Minerals Engineering 18 (2005) 219224 This article is also available online at: www.elsevier.

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Reagents in iron ores otation

A.C. Araujo a, P.R.M. Viana a, A.E.C. Peres
a b

b,*

Department of Mining Engineering, UFMG Rua Espirito Santo, 35/702 30160-030 Belo Horizonte, MG, Brazil Department of Metallurgical and Materials Engineering, UFMG Rua Espirito Santo, 35/206 30160-030 Belo Horizonte, MG, Brazil Received 22 July 2004; accepted 24 August 2004

Abstract The role of reagents utilised in iron ores otation is reviewed. Desliming and otation stages should be performed at pH levels as low as possible to reduce the expenses with caustic soda. Ether amines are by far the mostly utilised class of collector. The degree of neutralisation of the ether amine is an important process parameter. The partial substitution of amine by non-polar oils seems to be an attractive route. Part of the amine may be also replaced by polyglycols in its frother role. Starches still represent the most important class of iron oxides depressant. Very pure corn starch may be successfully replaced by products from the food industry containing proteins. Oil grades in the starch higher than 1.8% may act as froth inhibitors. Cassava starch may be an economically attractive option since the production capacity meets the required demand level. 2004 Elsevier Ltd. All rights reserved.
Keywords: Froth otation; Flotation reagents; Flotation collectors; Flotation depressants

1. Introduction Quartz is the major gangue mineral present in iron ores. Flotation is the usual concentration method employed for the ores in the ne size range (<149 lm). Different otation routes are available: (i) reverse cationic otation of quartz; (ii) direct anionic otation of iron oxides; (iii) reverse anionic otation of activated quartz. Most of this research took place in the USA during the decades of 1930 and 1940. Hanna Mining in association with Cyanamid developed the two anionic otation routes, later employed industrially during the 1950s in Michigan and Minnesota. Concurrently, the USBM branch in Minnesota developed the reverse cationic otation route that eventually became the most feasible approach for iron ore otation in the USA and in other
Corresponding author. Tel./fax: +55 31 3238 1717. E-mail addresses: armando@demin.ufmg.br (A.C. Araujo), pviana@demin.ufmg.br (P.R.M. Viana), aecperes@demet.ufmg.br (A.E.C. Peres). 0892-6875/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.mineng.2004.08.023
*

western countries. The rst applications of reverse cationic otation relied upon fatty amines, later replaced by the more ecient ether amines. The reverse cationic route is by far the most widely utilised method. Quartz is oated with ether amines (R(OCH2)3NH2) partially neutralised with acetic acid. The degree of neutralisation is an important parameter. Higher neutralisation degrees enhance the collector solubility but impair the otation performance. Most ether amines are currently supplied with neutralisation degrees in the range between 25% and 30%. The otation performance of certain iron ore types is enhanced with the use of ether di-amines in combination with ether mono-amines. Amine is partially replaced by some kind of fuel oil in some concentrators. The emulsication of the fuel oil plays a relevant role in the process. The price of fuel oil is lower than that of amine and no signicant environmental impact was detected. Amine plays also the role of frother in iron ore otation. Considering that frothers cost less than amines, the possibility of partially replacing amines by ordinary frothers has been

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30 Selectivity index city index 25 20 20 20 15 10 5 0 0

investigated, but the subject still requires further studies. The iron minerals are depressed by non-modied starches. Corn starch is by far the most widely employed species due to its availability in large amounts. All types of large molecular weight non-modied starches must be put into solution in a process known as gelatinisation. Gelatinisation may be performed by means of warm water or addition of NaOH, with the latter being the most practical method. The composition of corn starches may vary from almost 100% amylopectin plus amylose, dry basis, to products containing impurities such as oil and proteins. The most abundant protein in the corn, zein, presents a depressant action towards hematite. Large oil contents in the starch act as an antifoam agent. Starches are present in other vegetable species. The most attractive among them, considering cost of production, is cassava or manioc, which grows widely in warm weather countries, with no need of fertilisers or soil correction. The lack of large producing groups is the major obstacle to its use. Manioc starches present low oil content and their gums show higher viscosities than those from corn starches, an indication of higher molecular weight and more eective depressant action. The anionic direct otation of iron oxides seems to be an attractive route for the concentration of low grade ores or material currently stored in tailings ponds. Fatty acids may be used as collectors, but the depression of gangue minerals is a challenge that still must be overcome. The anionic reverse otation of activated quartz was a route employed in the early days of quartz otation, when amines were not available to mineral processors.

5 ,0

10 10, 0

151 5, 0

20 20, 0

25 25, 0

303 0,

35 3

% by-pass (slimes in the flotation feed)

Fig. 1. Selectivity index (hematite/quartz) as a function of by-pass.

80 70 60 50 40 30 20 10 0 0 5 10 Attrition time (min) 15 20 mass recovery, pH 5.6 mass recovery, pH 9.8 selectivity index, pH 5.6 selectivity index, pH 9.8

Fig. 2. Bench scale tests showing the attrition inuence on the otation results.

2. Desliming Desliming prior to the reverse cationic otation of iron ores was introduced with the USBM process (Clemmer, 1947). An adequate degree of dispersion of the particles in the pulp is a requisite for ecient desliming. A simple and inexpensive way of reaching a high dispersion degree is raising the pH with the use of large amounts of NaOH, increasing the electrostatic repulsion among the particles. Simple and reliable laboratory experiments provide a correlation between the dispersion degree and the desliming eciency, representing a tool for predicting the otation performance. Peres et al. (2003) investigated the above mentioned correlation for nine samples collected from CVRDs mines, in Brazil. For all samples, the dispersion degree did not increase signicantly for pH values above 8. Except for two samples that intrinsically presented a high dispersion degree, the by-pass (a quantitative determination of the slimes content of the otation feed) aected the otation performance. Results for seven samples correlating the by-pass and the Gaudins selectivity index for bench otation tests are presented in Fig. 1.

Queiroz (2003) veried that, for certain itabirite ore types, the use of attrition allows the increase of the mass recovery to the slimes and otation concentrate fractions and the decrease of iron grade in the otation tailings, iron grade in the slimes and SiO2, Al2O3 and P grades in the concentrate, resulting in higher gures for Gaudins selectivity index. In addition to improving the otation process performance, attrition causes a decrease in the collector consumption. Flotation test results are depicted in Fig. 2.

3. Cationic collectors Primary fatty amines, utilised in the pioneer USBM process, are no longer employed in the otation of iron ores. They were modied with the insertion of the polar group (OCH2)3 between the radical R and the polar head NH2 of the primary amine. Due to the presence of the covalent bond CO, characteristic of the organic function ether, reagents belonging to this class are known as ether amines. The presence of the extra hydrophilic group improves the solubility of the reagent, facilitating its access to the solid-liquid and li-

Mass recovery (%) and Selectivity Index

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quidgas interfaces, enhances the elasticity of the liquid lm around the bubbles, and also aects the dipole moment of the polar head, reducing the main di-electric relaxation time (time for dipoles re-orientation). This feature is relevant regarding the frothing ability of the amine. The frother aects the particle bubble adhesion kinetics, rendering the relaxation time shorter than the contact time. Under these conditions, the collision time is longer than the time required for thinning and rupture of the lamella surrounding the bubble. Papini et al. (2001) performed a large number of rougher only bench scale otation experiments of an iron ore from the Iron Quadrangle, Brazil. Dierent cationic collectors were selected: fatty mono-amine, fatty di-amine, ether mono-amine, ether di-amine, condensate, and kerosene combined with amine. Fatty amines and condensates yielded concentrates with very high silica contents. For the particular ore under investigation, ether mono-amines proved to be more ecient collectors than ether di-amines, in disagreement with the expectation that the presence of a second polar group would reinforce the collecting power. On the other hand, for the same ore type, di-amines were more eective than mono-amines when utilised in conjunction with kerosene. Blending di-amines and mono-amines is a usual plant practice in a large concentrator to achieve low silica contents in the concentrate. The proportion of diamine is larger when concentrates with specications for direct reduction are being produced. The conjunction of ether amine and the Brazilian diesel oil has also been utilised in plant practice. This product is similar to the fuel oil ASTM #5, widely employed in phosphate otation in Florida. The emulsication of the oil phase in the amine solution is the key to the success of this technique (Pereira, 2003). The proportion of oil in the collector blend is around 20%. It is claimed that a reduction in amine consumption is achieved without aecting the metallurgical recovery (Araujo and Souza, 1997). The wastewater from the tailings pond of a concentrator that had been operating with diesel oil for over one year was analysed. No detrimental eect was observed towards test species. The characteristics of the wastewater are similar to those observed prior to diesel use. An increase in phenols content was detected, but there is a possibility that these phenols might come from other sources (maintenance shop, for example). Non-polar oils were successfully used in the past, emulsied with fatty acids, in anionic otation of iron oxides, in Sweden and Russia (Glembotsky, 1963).

ted that it is evident, therefore, that reverse cationic otation possesses no fundamental technological advantages over direct anionic otation, and the choice of collector is mainly a matter of economics and the eectivity of the modifying agents used in each particular case. The use of direct otation of iron oxides seems still attractive in the case of low grade ores, marginal ores that might be oated to increase the stripping ratio, and also in the recovery of material stored in tailings ponds. Nevertheless, most of the laboratory investigations indicated that the otation of iron oxides with either anionic (fatty acids) or amphoteric collectors (sarcosinates and sulphosuccinamates) yields concentrates with high silica contents. Sodium silicates are not eective depressants in these systems (Vieira, 1995; Luz, 1996; Casquet, 1995). The potential of hydroxamates has not yet been fully explored due to its high cost.

5. Depressants Starches are the universal depressants of iron oxides in the otation of iron ores. Starch may be extracted from several vegetable species such as corn, cassava, potato, wheat, rice, arrowroot, etc.). In the mineral industry, corn starches are by far the most widely used species. Corn starch has been used in iron ore otation in Brazil since 1978. The trade name of the reagent was Collamil, consisting of a very ne and very pure product. The amylose plus amylopectin content reached 98% to 99%, dry basis, the balance being represented by minor contents of bres, mineral matter, oil and proteins. This starch was used at Samarco and also at phosphate concentration plants. There were no technical reasons to search for alternatives to Collamil. On the other hand, one company held the monopoly of its supply. Serious commercial problems arose from this monopoly and Samarco performed laboratory scale investigations on the performance of alternatives to Collamil (Viana and Souza, 1988). One product, utilised in beer making, was available at attractive commercial conditions, the grits starch. The designations conventional starch and non-conventional starch will be used, respectively, for Collamil and grits. Typical physicochemical and size analyses are presented in Table 1. Results from plant practice showed that the use of non-conventional starch did not impair the metallurgical performance of the concentrator in terms of iron recovery and contaminants contents in the concentrate. The price of the alternative depressant was approximately one half of the price of conventional starch. There was a strong competition among eight dierent suppliers, a scenario by far more comfortable than the previous monopoly.

4. Anionic collectors The anionic otation of iron oxides represented the usual plant practice in the past. Glembotsky (1963) sta-

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Table 1 Typical physico-chemical and size analyses of conventional and non-conventional starches (Viana and Souza, 1988) Conventional starch Moisture % Starch content % Protein content % Oil content % Fibre + mineral matter content % +149 lm (100#) +74 lm (200#) +44 lm (325#) 13.5 85.5 (99 dry basis) 1.0 0.0 0.5 1.0 Non-conventional starch Moisture % Starch content % Protein content % Oil content % Fibre + mineral matter content % +1000 lm (16#) +600 lm (28#) +300 lm (48#) +212 lm (65#) +149 lm (100#) 13.0 76.8 (89.9 dry basis) 8.6 0.6 1.0 0.0 20.0 98.0 99.5 100.0

Despite the practical industrial evidence that both types of starch yielded similar performances, the suppliers of conventional starch claimed that the proteins content might be harmful to the otation performance. Experimental results from microotation tests in a modied Hallimond tube showed that zein, the most abundant corn protein, is a hematite depressant as ecient as amylopectin and conventional corn starch (Peres and Correa, 1996). Fig. 3 shows the oatability of hematite as a function of the ether amine concentration for zein and other depressants. Therefore, the adequate industrial performance of non-conventional starch was not accidental. Pinto et al. (1992) observed, from microotation experiments presented in Fig. 4, that amylopectin is the starch component that depresses more eectively the mineral hematite. One corn products supplier developed a genetically modied corn species, waxy corn, presenting an amylopectin content of 96%, higher than the 75%/25% amylopectin/amylose ratio in the regular yellow corn. The benet of using the waxy corn starch was not observed at industrial scale, and the product was also fairly expensive.
20 depressant:amine ratio = 2:1 pH = 11 15 % FLOATED
starch gluten amylose amylopectin zein

1.0 0.8
FLOATABILITY %

starch amylose amylopectin

0.6 04 0.2 0.0

10

20

30

40

60

DEPRESSANT CONCENTRATION (mg/L)

Fig. 4. Floatability of hematite as a function of depressant concentration.

10

0 60 64 6 68 7 72 Amine (mg/L) 76 80

Fig. 3. Depression action of zein and other depressants on quartz.

The demand for corn grits by the snacks food industry, at a much higher price than the mineral industry could aord, pushed the corn industry to oer another food segment product, locally known as fuba. Fuba is ner than grits and presents a larger content of oil. The corn grains are initially degermed, for the germ, containing basically proteins and oil, is a valuable product for the food industry. The degermed grains are then abraded, for removal of the pericarp or hull, and dry ground in hammer mills, producing dierent size fractions. Because the germ and the portion of the endosperm near the germ are softer than the rest of the grain, the ner fractions are richer in oil. The fact that oils are froth and foams inhibitors is well known from theories on the elasticity of lms surrounding gas bubbles, but plant operators came to well understand the eect on the hard way. Some small suppliers occasionally do not nd a market for the germ fraction and decide to grind the whole corn kernel. The result is a starch with an extremely high oil content that may surpass 3%. The consequence on the otation machine operation is complete froth suppression, representing many hours of production interruption.

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Oil contents higher than 1.8% in starches are considered to represent a risk concerning froth stability. The risk increases if the loss on ignition content of the ore is high. Concerning the solubilising of corn starch, there are two possibilities: heating the suspension of starch in water at 56 C or adding NaOH. Due to the hazards of employing hot water in a concentrator, as used in the rst operation, all companies utilise at present the caustic soda route. Due to the high cost of NaOH and also to the frequent price uctuations, the thermal route deserves attention and may become attractive again. Corn is not the only natural source of starch. In many tropical areas of countries, such as Brazil, a vegetable called cassava, manioc or yuca, grows extensively and almost wildly. The cost of production is lower compared with corn. A rst class starch may be extracted from cassava, with the advantage that the starch fraction content (amylopectin + amylose) is higher due to the fact that the proteins and oil contents are low. The low oil content prevents the risk of froth suppression. The viscosity of the gelatinised solution is higher than that for corn starch, a strong indication of a higher molecular weight of the starch. A less pure product cassava scrap is achieved by grinding the root with its inner skin. The depressant action of this cheaper product is still acceptable. Cassava has attracted the attention of plant operators for many years, but commercial problems have prevented its wide utilisation. There are no large groups growing cassava in Brazil and co-operative eorts to supply the amounts necessary to meet the demand have not been successful. When the price of soybean and corn increases in the international market people quit growing cassava to grow the exportable former species. Potato starch has been used industrially in Europe, but there are no records of its use in the mining industry. The vegetable potato degrades much faster than corn, for example. Among depressants from other sources, carboxy methyl cellulose (CMC) is one that presents a strong potential. Technically, this reagent was approved as an alternative to starch. Several laboratory test programmes, with dierent iron ores from the Iron Ore Quadrangle, have already been performed with commercial grade CMCs, of varying degrees of substitution and diverse molecular weights. In general all CMCs tested gave concentrate grades of lower silica than starch but Fe grades of the tailings are slightly higher for CMCs tested so far (Viana and Araujo, 2003). Flotation test results with three dierent types of CMC are presented in Fig. 5. To be competitive in terms of operational cost, CMCs dosage must be at least 5 times smaller than that of starches. Tested dosages were in the range from 1/10 to 1/5 of starch. Some CMCs presented fairly good results even when used at 1/10 of the starch dosage. Another option under investigation is the use of synthetic polymers, employed as occulants, as partial

Fig. 5. Iron recovery and silica content in the concentrate as a function of dosage for three types of CMC (1 slightly cationic CMC; 2 and 3 mixture of anionic CMCs with dierent degrees of substitution).

replacement for starch (Turrer, 2003). Anionic, cationic and non-ionic polyacrylamides are being tested at laboratory scale. The much higher price of these reagents may be counteracted by the much smaller addition level.

6. Frothers Despite the existence of records of the use of specic frothers (alcohol and polypropylene glycol) in the reverse otation of iron ores in the USA (Houot, 1983), their use is not a common plant practice. Flotation is being performed in a pH range that stabilises both, the cationic and the molecular species of the amine, rendering possible that the cationic species act as collector and the molecular species act as frother. The partial replacement of amine by a specic frother is under investigation, at laboratory scale (both single mineral otation and ore otation). The results so far are attractive. Microotation test results performed with some commercial frothers are presented in Fig. 6. Synthetic polyglycol-type frothers, replacing about 10% of the total amine dosage, increased both recovery and selectivity in several tests. Pine oil frothers also
90 MIBC 80 70 YSEROL CYTEC F507 FLOTANOL D14 FLOTANOL C7 NO FROTHER 50 40 30 20 10 0 0 20 40 60 80 100

% FLOATEDD

60

Proportion of frother (%)

Fig. 6. Microotation tests showing the amine substitution by frother.

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A.C. Araujo et al. / Minerals Engineering 18 (2005) 219224 Proceedings of the 70th Annual Meeting Minnesota Section SME and 58th Annual University of Minnesota Mining Symposium, Duluth, Minnesota, pp. 111122. Casquet, R.Q., 1995. Mineralogical and technological characterisation of the itabirite iron ore from the Alegria South mine, Ouro Preto-MG. M.Sc. thesis, CPGEM-UFMG, p. 240 (in Portuguese). Clemmer, J.B., 1947. Flotation of iron ore. 8th Ann. Min. Symposium, January. Glembotsky, V.A., 1963. Reagents for iron ore otation. In: Proceedings VI IMPC, Cannes, pp. 371381. Houot, R., 1983. Beneciation of iron ore by otationreview of industrial and potential applications. International Journal of Mineral Processing 10, 183204. Leal Filho, L.S., Rodrigues, G.A., 1992. The use of ethoxylated nonionic surfactants on the cationic otation of quartz. In: Salum, M.J.G., Ciminelli, V.S.T. (Eds.), Flotation: Fundamentals, Practice and Environment. Proceedings of the III Meeting of the Southern Hemisphere on Mineral Technology. ABTM, Belo Horizonte, Brazil, pp. 5064 (in Portuguese). Luz, J.A.M., 1996. Anionic otation of itabirite tailings: study on alternative reagents and polyphasic process modelling. Ph.D. thesis, CPGEM-UFMG, p. 253 (in Portuguese). Papini, R.M., Brandao, P.R.G., Peres, A.E.C., 2001. Cationic otation of iron ores: amine characterisation and performance. Minerals & Metallurgical Processing 17 (2), 15. Pereira, S.R.N., 2003. The use of nonpolar oils in the cationic reverse otation of an iron ore. M.Sc. thesis project, CPGEM-UFMG, p. 253 (in Portuguese). Peres, A.E.C., Correa, M.I., 1996. Depression of iron oxides with corn starches. Minerals Engineering 9 (12), 12271234. Peres, A.E.C., Lima, N.P., Araujo, A.C., 2003. How dierent iron ore types behave in desliming in hydrocyclones and otation. In: Hydrocyclones 03, Cape Town, p. 8. Pinto, C.L.L., Araujo, A.C., Peres, A.E.C., 1992. The eect of starch, amylose and amylopectin on the depression of oxi-minerals. Minerals Engineering 5 (35), 469478. Queiroz, L.A., 2003. Use of attrition in the desliming: eects on the reverse otation of itabirite ores. M.Sc. thesis, CPGEM-UFMG, p. 165 (in Portuguese). Silva, R.R.R., 2004. Reagents systems in the reverse cationic otation of iron ores: collector and frother. M.Sc. thesis project, CPGEMUFMG, p. 102 (in Portuguese). Turrer, H.D.G., 2003. Study on the utilisation of synthetic occulants in the reverse cationic otation of an iron ore. M.Sc. thesis project, CPGEM-UFMG, p. 44 (in Portuguese). Viana, P.R.M., Souza, H.S., 1988. The use of corn grits as a depressant for the otation of quartz in hematite ore. In: Castro, S.H.F., Alvarez, J.M. (Eds.), Proceedings of the 2nd Latin-American Congress on Froth Flotation, 1985, Developments in Mineral Processing, vol. 9. Elsevier, Amsterdam, pp. 233244. Viana, P.R.M., Araujo, A.C., 2003. Condential Report. Vieira, A.M., 1995. Study on the technical feasibility of concentrating a mine waste containing iron. M.Sc. thesis, CPGEM-UFMG, p. 145 (in Portuguese).

performed well when replacing amines. On the other hand, linear branched alcohol did not present improvements in comparison to amine only tests. Next steps will include industrial scale tests in at least two plants in Brazil (Silva, 2004). 7. Non-ionic surfactants The inuence of non-ionic surfactants on the cationic otation of quartz with etheramine was investigated at bench scale by Leal Filho and Rodrigues (1992). The reagents tested were nonylphenol ethoxylated with two and four groups of ethylene oxide and an ethoxylated fatty alcohol. The nonylphenol ethoxylated with two groups of ethylene oxide combined with etheramine, in a mass ratio 1:4, was able to increase quartz oatability by approximately 20%. The reagent also changed significantly the froth characteristics of the system, reducing the surface tension of the system to a level lower than that in the presence of amine only. 8. Conclusions The plant practice of iron ores otation involves the conventional reverse cationic route, with ether amines employed as quartz collector and gelatinised corn starch used as iron oxides depressant. Options already incorporated in industrial operation, concerning the collector, include combining monoamines with di-amines and partial substitution of amines by fuel oil. The high purity corn starch (99% starch, dry basis) was successfully replaced by less pure products used in the food industry, including cassava starch. The oil content of the starch is a major concern due to its froth inhibiting action. The caustic soda consumption may be lowered in concentrators where the desliming stage has been optimised. References
Araujo, A.C., Souza, C.C., 1997. Partial replacement of amine in reverse column otation of iron ores: 1Pilot plant studies. In: