Processes for phosphorus removal from iron ore - a review

Abstract

This paper aims at reviewing literature on the occurrence of phosphorus in iron ores from the mines around the world. The review extends to the phosphorus removal processes of this mineral to meet the specifications of the steel industry. Phosphorus is a contaminant that can be hard to remove, especially when one does not know its mode of occurrence in the ores. Phosphorus can be removed from iron ore by very different routes of treatment. The genesis of the reserve, the mineralogy, the cost and sustainability define the technol ogy to be applied. The articles surveyed cite removal by physical processes (flotation and selective agglomeration), chemical (leaching), thermal and bioleaching processes. Removal results of above 90% and less than 0.05% residual phosphorus are noticed, which is the maximum value required in most of the products generated in the processing of iron ore.

iron ore; phosphorus removal

1. Introduction

Sometimes, the usual methods of processing are not able to completely remove the phosphorus present in some types of iron ore when trying to make the content of this contamination acceptable (below 0.05%).

The way in which phosphorus is found in iron ore is not well known. Based on results for synthetic samples of goethite (α-FeOOH) and hematite (α-Fe₂O₃), it can be inferred that phosphorus occurs, probably, in the form of phosphate adsorbed on the particle surface or occluded in the micropores. Another possibility is that the phosphorus is located within the structure of the oxyhydroxides or as a phosphate mineral. For synthetic samples, literature reports that goethite has a greater adsorption capacity of phosphate than hematite, certainly due to the higher surface area and porosity of the particles of goethite. Understanding the mode of occurrence of this element in ores will bring new information that can inform the development of methods for their removal (Curi, 1991).

2. Results and discussion

2.1 Phosphate occurrences

Iron ore of high phosphorus content coexists with other minerals in the form of apatite or fluorapatite. Phosphorus is spread on the edge of mineral particles of iron oxide and embedded in quartz or carbonate minerals and a small amount is present in the iron mineral grid (Xia et al., 2011).

The most frequent and important constituent of the class of phosphates is apatite. Besides apatite, various other phosphates may be found in deposits of iron ore (Table 1).

Table 1
Main Phosphorus Minerals Found in Iron Ore (Nunes, 2012)

Mineral	Chemical Formula
Apatite	Ca5(PO4)(F,Cl,OH)
Wavellite	Al3(PO4)2(OH)3.5(H2O)
Senegalite	Al3(PO4)(OH)3.(H2O)
Turquoise	CuAl6(PO4)4(OH)8.5(H2O)
Strengite	Fe3+(PO4).2(H2O)
Rockbridgeite	Fe2+0.75Mn2+0.25Fe3+4(PO4)3(OH)5
Frondelite	Mn2+Fe3+4(PO4)3(OH)5
Gorceixite	BaAl3(PO4)2(OH)5.H2O
Barrandite	(Al,Fe)PO4.2(H2O)
Variscite	Al(PO4).2(H2O)

The most common side phosphates in iron ore are rich in aluminum phosphate or iron phosphate. The wavellite, senegalite and turquoise are commonly found in Brazilian iron ore (Nunes, 2012).

2.2 Extraction processes

2.2.1 Chemical Processes

Acid leaching has been considered as an alternative to flotation for removing phosphorus from iron ore. Technologically, the leaching process is a simpler way to treat the fine-particle sinter feed without the restrictions that are necessary in flotation.

Jin et al. (2006) studied the extraction using either an acid media or basic media. Samples of Changde (China) were submitted to assays. Samples were ground to a particle size smaller than 0.075mm and the chemical analyzes indicated a phosphorus concentration of 1.12%. The minerals were hematite, quartz and kaolinite. The phosphorus was distributed as follows: 22.3% occurring as apatite, 67.9% was disseminated in the iron matrix and only 9.8% was present in silicates. The following leaching media were used: sodium, hydrochloric acid, sulfuric acid and nitric acid hydroxide. The following considerations were taken for chemical treatment:

• Alkaline leaching is ineffective in removing phosphorus from the widespread iron matrix, even increasing the concentration of sodium hydroxide. The increased residence time decreases the removal of phosphorus due to the re-precipitation phenomena;

• Alkaline leaching is effective for removal of the phosphorus present in apatite and silicates;

• Acid leaching is the most efficient method for removal of phosphorus from iron ore. Among the tested acids, sulfuric acid is the most effective for this purpose. The leaching time is low (~20 minutes) and the iron loss is negligible (less than 0.25%).

Zhang and Muhammad (1989) used nitric acid to remove phosphorus from the iron ore of the Kiruna region, Sweden. A concentrate of sinter, moist, and without treatment was used. Chemical analysis showed the composition of 0.98% phosphorus (as P₂O₅ 22.25%) and 60.85% iron. Nitric acid was chosen due to the low reactivity of the acid with the magnetite which was the major constituent of the ore tested. The disadvantage of using nitric acid was the formation of NO₂ or NH⁴⁺. The main conclusions of the researchers were:

• The content of the final match of sinter met the specification required for the production of steel;

• The removal of phosphorus reached 95%;

• Controlling the acidity of the solution, maintained at high concentration, resulted in a low extraction of iron, causing a loss of less than 0.5% because the dissolution of magnetite is very sensitive;

• Small increase in humidity from 2% to 2.7%;

• The control of the reaction of dissolution of apatite is by diffusion.

2.2.2 Bioleaching

The main methods used in the operation of bioleaching processes are: heap leaching, dump leaching and leaching in stirred tanks (Watling, 2006).

Biometallurgy is an option for the removal of phosphorus of iron ore, as there are many microorganisms, especially in environments with limited nutrients which are able to extract the phosphorus contained in minerals (Nautiyal, 1999).

Some studies have been published on the removal of phosphate from iron ore using acid-producing microorganisms, including filamentous fungi and iron-oxidizing bacteria (Buis, 1995).

2.2.3 Physical processes

2.2.3.1 Selective agglomeration

Selective agglomeration is a technology of agglomeration where an immiscible product is added to a suspension of fine particles. This causes the formation of a second phase consisting of particles with the immiscible product. The main cohesive forces are the capillary forces. The result is the formation of flakes or spherical clusters with diameters up to 5mm. The process of removing phosphorus from iron ore linked to the concept of selective agglomeration is well grounded in the work of Sirianni et al. (1969).

Sparks and Sirianni (1974) applied the technique to remove the iron ore’s phosphorus from Snake River, northern Canada. The content of phosphorus was in the range of 0.34% unacceptable for steel production. The iron content was from 44% to 53%, making it very attractive for exploration considering this item. The mineral body mainly consists of the mineral hematite and microcrystalline chalcedonic quartz aggregate in various proportions. Calcite (CaCO₃), dolomite (Ca,Mg (CO₃)₂), apatite Ca₅(PO₄)₃(Cl,F,OH) goethite (FeOOH) and very fine quartz crystals were the smallest constituents which were locally abundant. The gravity separation by jigging achieved an acceptable enrichment of iron concentrate, but the phosphorus was beyond the acceptable level for commercialization (less than 0.07% at that time). Acid leaching, using H₂SO₄, applied directly on the jig, did not get good results because of the precipitation of sulfur compounds. The pH dependence on the collection of fatty acids had already been studied by the authors in a previous work (Sirianni, et al., 1968). The results showed the possibility of using selective agglomeration to separate iron ore and apatite. The assays were applied to a concentrate obtained by jigging. The sample was ground to a particle size smaller than 400 meshes, to ensure release of the apatite. Oleic acid was used as collector and the pH was controlled with NaOH or H₂SO₄. Raw or refined petroleum was used for clustering. Anhydrous calcium chloride was used as the source of calcium ion for activation and sodium silicate as a depressant of iron oxides. The agglomeration process was performed in a ball mill, in which conditioners were added, collector and binder. The dilution of the pulp allowed the formation of agglomerates of phosphorus-bearing mineral with large lumps. The pulp (5 to 10% solids) was placed in a mixer with light oil, like kerosene, after which it was separated by differential sedimentation. After all these stages of processing and treatment, the initial ore which came with 54.6% iron, 0.39% phosphorus, resulted in a concentrate with 65.9% iron, less than 0.02% phosphorus and 5.3% silica. Figure 1 summarizes the operations for this phosphorus removal process:

Figure 1
Flowsheet for Selective Agglomeration

2.2.3.2 Flotation

There are many citations in literature on the reduction of phosphorus in iron ore through anionic flotation, using a fatty acid as collector and sodium silicate as a depressant of iron oxides, when the mainphosphorus-bearing mineral is apatite (Ranjbar, 2002; Siirak and Hancock, 1990; Pyatt, 1990).

Nunes et al. (2012)conducted research on floatability of the mineral phosphorus-bearing wavellite. They evaluated the reduction of the phosphorus content of a Brazilian iron ore with an initial phosphorus content of 0.82%. The best result was obtained with dodecyl amine (approximately 100% of floatability) in pH 8. A concentrate containing 0.201% phosphorus, 62.31% mass recovery was obtained at a dosage of 150g/t of Flotigam EDA (etheramine collector). The authors evaluated Flotigam 2835-2L (collector) in an ore concentrate containing 0.654% phosphorus. The phosphorus content dropped to 0.312% and the mass recovery was 90.24%.

2.2.3.3 Thermal Process - sintering

Sintering is a thermally activated phenomenon that transforms a shaped body composed of crystalline and / or amorphous particles into a rigid body due to diffusion phenomena. A common feature is the decrease in surface area of particles (or grains) with a simultaneous increase of resistance of the shaped body. It can be divided, when considering ceramic reactions, at sintering in states: liquid, solid and viscous (Molisani, 2009).

Feld et al. (1966)patented a process consisting of the mixture of chlorides of alkali metals (sodium, lithium, calcium, magnesium, strontium and barium) with ammonium chlorides, manganese, zirconium and copper in ore in a proportion of 10% by weight. The mixture of ore and additives is calcined at a temperature of 900ºC for 120 minutes. The mixture is cooled and leached at room temperature for 30 minutes with hydrochloric, sulfuric or nitric acid for dissolving the phosphorus compound formed in the furnace. The phosphorus extraction was above 80%, reaching final values of 0.018% from an initial value of 0.421% power.

Xu et al. (2012)investigated the phosphorus removal of oolitic hematite ore of high content of iron by applying a reductive calcination with dephosphorizing agent (Na₂SO₄ and Na₂CO₃). The calcined mass was subjected to two stages of magnetic separation and grinding. The phosphorus content dropped from 0.82% to 0.06% and iron from 43.65% to 60.23% with 87% mass recovery. Analysis showed that 20% of apatite reacted with SiO₂, Al₂O₃ and carbon, generating elemental phosphorus in the form of gas. About 80% of the phosphorus was incorporated into the slag and it was separated from the grinding and magnetic separation. A small residual remains in the apatite concentrate.

Zhu et al. (2013)investigated direct reduction technology by adding sodium carbonate (Na₂CO₃) and afterwards magnetic separation, to treat iron ore from Western Australia with high phosphorus content. They found that phosphorus was inside of the limonite in the form of solid solution that cannot be removed by traditional methods. During the reductive calcination, Na₂CO₃ reacts with gangue minerals (SiO₂and Al₂O₃) forming phosphorus-containing aluminum silicate and modifying the structure of the mineral, promoting the separation of iron and phosphorus during magnetic separation. The composition of iron concentrate obtained: 64.12% Fe and 0.07% phosphorus with an iron recovery of 96.83%, and a rate of dephosphorization of 74.08%. Figure 2 shows a flowsheet for concentration by reductive sintering and removal of phosphorus.

Figure 2
Reductive sintering for phosphorus removing.

2.2.3.4 Mixed processes

Fisher-White et al.(2012) investigated ore from the Pilbara region, Western Australia, in two steps: thermal preconditioning and alkaline leaching using caustic soda. Goethite from Pilbara's ores were formed by supergene metasomatic alteration of fine grains of flint and other ganga minerals in the ore initially precipitated as ferrihydrite, initial product of the rapid hydrolysis of Fe (III), with subsequent dehydration and recrystallization to form goethite. The thermal processing to disrupt the structure of goethite has been shown to be effective in releasing phosphorus associated with this mineral and becoming available to be extracted by a leaching solution. Researchers performed heat treatment in the range of 300-350ºC with 10% NaOH and subsequent leaching in water, succeeded in reducing the phosphorus from 0.15% to 0.075%. The same effect was achieved by heating the ore and leaching the same temperature in a solution of 1 5M sodium hydroxide, close to boiling for three hours.

Yi et al. (2008)investigated the reverse flotation of oolitic iron ore from Hubei, China region, previously subjected to a reductive calcination and were able to obtain a concentrate with 60.14% Fe and 0.22% P. They concluded that the result is more effective than when using flotation, in ore, without treatment.

3. Conclusions

Phosphorus can be removed from iron ore by very different routes of treatment. The genesis of the reserve, mineralogy, cost and sustainability define the technology to be applied.

It is important to stimulate fundamental studies of the mineralogy of phosphorus in iron ores, since the more complex ores require more knowledge about the distribution of this element in the iron matrix, which ensures a more effective route to their mobilization.

The development of technologies for phosphorus removal by physical and biological processes is most likely to achieve economic viability and sustainability to ensure the processing operations of iron ore; that is, those that require minimal amount of reagents, low power requirement, simplicity of facilities, availability of commercial equipment, unskilled labor and do not pollute the environment significantly.

Chinese studies show that for ores with widespread phosphorus in the iron matrix and low release, thermal or mixed processes are closer to reality technical solutions. Due to their higher operating costs, it will be necessary to rethink the processes of sintering and pelletizing, such that these operations also become phosphorus removal steps.

With the exhaustive processing of the known reserves of hematite from Iron Ore Quadrangle (Minas Gerais-Brasil), there will be no shortage of granules in the not too distant future. Therefore, there is an expectation that the ore mined will have higher levels of phosphorus. This expectation is not reflected in publications of national authors, thus translating into a risk for the activity.

4. References

• BUIS, P. Bioremediation techniques for the removal of phosphorus from iron ore. Michigan: Michigan Technological University USA, 1995. 129p. (Dissertation - PhD for Mining Engineering).
• CURI, A. Estudos para remoção de fósforo em minério de ferro Belo Horizonte: Universidade Federal de Minas Gerais, 1991. (Mestrado em Engenharia Metalúrgica e de Minas. Área de concentração: Tecnologia Mineral)
• FISHER-WHITE, M. J., LOVEL, R. R., SPARROW, G. J. Phosphorus removal from goethitic iron ore with a low temperature heat treatment and a caustic leach. ISIJ International, v. 52, n. 5, p. 797-803, 2012.
• JIN, Y. et al. Removal of phosphorus from iron ores by chemical leaching. Journal of Central South University of Technology, v. 13, n. 6, p. 673-677, 2006.
• MOLISANI, A. L. Sinterização e caracterização de propriedades mecânicas de cerâmicas de nitreto de alumínio São Paulo: Universidade de São Paulo, 2009. (Tese de Doutorado em Engenharia Metalúrgica e de Materiais - Área de concentração: Tecnologia Mineral).
• NAUTIYAL, C. S. An efficient microbiological growth medium for screening phosphate solubilizing microorganisms. FEMS Microbiology Letters, v. 170, n. 1, p. 265-270, 1999.
• NUNES, A. P. L. Estudos eletrocinéticos e de flotabilidade de wavellita, turquesa, senegalita e apatitaBelo Horizonte: Universidade Federal de Minas Gerais, Minas Gerais, 2012. (Tese de Doutorado apresentada ao Curso de Pós-Graduação em Engenharia Metalúrgica e de Minas. Área de concentração: Tecnologia Mineral).
• NUNES, A. P. et al. Floatability studies of wavellite and preliminary results on phosphorus removal from a Brazilian iron ore by froth flotation. Minerals Engineering, v. 39, p. 206-212, 2012.
• PYATT, J. L. Dephosphorization of pelletizing concentrate At Pea Ridge Iron Ore Co. Skilling's Min. Rev, v. 79 , n. 9, p. 4-6, 1990.
• RANJBAR, M. Dephosphorization of iranian iron oxide fines by flotation. Erzmetall, v. 55, n. 11, p. 612-620, 2002.
• SIRIANNI, A.F., CAPES, C. E., PUDDINGTON, I. E. Separation studies of iron ore bodies containing apatite by spherical agglomeration methods. Can. Min. Metal. Bull, v. 731, 1968.
• SIRIANNI, A.F., CAPES, C. E., PUDDINGTON, I. E. Recent experience with the spherical agglomeration process. The Canadian Journal of Chemical Engineering, v. 47, n. 2, p. 166-170, 1969.
• SIIRAK, J., HANCOCK, B. A. Progress in developing a flotation phosphorous reduction process at the tilden iron ore mine. In: PROCEEDINGS OF 63rd ANNUAL MEETING OF THE MINNESOTA SECTION AND 51st ANNUAL MINING SYMPOSIUM, AIME, Duluth, Minnesota. Proceedings... Minnesota: AIME, 1990. p. 309-320.
• SPARKS, B. D., SIRIANNI, A. F. Beneficiation of A phosphoriferous iron ore by agglomeration methods. International Journal of Mineral Processing, v. 1, n. 3, p. 231-241, 1974.
• Feld, J., Franklin, T. W., Lampkin, W. M. Process for removing phosphorus from iron ores US nº 3,402,041. ( United States Patent, USA).
• WATLING, H. R. The bioleaching of sulphide minerals with emphasis on copper sulphides - a review. Hydrometallurgy, v. 84, n. 1-2, p. 81-108, 2006.
• XIA, W., REN, Z., GAOY. Removal of phosphorus from high phosphorus iron ores by selective HCl Leaching method. Journal of Iron and Steel Research, International, v. 18, p. 01-04, 2011.
• XU, C. et al. Mechanism of phosphorus removal in beneficiation of high phosphorous oolitic hematite by direct reduction roasting with dephosphorization agent. Trans. Nonferrous Met. Soc China, v. 22, p. 2806−2812, 2012.
• YI, X., YANG, D., LI, Y. Research on dressing technology of iron increase phosphorous reduction of oolitic hematite ore in southern Hezhang. Metal Mine, v. 11, p. 179−182, 2008.
• ZHU, D. Q. et al. Upgrading and dephosphorization of Western Australian iron ore using reduction roasting by adding sodium carbonate. International Journal of Minerals, Metallurgy and Materials, v. 20, n. 6, p. 505-513, 2013.

Publication Dates

• Publication in this collection
  Jul-Sep 2015

History

• Received
  23 Oct 2014
• Accepted
  18 May 2015