations [71, 77, 114]. It is obvious from Table 6 that the reactivity index is different for different phosphate deposits differing in geographic locations. It also shows that the drop in reactivity index of the

A.M. Abouzeid/The Journal of ORE DRESSING 2007

27
amount of calcium carbonate and calcium oxide affect the reactivity index to a noticeable extent.

calcined product can be as high as 88% of the uncalcined rock and as low as 5%. Also, due to the limited amount of dissolving acid, the relative

Table 6. Percent relative reactivity of some phosphate rocks of different geographic locations, Geographic location of the deposit Jordanian phosphate Jordanian phosphate Morocco phosphate Utah phosphate Peru phosphate Florida phosphate using neutral ammonium citrate solutions (ref. 77,114). Reactivity Percent of Calcinations index of reactivity index of o uncalcined temperature, C uncalcined rock phosphate rock 24 43 87 60 75 52 950 950 910 775 900 815 12.5 41.9 53.4 89.7 93.8 95.0

Remarks CO2(total) = 19.1% CO2(apatite)=6.1% Calcite-free CO2(apatite)=6.1% CO2(total) =5.2% CO2(apatite)=4.8% CO2(total) =2.7% CO2(apatite)=1.6% CO2(total) =4.6% CO2(apatite)=4.2% CO2(total) =2.4% CO2(apatite)=2.2%

SUMMARY
Techniques for beneficiation of phosphate rocks depend on the type of the phosphate deposit, the phosphate minerals existing in the ore as well as the associated non-phosphatic material. Simple beneficiation techniques such as crushing and screening or scrubbing and desliming are successfully used when the main gangue material is hard siliceous material, silicates and/or clayey material. Ores containing quartz, chalcedony or different forms of silica, may be upgraded using gravity and/or electrostatic techniques. However, the use of these techniques for large scale production is limited due to their limited capacities. The main conventional concentrating technique for such ore is flotation. Flotation in this case is carried out either in one stage or two-stage operation. The one stage technique is mainly to float the phosphate minerals using oleic acid or sodium oleate with the addition of fuel oil (kerosene) as collectors at pH=8. the twostage process includes, in addition to the previous step, decreasing the value of pH to 4, skimming the desorbed oleic acid, and adding cationic collector to float the trapped silica. This technique produces a clean high grade phosphate product. Igneous phosphate rocks are concentrated mainly by anionic flotation of phosphates. The flow-sheet for upgrading this type of ore may include intermediate steps depending on the type of gangue minerals associated with the phosphate minerals. If sulfides exist, they are removed by flotation. Magnetic

minerals are removed by magnetic separation, and clays and fine impurities are removed by attrition scrubbing and desliming. Phosphate ores containing high content of organic material as the main ingredients are processed by calcination at about 500 to 750 oC to burn out the organic material. Sometimes, calcination temperature is higher than this range, which may be as high as 800 oC to burn the residual carbon. At this low range of temperature, physical and chemical properties of the phosphate minerals are not significantly affected and hence, the reactivity index of the phosphate is not remarkably affected. The reactions taking place as a result of raising temperature are exothermic reactions which does not need large additional amount of energy. The calcined product in this case is suitable for the manufacture of clear green phosphoric acid which is used as a source for producing super phosphoric acid and other high grade chemical reagents. The calcareous sedimentary phosphate ores form the main challenging problem in phosphate processing. Electrostatic and gravity separation are not yet up to the large scale production techniques. Extensive efforts have been spent to use flotation, which is the most widely technique used in processing most of the ores with different modifications and developments, for upgrading the calcareous sedimentary phosphate ores. On the laboratory scale, some of these approaches were successful, but they are not tested in pilot or industrial scales. The rest of these efforts were neither practical nor successful. To

28
utilize these natural phosphate deposits, some of them are being calcined and/or defluorinated. Although these products are of inferior quality with respect to the chemical reactivity and extensive amounts of energy are used, they are almost pure products suitable for producing high grade chemical reagents and/or defluorinated phosphates for animal feed stocks. These calcines are of high quality and are sold as expensive commodities for special purposes. In the case of using these products for producing phosphoric acids defrothing reagents are not needed, and filtration of residual solids are made easier. Researches for economic and technical utilization of the huge calcareous phosphate deposits around the world are urgently needed. Thorough understanding of the thermodynamics of the carbonate/phosphate/water systems is of high priority. Development of suitable flotation collectors that are more selective to phosphate or carbonate minerals is another incentive to apply flotation in upgrading the calcareous sedimentary phosphate rocks. Carefully adjusting the suspension environment ( pH, ionic strength, etc. ) to differentiate between surfaces of phosphates and carbonates for better particle/collector interaction should be considered. The possibility of using electrostatic and/or gravity separators for concentrating phosphates on industrial scale may help solving the problem. Finally, the flash calcination is a promising technique for economic calcination of phosphate ores when it is scaled up to produce large tonnages of phosphate calcines. The product obtained by this technique is of superior quality than that produced by the other conventional calcinations techniques. [1]

Volume 9 - Issue 17

Emich, G. D., 1984, Phosphate Rock "Industrial Minerals and Rocks, vol. 2, pp. 1017-1047. Jasinski, S. M., 2007 "Phosphate Rock," USGS, pp. 120-121 Straaten, P. V., 2002, " Rocks for Crops , Agro minerals of sub-Sahara Africa, " pp. 7-24 USGS survey , Mineral Commodity Summaries, Jan 2003, Global Reserves and Availability. Haarr, A., 2005, " The Reuse of Phosphorus," Eureau Position paper EU2-04-SL09,pp. 1-2 Steen, I., 1998, Kemira Agro, in Phosphorus and Potassium, Issue no. 217, Proceedings from JRC Workshop on problems around sludge, Stresa, 1999. Evans, T. D., and Johnston, A. E., 2004, Phosphorus in environmental technologies, in E. Valsami-Jones (ed), IWA. Jasinski, S. M., 2005, Phosphate Rock, Minerals Yearbook, Vol.56, pp. 1-10. Cathcart, B., 1967, Proc. Escafe Seminar, Bangkok, Thailand, Minerals Resources Development Series Rep. No. 32, United nations, New York, 1968.

[2] [3] [4] [5] [6]

[7]

[8] [9]

[10] Service, A. L. and Popoff, C. C., 1967, U.S. Bur. Mines Rep. RI-6935. [11] Wilson, M. A. and Ellis, B. G., 1984, Soil.Sci., Vol.138, pp. 354-359. [12] Blazy,P., and Bouhaouss, A., 2005, Minerals and Metallurgical Processing vol. 22, no. 2,pp. 107-115. [13] Henin, J. P. and Lectard, A., 1983, Engineering and Mining Journal, vol. 10,pp. 77-84. [14] Henin, J. P. and Pinoncely, A., 1986, Industrie Minerals, Mines and Carrieres, Les Technologues, pp. 249-252. [15] Phosphate Rock Processing, Mineral Products Industry, Emission Factors, 1993, Section 11. 21, pp. 1-10. [www.epa.gov] [16] Ciccu, R., C. Delfa, G. B. Alfanu, P. Carbini, L. Currelli, and P. Saba, 1972, International

ACKNOWLEDGEMENT
The author would like to thank Dr. Bhaskar Bandyonadhyay, consultant, Professor Peter van Straaten from the University of Guelph, Canada, Miss Karen Stewart, Librarian at Florida Institute of Phosphate Research, and the phosphate Staff at the United States Geological Survey for their close contact and appreciable help. They provided the author, generously, with the necessary information regarding the subject. The author's appreciation is also extended to Miss Eanass Abouzeid for her patience in typing the draft of the paper and reproducing the attached Figures.

REFERENCES

A.M. Abouzeid/The Journal of ORE DRESSING 2007

29
[31] El-gillani, D. A., 1992, The Third Mining, Petroleum, and Metallurgical Engineering conference, Cairo, Egypt, pp. 204-211. [32] El-gillani, D. A. and Abouzeid, A. -Z. M., 1993, International J. of Minr. Process, vol. 38, pp. 235-256. [33] Zafar, I. Z., Anwar, M. M. and Pritchard, D. W., 1995, Int. J. Miner. Process, vol. 43, pp. 123-134. [34] Hignett, T. P., Doll, C. E., Livingston, O. H., and Raistrick, B., 1977, Utilization of Difficult Ores, L. J. Carpentier (ed. )m New Developments in Phosphate Fertilizer Technology, Proceedings, pp. 273-288. [35] Mew, M. C., 1980, World Survey of Phosphate Deposits, 4th Edn., The British Sulphur Corp., London, p. 2. [36] Baudet, G., 1988, The Processing of Phosphate Ores, Chron. Rch. Miner., Special Issue on Phosphates, p. 67. [37] Crago,A, 1940, Process of Concentrating Phosphate Minerals, US Patent No. 2,293,640. [38] Lawver, J. E., Murowchick, B. L., and Snow , R. E., 1978, ISMA, Technical Economic Conferences, Orlando, Florida, Preprint TA/78/1. [39] Lawver, J. E., Wiegel, R. L., Snow, R. E., and Hwang, C. L., 1982, Min. Congr. J. vol. 68, p. 27. [40] Snow, R. E., 1979, Beneficiation of Phosphate Ores, US Patent No. 4,144, 969. [41] Dufour, P., Pelletier, B., Predali, J. J., and Ramchin, G., 1980, Proceedings, Second International Symposium on Phosphorus Compounds, Boston, MA., pp. 247. [42] Lehr, J. R., Hsieh, S. S., 1981, Beneficiation of High Carbonate Ores, US Patent No. 4, 287,053. [43] Moudgil, B. M., and Chanchani, R. 1985, Metall., Process, vol. 2, No. 1 pp. 13-18. [44] Moudgil, B. M., and Chanchani, R. 1986, Metall., Process, vol. 2, No. 1 pp. 19-25.

Mineral Processing Congress, University of Cagliari, Italy. [17] Hammoud, N. S., Khazback A. E., and Ali M. M., 1977, International Mineral Processing Congress. [18] Abdel Moneim, H. M., 1971. "Geological investigations and Physical beneficiation of Some Low grade Phosphate rocks in Egypt", M. Sc. Thesis, Ein- Shams University. [19] Abouzeid, A. -Z. M., Khazback, A. E., and Hassan, S. A., 1996, International Mineral Processing Symposium, Izmir, Turkey, Changing Scopes in Mineral Processing, Kemal, Arsalan, Akar, and Cambazoglu (eds. ), pp. 161170. [20] Taggart, A. F., 1964, Handbook of Mineral Dressing, New York. [21] Lovell, V. M., 1976, Flotation A. M. Gaudin Memorial volume. M. C. Fuerstenau. (ed)., New York, AIME. [22] Silvia, A. F. and Andery, P. A., Jan. -Feb. 1972, Phosphorus and Potassium, No. 57, the British Sulphur corp., London, pp. 37-40. [23] Breathitt, H. W. and Finch, E. P., 1977, Preprint 77-H-143, SME, AIME. Annual Meating, Atlanta, 31 pp. [24] Personal Communication with the Minestry of Industry and Mineral Wealth, Abu-Tartor Phosphate Project, Egypt. [25] Electronic Communication with USGS Staff. [26] Hanna, H. S., 1964, M. Sc. Thesis, Faculty of Science, Cairo University. [27] Personal Communication with Abu-Zaabal Company for Chemicals, Cairo, Egypt. [28] Hanna, J. S. and Anazia, I., 1990, Minerals and Metallurgical Processing, vol. 10, pp. 84-89. [29] Elgillani, D. A., 1978/1979, Bulletin of Faculty of Engineering, Cairo university, pp. 237-245. [30] Elgillani, D. A., Abouzeid, A. -Z. M., and Negm, A. A., 1984, Final Report to the supreme Council of Universities (FRCU) of Egypt.

30
[45] Ince, D. E., 1987, Ph. D. Thesis, University of Florida [46] Moudgil, B. M., Ince, D. E., Vasudevan, A. N., and Sober, D., 1990, Miner. Metall. Process, vol. 7, No. 1, pp. 53-60. [47] Zhong, T. V., Vasudevan, A. N., and Sumasandaran, P., 1991, J. Miner. Eng. vol. 4, pp. 563-571. [48] Bell, L. C., Posner, A. M., and Quirk, J. P., 1973, J. Colloid and Interface Sci., vol. 42, pp. 124-134. [49] Doss, S. K. T., 1976, J. Dent. Res., vol. 55, pp. 1076-1083. [50] Mishra, R. K., Chander, S., and Fuerstenau, D. W., 1980, Colloids and Surfaces, vol. 1, pp. 105114. [51] Mishra, R. K., 1978, Int. J. Miner. Process, vol. 5, pp. 69-76. [52] Smany, M. S., Blazy,P., and Cases, J. M., 1975, Parts: I, II, III, and IV, Trans AIME, vol. 258, pp. 168. [53] Somasandaran, P., and Agar, G. E, 1972, Trans. AIME, vol. 252, pp. 348-356. [54] Somasandaran, P., and Agar, G. E, 1967, J. Colloid Interface Sci., vol. 24, pp. 433-440. [55] Eigeles, M. A., 1958, 4th International Mineral Processing Congress, Stockholm, pp. 391-401. [56] Saleeb, F. Z., and DeBruyn, P. L., 1972, Electro analytical Chem. And Interfacial Electrochemistry, vol. 37, pp. 99-108. [57] Somasandaran, P., 1968, J. Colloid Interface Sci. vol. 27, pp. 659-665. [58] Aplan, F. F., and Fuerstenau, D. W., 1962, Froth Flotation, D. W. Fuerstenau (ed), pp. 170-178. [59] Hanna, H. S., Somasandaran, P., 19769, A. M. Gaudin, Memorial volume, Flotation, AIME, M. C. Fuerstenau (ed), pp. 197-205. [60] Johnston, D. J., and Leja, J., 1985, Trans. IMM, pp. C315-C326.

Volume 9 - Issue 17

[61] Mitzmager, A., Mizrahi, J., and Fischer, E., 1966, Trans. IMM, pp. C257-C266. [62] Bertolucci, M., 1968, Adv. Chem. Series (ACS), R. R. Gould (ed), pp. 124-135. [63] Soto, H. and Iwasaki, I., (August) 1985, Minerals and Metallurgical Processing, pp. 160171. [64] Rule, A. R., Clark, C. W., and Buttler, M. O., 1974, U. S. Bureau of Mines RI 7864, 18 p. [65] Llewellyn, T. O., Davis, B. E., Sullivan, G. V., and Hansen, J. P., 1982, US Bureau of Mines RI 8609,16p. [66] Moudgil, B. M., Blanchard, F. N. Shah,D. O., Onoda,G. V., and Whitney, E. D., 1986, Internal Report FIPR, vol. III. [67] Johnston, D. J. and Leja, J., 1978, Trans. IMM, pp. C237-C245. [68] El-gillani, D. A., and Abouzeid, A. -Z. M., 1994, 5th Int. Mineral Processing Symposium, Cappadocia, Turkey, pp. 179-191. [69] Rule, A. R., Kirby, D. E., and Dahlin, D. C., 1978, Min. Engng., vol. 30, pp. 37-44. [70] Zhang, P., Albarelli, G. R., and Stewart, K., 1999, Phosphate Beneficiation Bibliography, FIPR, Project no. 96-02-114. [71] Personal Communication with Dr. Bhaskar Bandyopadhyay, Consultant. [72] Kunii, D., and Levenspiel, O, 1969, Fluidization Engineering, John Wiley & Sons, Inc, Ch. 1 & 2, pp. 1-63. [73] Bandyopadhyay, B., Preserve. Nal. USDA, vol. 61. [Preserve.Nal.usda. gov:8300/jag/v61/v61i07/610539/a610539.ht m] [74] Coffey, R. D., Mooney, K. W., Cromwell,G. I., and Aaron, D. K. -J., 1994, Animal Sci. vol. 72, pp. 2653-2660. [75] Ullmann's Encyclopedia of Industrial Chemistry, 1991, vol. A19, pp. 448-455. [76] Abouzeid, A. -Z. M., Energy Balance in Phosphate Calcination, paper to be published.

A.M. Abouzeid/The Journal of ORE DRESSING 2007

31
Organization Public relations division, pp. 194242. [92] Lehr, J. R., 1964, Proceedings, 17th Annual Meeting of Fertilizer Industry Round-table, Washington D.C., pp. 61-67. [93] Le Geros, R. Z., Trautz, O. R., 1967, Science, vol. 155, pp. 1409-1411. [94] Cuthbert, F. L., and Rowland, R. A., 1947, Ame. Mineralogist, vol. 32, 1947. pp. 111116. [95] Plotzki, E., 1937, Arch. Eisenhutten, vol. 11, 1937. pp. 263-272. [96] Faust, G. T., 1944, Econ. Geol., vol. 39,1944. pp. 142-151. [97] Faust, G. T., 1950, Ame. Mineralogist, vol. 35, 1950. pp. 207-224. [98] El-Jallad, I. S., 1977, Investigations on the upgrading processes of the low grade phosphate. Ph. D. Thesis, Cairo University. [99] McConnell, D., 1959, Econ. Geol., vol. 54, pp. 749-751. [100] Ames, L. L., 1959, Econ. Geol., vol. 54, pp. 829- 841. [101] Khalifa, H., Orphy, M. K., and Gharib. E. A., 1972, Concentration of phosphate ores, Safaga Area., MSc. Thesis., Cairo University. [102] Stern, S., 1965, Internnational Superphosphate Manufacturing Association, Technical Conference, vol. VI, pp. 1-12. [103] Rudis, 1967, Mining .Industrial Association TRBOVLJE, Yugoslavia, Safaga Engineering Report No. 2. [104] Nikitin, A. A., and Vorob'ev, Yu-M, Kh. S., 1966, Sb. Tr. Gos. Vesses. Nauchn. Issled. Inst. Stroit, Materialov, Konstraktsil, no. 6, pp. 153-171. [105] Hegner, P., and Pacl, Z., 1974, Research Institute of Inorganic Chemistry, Czechoslovakia, Internal Report. [106] Saadi, T. A. K., 1969, Mineralogy, crystal chemistry and genesis of some ores, M.Sc. Thesis, University of Durham.

[77] Abouzeid, A. -Z. M., El-Jallad, I. S., and Orphy, M. K., 1980, Minerals Sci. Engng. vol. 12, No. 2, pp. 73-83. [78] Priestly, R. J., 1967, Prac. Intern. Symposium on Fluidization Netherlands Univ. Press, Amsterdam, pp. 81. [79] Perry, R. H., Chilton, C. H., and Kirkpatrick, S. D., 1963, Chemical Engineering Handbook, 4th Edition, Gas-Solid systems, pp. 51. [80] Disanto, B. J., SME Mineral Processing Handbook, Ch. 12 Pyrometallurgy, Ch. 12, pp. 1-59. [81] Ball, D. F., Dartnell, S., Davison, J., Grieve, A., and Wild, R, 1973, Agglomeration of Iron Ores, Heineman. Educational Books Liol., London, Ch. 3, pp. 253-364. [82] Ersahan, H., Ekmekyapar, A., and Sevim, F., 1994, Int. J. Miner. Process., vol. 42, pp. 121136. [83] Bridson, D., Davies, T. W., and Harrison, D. P., 1985, Clays and Clay Minerals, vol. 33, No. 3, pp. 258-260. [84] McClellan, G. H., and Lehr, J. R., 1969, Ame. Mineralogist, vol. 54. pp. 1374-1391. [85] Palache, C., Berman, H., and Frondel, C., 1951, Dana's system of mineralogy, 7th ed. vol. H, 1951, New York, Wiley. pp. 877-889. [86] Hendricks, S. B., 1952, Trans. Macy Conf., vol. 4, pp. 185-212. [87] Altschuler, Z. S., Cisney, E. A., and Barlow, I. H., 1952, Bull. Geol. Soc. Am., vol. 63, pp. 1230-1231. [88] Silverman, S. R., Fuyat, R. K., and Weiser, J. D., 1952, Ame. Mineralogist, vol. 37, pp. 211222. [89] Maslennikov, B. M., and Kavitskaya, F. A., 1956, Dokl. Akad. Nauk. S. S. S. R., vol. 109, pp. 990-992. [90] Alden, K. I., and Lindgvist, I., 1964, Z. anorg, allg. Chem., vol. 328, pp. 219-222. [91] Lehr, J. R., and McClellan, G. H., 1974, CentoSymposium on the Mining and Beneficiation of Fertilizer Minerals, Ankara, Central Treaty

32
[107] Rosch, H., and Saadi, T. A., Phosphate exploration and beneficiation studies, Jordan, United Nations, Technical Report, DP/UN/JOR-70-521/2. [108] EL-Jallad, I. S., 1968, Beneficiation of the low grade hard phosphate deposits in Roseifa Area, Jordan, M. Sc. Thesis, Cairo University. [109] Masson, J., 1959, Rev. Ind. Mineral, Enrichment by calcinations of phosphate carbonate ores, vol. 41, 1959. pp. 651-661. [110] Alekseev, V. S., and Shakmatova, N. U., 1964, Akad. Nauk. U.S.S.R. Kolsky Filial, Gornometallurgy Institue. [111] Flaszenberg, A. I., prulov, I., and Lapidot, M., 1962, Upgrading of phosphate rock. U. S. Patent 3,037,023. [112] Orphy, M. K., Yousef, A. A., and Bibawy, T. A., 1969, Min. Mag., vol. 121, pp. 25-28. [113] Stolovitskaya, M. M., 1966, Sb, Tr. Gos. Vses., Nauch-Issled, Inst. Stroit, Materialov Konstruktsii, no. 6, pp. 114-117. [114] Freeman, H. P., Caro, J. H. and Heinly, N., 1964, J. Agric. Food Chem., vol. 12, 479486. [115] Ando, J., and Matsono, S., 1966, Bull Chem. Soc. Japan, vol. 39. pp. 64-70. [116] Smith, J. P., and Lehr, J. R., 1966, J. Agr. Food Chem., vol. 40, pp. 342-349.

Volume 9 - Issue 17