The 2nd International Conference on Energy Engineering ICEE-2, December 27-29, 2010 - Aswan, Egypt

MECHANICAL ACTIVATION OF PHOSPHATE ROCK FOR FERTILIZER APPLICATION

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Suzan S. Ibrahim1, Ayman A. El-Midany2, and Tawfik R. Boulos1

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Central Metallurgical R&D Institute (CMRDI), P.O. Box 87, Helwan, Egypt, suzansibtahim@gmail.com

Mining, Petroleum, and Metallurgy Dept, Faculty of Engineering, Cairo Univ., Egypt

ABSTRACT The direct application of phosphate rock as fertilizer is both technically and economically bases is justified in terms of both actual economic recession and the high demand of energy in sophisticated wet processes. Mechanical activation of the phosphate rock, causing substantial distortion in the crystal lattice proved to be the appropriate alternative for improving the solubility and availability of P at a better economic level. The chemical reactivity of the activated crude ore in 2% citric acid and neutral ammonium citrate (at 65Co) showed better leaching conditions through all the milling stages. KEYWORDS Mechanical activation, crystal lattice disorder, chemical reactivity, phosphate fertilizer. INTRODUCTION Following a deep recession in 2008/09, the global economic recovery is evolving better than was anticipated a year ago. Growth in gross domestic product (GDP) started to pick up in the second quarter of 2009. According to the International Monetary Fund (IMF), world output is expected to expand by 4.2% in 2010 and 4.3% in 2011, following a 0.6% contraction in 2009. Emerging and developing economies have been less impacted by the downturn and are, on average, recovering much faster. This rapid improvement in the economic outlook has been made possible by strong monetary and fiscal policy measures to sustain growth and employment. Priority is now being given to containing and reducing public debt. It is anticipated that the effectiveness of austerity measures in many of the advanced economies will affect confidence and growth in years to come, particularly in Europe (Patrick Heffer and Michel Prudhomme, 2010). The current economic and financial situation is expected to impact fertilizer demand in several ways. A return to more stable commodity prices makes it less risky for farmers to invest in fertilizers than a year ago; this is resulting in a more rapid recovery in phosphate (P) and potassium (K) fertilizer demand than had been foreseen (Heffer and Prudhomme, 2010).

The majority of phosphate fertilizers produced in the world today is obtained from acidulation of phosphate rocks or containing over 95% of the total P 2O 5 in water soluble forms. Global phosphoric acid capacity in 2008 grew by 3 Mt to 46 Mt P 2O 5 mostly due to the expansion in China, Morocco, Mexico, and Vietnam. In the meantime global MAP-DAP capacity in 2008 grew by 2.4 Mt P 2O 5, (IFA, 2008). Table 1 shows the water soluble and available P2O5 in common phosphate fertilizer, (Abouzeid, 2008). However, the MATERIALS & MECHANICAL DESIGN IN THE FIELD OF ENERGY (MD)
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The 2nd International Conference on Energy Engineering ICEE-2, December 27-29, 2010 - Aswan, Egypt major problem which significantly threatens the near future prospects of the wet processes is the availability of raw materials with specific chemical composition. Consequently sophisticated beneficiation flow-sheets of higher expenses are required to treat marginal and low quality ores. On the other hand, the increase in energy demand is reported due to the rising of fertilizers consumption and a shift towards less energy intensive fertilizers is becoming a priority. In this respect the trend towards direct application of phosphate rocks is growing to reduce the production expenses of fertilizers and to maintain micronutrients in the raw phosphate from its loss during the wet technologies. However, the low solubility and consequently the low availability of the P for the plants growing represent the main problems of direct application of phosphate rocks. In this particular aspect comes the effect of highly intensive size reduction equipments like vibrating, centrifugal, jet, and others to increase the phosphate rock solubility. In spite of some disadvantages, the development of the rotary-chamber vibrating mill, which is based upon the introduction of freely moving chamber wheel in the milling tube, (Gock et al, 1986) was the least alternative to ultra-fine grinding methods. Beyond the surface expansion which occurs through the vibrating tube mill, the high collision energy conveyed by this method induces lattice defects through disintegration. These lattice defects, which deviate from the initial lattice structure lead to a growth of the free enthalpy, (Gock et al, 1986). The article deals with the intensive grinding, or mechanical activation, of some Egyptian phosphate ores and phosphor-concentrates, using the same rotary chamber vibrating mill to increase their solubility.

Figure 1. Projected evolution of regional fertilizer demand in 2008/09 and 2009/10 (Abouzeid, 2008). Table 1. Global fertilizer consumption, 2006/07 to 2009/010 (Mt nutrient) (Abouzeid, 2008).

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The 2nd International Conference on Energy Engineering ICEE-2, December 27-29, 2010 - Aswan, Egypt Figure 2. Production, imports, exports and consumption of fertilizers, (Abouzeid, 2008). 2. EXPERIMENTAL 2.1. Materials& Methods A Phosphate ore sample from Red Sea region, Egypt was applied in this study. About one kg sample with D50 and D90, reaching 0.315mm and 0.063mm was fed to the three tube rotary chamber vibrating mill (Gock et al, 1986) at 15, 30, 45, 60, and 90min milling time. In every milling time a sample of about 40g was taken every 15min for particle size measurements as well as following up the structural changes by XRD, IR spectroscopy, and thermal analyses. A Philips PW1050/25 X-ray diffractometer was used for XRD examination. The relative intensities, I/Io, of the X-ray impulses at the lattice plane of the sample to be activated, was carried out, (Io= before, and I= after the grinding). Every I/Io was assigned to a definite reaction behavior, e.g. lattice defects as well as one-or multi-phased solid state reactions. Measuring the integrated relative area under each diffracted peak for each milling period, could be another mean to emulate how much the crystal lattice was distorted. Planometer was used to measure such areas. Infrared spectra was conducted using PYE-Unicam Philips, SP 2000 IR spectrometer. Both differential thermal analysis (DTA) and thermo-gravimetric analysis (TGA) of the original and milled products were conducted using Linseis unit and Gerbruder Netzsch, Selb sensitive thermo-balance, successively. The heating rate was 2C/min up to 1000 C, sample weight 350mg, and reference material Al2O3. Particle size determination of the ground samples was done by using a PABISCH type 715 Laser granulometer. 2.2. Process Kinetics Solubility tests were carried out using 2% citric acid (CA) and neutral ammonium citrate (NAC) at 65C solutions, (Lehr et al., 1973). The following conditions have been maintained to perform the previous tests: weight of sample: 2.5g, volume of the citric acid and citrate solutions 250 ml, duration time of the reaction 30 min, at temperature 20 C, separation solid/liquid: centrifuged 2 min at 4000 rpm, and reproducibility 1%. 3. RESULTS & DISCUSSION 3.1. Samples Characterization The phosphate sample was identified as calcareous phosphate type with minor clayey content. The phosphate mineral was ranging in size between 150-3000 micron for collophane grains and 150-2250 micron for bone fragments. The hardness of the ore varied from friable to hard phosphate type. Microscopic evaluation showed that the ore consisted mainly of collophane, bone, and fossil fragments, Figure 3. The phosphate mineral was impregnated with hematite, pyrite, and other ferruginated materials. The ore is distinguished in rounded, elongated and irregular grains. Bio-detrital phosphate in the form of bone fragment, vertebrae and teeth are also identified in phosphate cemented with calcareous siliceous matrices. The calcareous cement, most probable dolomite, was observed partially replacing the bone fragments and cellophane especially along the borders of the sample, Figure 3. A B C

Figure 3. (A) Rounded collophane grain embedded in calcareous matrix, (B) Ankerite and dolomite cementing phosphate mineral, and (C) Colloferm texture in collophane and fossil debris cementing with calcareous and ferruginous minerals, (P.P.L., x 120). Table 2 illustrated the main constituting oxides of the sample. X-ray diffraction analysis indicated the presence of hydroxyl-apatite, carbonate-apatite, montmorillonite, glauconite, dolomite, and calcite, Figure 4. The thermal behavior of the sample showed an endothermic peak between room temperature up to 200 oC with a maximum at 90 oC, indicating the dehydration of montmorillonite mineral, Figure 5. A broad faint endothermic MATERIALS & MECHANICAL DESIGN IN THE FIELD OF ENERGY (MD)
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The 2nd International Conference on Energy Engineering ICEE-2, December 27-29, 2010 - Aswan, Egypt peak was appeared at 230-350 oC with a maximum at 285 oC due to the dehydration of some hydroxides, while the dissociation of the inorganic carbonate appeared at 700-800oC, Figure 5. Table 2. Chemical constituents of the sample Constituents Wt.% 22.23 P2O5 38.05 CaO 4.90 MgO 10.20 SiO2

Figure 4. XRD patterns of original phosphate sample

-1 0 1 A ,m T V 2 3 4 5 6 0 200 400 600 Temperature, C 800 1000 DTA TGA 0 1 2 3 4 5 6 7 1200 W loss, % t

Figure 5. Thermal analyses of original phosphate sample 3.2. Physical Characteristics of the Milled Products 3.2.1. X-ray Diffraction Patterns The XRD patterns of the sample after 90min milling showed drastic disintegration in the ore minerals related peaks, e.g., quartz, iron oxide, and carbonate minerals, Figure 6. Complete disappearance of some peaks such as dolomite and calcite peaks were observed which indicates complete crystal lattice distortion or phase transformation from one form to another, (Ibrahim, 1990). Generally, the extraneous gradual decay in all the XRD peaks with increasing milling times indicated the validity of the grinding process, Figure 6. The integrated relative areas under each diffracted curve for each milling period, as another mean to emulate how much the crystal lattice was disordered, was depicted in Table 3. The rational amounts of lattice imperfection reached 43.95% after 90min milling time, Figure 6. It could be concluded that the destroy of the dolomite or calcite lattice plane indicating the transformation of carbonate to oxide forms through CO2 split off by the heat evolved during milling, (Cock and Jacob, 1984). Formation of a new compound like Ca7 (CO3) (Si6O18).2H2O, was formed as a result of the reaction between the highly activated carbonate and silica fragments, was also concluded, (Ibrahim, 1990): Ca CO3 + SiO2 (High pressure and temperature) = Ca5 (SiO4)2 CO3 Ca5 (SiO4)2 CO3 + Humidity = Ca7 (CO3) (Si6 O 18. H2O = Ca6Si6O18.2 H2O. CaCO3

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The 2nd International Conference on Energy Engineering ICEE-2, December 27-29, 2010 - Aswan, Egypt

Figure 6. The XRD Patterns of the sample after different milling times Table 3. The integrated relative areas under XRD peaks for each milling time Milling Time, min Peak Area, cm2 Disorder% 0 15 30 45 60 75 90 223 188 166 140 137 130 125 15.69 25.56 37.22 38.56 41.70 43.95

3.2.2. Infra-Red spectroscopy The effect of intensive grinding of the sample with time by IR technique was illustrated in Figure 7. The gradual corruption in the major P-O bands at V1 and V3 modes was obvious, Figure 7. Complete disappearance in the calcite related peaks at 878 and 1420 cm-1 was recorded. Remarkable decrease in the peak intensity related to quartz at 798 cm-1 frequency was also observed, Figure 7.

Figure 7. IR spectra of phosphate sample after different milling times 3.3. Process Kinetics: Chemical Reactivity and Solubility The absolute solubility indices (ASI) of the raw phosphate sample in 2 % citric acid, CA and neutral ammonium citrate (NAC) were shown in Figures 8 and 9. A remarkable increase in the dissolution rates of the activated products were recorded, indicating the efficiency of the intensive grinding treatment on the solubility behavior of the sample. Gradual improvement in the ASI values of the milled products with increasing milling time, signifying the utility of the grinding with time, Figures 8 and 9.

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The 2nd International Conference on Energy Engineering ICEE-2, December 27-29, 2010 - Aswan, Egypt

Figure 7. Solubility index of phosphate samples in 2% CA at different milling times

Figure 8. Solubility index of phosphate samples in NAC after different milling times 3.5. Size Distribution & Surface Area Measurements of the Milled Products Table 4. illustrated the particle size distribution of the milled products after different milling times. Surface area measures of milled products after 15min and 90min were 2.21 m2cm3, 2.81m2cm3 for the raw phosphate sample. Gradual increase in the %D90 values with increasing milling time till 60min milling was noticed, Figure 7. The sharp decrease after 60min i.e. at 75min and 90min indicated the invalidity of increasing time to improve the grindability characteristics of the sample, Table 4. The solubility optima for the milled samples at same milling time of 60min in CA and NAC were observed, Figures 7 and 8. This latter trend was identical with that of the change in %D 90 of the phosphate samples by increasing in milling time, Table 4, which indicated the effect of the sample size on its solubility. Evidently, symptoms of agglomeration were recorded after 60 min and 75 min for both samples. In the mean time, progressive structural changes in the apatite lattice with time proving that dispersion is not necessarily the main process affecting rock reactivity during intensive milling or mechanical activation. Table 4. Mean particle size analyses of the milled products after different milling times Property 15min 30 min 45min 60min 75min 90min . D10 1.50 0.97 0.95 1.10 1.20 0.75 D50 6.10 7.30 7.50 10.9 7.80 8.20 D90 33.10 40.20 43.90 50.90 46.30 37.40 3.6. Effect of Activated Phosphates on Cultivated Lands of Different Nature The influence of the mechanical activation was correlated with the pH-values (Cock and Jacob, 1984). It was shown that within a pH-range between 5 and 7, which is of great importance for the Egyptian cultivated lands, a good initial leaching velocity can be achieved, which, however, increases strongly with the progressive mechanical activation. In addition to the leaching velocity, the phosphorous-equilibriumconcentration is also important for the fertilizing effect. Hence, further investigations are necessary to establish the existence of a relationship between the mechanically activated phosphorite and the phosphorous- equilibrium of the refined phosphate fertilizer. A large proportion of potentially onable land in the tropics is strongly acidic and tends to be extremely deficient in phosphorus, a case which could be typical for natural phosphate application 3.7. Economic Preference of Mechanical Activation The simple rough comparison between the costs of just mechanical activation of the phosphate ore with the running different beneficiation steps to produce a concentrate suitable for the production of the phosphoric acid, which is an intermediate step of all the fertilizer manufacturing process. This comparison MATERIALS & MECHANICAL DESIGN IN THE FIELD OF ENERGY (MD) [MD 300] 6/8

The 2nd International Conference on Energy Engineering ICEE-2, December 27-29, 2010 - Aswan, Egypt shows that the activation will lead to impressive savings, Table 7. Initially, the saving is due to the reduction in the costs (capital and operating costs) of the beneficiation steps. Moreover, the same thing will happen to the wet process that cost much more than beneficiation processes due to dealing with acids (i.e., one ton of sulfuric acid costs about 700 $), besides the corrosion problems, which increase the maintenance costs as well. Table 7. Costs of Mechanically Activated Raw- and the Processed Phosphate Fertilizers Costs/ton Wet Processed Phosphate Mechanically Activated Fertilizer Raw-phosphate Fertilizer Mining 70-80 $ 70-80 $ Processing 50-60 $ Min. P2O5= 32% -H2SO 4 700 $ -Energy 35$ (350 kWh/t) 2.50 $ (25kWh/t) 8.0 $ (80 kWh/t) Market price/ton 1000-1200 $ 400 $ Calculations based on 10 cents/ kWh CONCLUSIONS The higher demands of energy in the current fertilizer industry mandate the searching for other methods/ techniques. Mechanical activation represents one of these solutions that overcome the limitations of the raw phosphate, in terms of lattice structure and low solubility, to be used as a direct fertilizer in so many developing countries and serve capital regional markets when arbitrary grade specifications do not apply. The mechanical activation results showed a remarkable increase in the reactivity of the treated phosphate samples. The chemical reactivity of activated raw samples in 2% citric acid and neutral ammonium citrate, showed better leaching attitude through all the milling stages. REFERENCES Heffer, P and Prudhomme, M, (2010). Fertilizer Outlook 2010 2014. 78th IFA Annual Conference, Paris. Abdel-Zaher M. Abouzeid, (2008). Physical and thermal treatment of phosphate ores an overview. Int. J. Miner. Process. 85, 5984 Gock, E., Kurrer, K, and Michealis, S., (1986). Vibrating milling: progress in theory and industrial application. 1st World Congress Fine Particle Technology, Part II, 653-666. Lehr, J.R. and McClellan, G.H., (1973). A revised laboratory reactivity scale for evaluating phosphate rocks for direct applications. TVA Bull., Y-34, pp. 36, NFDC, Muscle Shoals, Alabama. V.V Boldyrev, D. Berlincourt, (1976). Ferroelectrics 10, pp. 111. 23. Gock, E., and Jacob, K.H., (1984). Conceptions for processing the pyrite-bearing phosphorites of AbuTartur . Berliner Geowissen Abh. (A) 50, 381-397, Berlin, Germany. Ibrahim, S.S., (1990). Some Tribo-chemical Aspects on the Treatment of Indigenous Egyptian Phosphates. Ph.D. Thesis, Cairo Univ., Egypt. McClellan, G.H., and Gremillian, L.R., (1976). Evolution of phosphate raw materials. The role of phosphorus in agriculture Symposium, NFDC, Muscle Shoals, Alabama, USA. Gock, E., Kurrer, K, and Michealis, S., (1984). Vibrating milling: progress in theory and industrial application . 1st World Congress Fine Particle Technology, Part II, 653-666. Latkin, A. S., and L. A. Samatova, (1998). Thermo-chemical methods of treatment of low-grade phosphate raw materials. Journal of Mining Science, Vol.34, No. 1. Seitnazarov, A.R., S. A. Musaeva, Sh. S. Namazov, and B. M. Beglov, (2007). Mechanochemical activation of ordinary phosphorite powder of Central Kyzylkum mixed with urea nitrate and ammonium carbonate salts. Russian Journal of Applied Chemistry, Vol. 80, No. 11. EGYPT (1996). Phosphate-Based Companies, APS Review Downstream Trends. L.M. Maene, (1999). Phosphate Fertilizer Production, Consumption and Trade, the Present Situation and Outlook to 2010 . The Sulphur Institute's 17th Sulphur Phosphate Symposium, Boca Raton, Florida. K. F. Isherwood, (2000). The State of the Fertilizer Industry Past, Present and Future. Annual General Meeting, 68th IFA Annual Conference, Oslo, Norway. S. H. Chien, P. W. G. Sale and D. K. Friesen, (1990). A discussion of the methods for comparing the relative effectiveness of phosphate fertilizers varying in solubility. Nutrient Cycling in Agro-eco systems, Vol. 24, No. 3, 149-157. MATERIALS & MECHANICAL DESIGN IN THE FIELD OF ENERGY (MD)
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The 2nd International Conference on Energy Engineering ICEE-2, December 27-29, 2010 - Aswan, Egypt J. D. Colwell and W. J. Goedert, (1988). Substitution rates as measures of the relative effectiveness of alternative phosphorus fertilizers. Nutrient Cycling in Agro-eco systems, Vol. 15, No. 2, 163-172. G. L. Mullins and F. J. Sikora, (1994). Effect of soil pH on the requirement for water-soluble phosphorus in triple superphosphate fertilizers, Nutrient Cycling in Agroeco-systems, Vol. 40, No. 3 / October, 207-214. Sikora FJ, Dillard EF, Copeland JP, Mullins GL , (1989). Chemical characterization and bioavailability of phosphorus in water-insoluble fractions of three mono-ammonium phosphate fertilizers. J Assoc off Anal Chem. 72(5):852-6. C. A. Ramrez, and E. Worrell, (2005). Feeding fossil fuels to the soil an analysis of energy embedded and technological learning in the fertilizer industry. Morris L., (2007). Economics of Fertilizer Application. CYMMT Economics working papers. Seitnazarov, A.R., S. A. Musaeva, Sh. S. Namazov, and B. M. Beglov, (2007). Mechanochemical activation of ordinary phosphorite powder of Central Kyzylkum mixed with urea nitrate and ammonium carbonate salts. Russian Journal of Applied Chemistry, Vol. 80, No.11. Latkin, A. S., and L. A. Samatova, (1998). Thermo-chemical methods of treatment of low-grade phosphate raw materials. Journal of Mining Science, Vol. 34, No. 1. Heinike, G., Paudert, R, Harenx, H, Steinike, U, and Poethin, R, (1977). Tribomechanical transfer of apatite to a soluble form. Zhurnal Prikladnoi khimii, Vol. 50, No. 5, 969-974. Kolosov, A.S., Boldyrev, V.V., Chaikina, M.V., Tranzova, M.I., Gordeewa, G.I., paudert, R., Harenz, (1979). The Reactivity of Native Apatites under Mechanical Activation, Proc. of the scientific academy of U.S.S.R. phy. Chemistry sec, 6, 148-55. Paudert, R., Harenz, H., Pothing, R, Heinike, G., KDT, Dunkel, L. and Schumann, H., KDT, (1978). Phosphate fertilizers through Tribomechanical Activation of apatite phosphate. Chem. Techn. 30, Jg., nr. 9, 470-475 Kozlov, V.I. and Kozyrev, S.A., (1982). Selection of apparatus in studies of mechanical activation of phosphate raw materials. Proc. of the scientific academy of U.S.S.R. phy. Chemistry sec, 6, 71-4. Kurrer, K and Gock, E., (1986). Effect of the operating conditions on motion and impact processes in vibratory tube mill. Journal of preparation and processing, 10, 546-554, 27. Malchikov, G.D., Terentyena, T.P., Rubailo, I.S., (1977). Decomposition of mechanically activated phosphate by nitrogen dioxide. Proc. of Scientific Academy of USSR (Phy. Chemistry Sec.), 233 (5), 892-5. Reem Nafie, (2007). Mixed Reactions To New Energy Pricing Strategy, Egypt. V. Balek, L.A. Prez-Maqueda, J. Poyato, Z. ern1, V. Ramrez-Valle, I.M. Buntseva and J.L. PrezRodrguez, (2007). Effect of grinding on thermal reactivity of ceramic clay minerals, Journal of Thermal Analysis and Calorimetry, 88 (1), 8791. M. Erdemolu, M. Sarkaya and M. Canbazolu, (2006). Leaching of celestite with sodium sulphide, Journal of Dispersion Science and Technology, 439442. M. Erdemolu, S. Aydoan and M. Canbazolu, (2007). A kinetic study on the conversion of celestite (SrSO4) to SrCO3 by mechanochemical processing, Hydrometallurgy 86 (12), 15.

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