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Minerals Engineering 16 (2003) 12131216

Technical Note

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The eect of grinding conditions on the otation of a sulphide copper ore

K.L.C. Gonc alves a, V.L.L. Andrade a, A.E.C. Peres
a b


CVRD, Diretoria de Desenvolvimento de Projetos Minerais, Br 262 km 296, Santa Luzia, MG 33030-970, Brazil UFMG, Department of Metallurgical and Material Engineering, Rua Espirito Santo, 35/206, Belo Horizonte, MG 30160-030, Brazil Received 10 April 2003; accepted 23 May 2003

Abstract The challenge of process development for the beneciation of Salobos copper ore started in 1978 and the studies still go on. Copper is predominantly present as secondary minerals, such as chalcocite, bornite, and digenite, and liberation requires very ne grinding. These minerals may undergo rapid oxidation at the alkaline pH range and under mildly oxidising conditions. The oxidation products may adsorb onto the minerals altering their surface characteristics, otation behaviour, and may also signicantly modify the mechanisms of interaction between the minerals and the collector. These facts impair the otation process performance and increase the reagents consumption, the required otation cells volume, and the overall processing costs. This paper describes the eect of grinding conditions on the otation performance. Dierent media and mill construction materials were tested at bench scale aiming at evaluating the eects of the pulp electrochemical potential and the availability of iron oxide and hydroxide compounds on the otation response. The results indicated that the grinding process aects signicantly the otation metallurgical performance of Salobos ore. The conditions that yielded the highest levels of copper recovery and the fastest otation kinetics were rubber lined steel mill and stainless steel media. 2003 Elsevier Ltd. All rights reserved.
Keywords: Froth otation; Grinding; Non-ferrous metallic ores; Sulphide ores

1. Introduction Grinding precedes otation in most concentrators (outstanding exceptions are some iron ore otation plants in Brazil). The understanding of fundamental aspects of the two operations is crucial for improving the concentrator performance. The oatability of ores and their separation selectivity are essentially determined by the surface properties. The surface properties of sulphide minerals are mostly controlled by the grinding processes and conditions (Xiang and Yen, 1998). During grinding, a galvanic contact occurs among the sulphide minerals themselves and also among the sulphide minerals and the grinding media, resulting in a galvanic current due to rest potential dierences. The rest potentials for sulphide minerals are much higher than that for iron (Rao et al., 1976), so the former act as
* Corresponding author. Tel.: +55-31-3238-1717; fax: +55-31-32381815. E-mail address: (A.E.C. Peres).

cathodes, while the iron grinding media act as anode, being galvanically oxidised, while oxygen reduction occurs on the sulphide mineral surface. The oxygen consumption due to grinding media results in a reducing environment that aects the sulphide and prevents xanthate oxidation and adsorption. At the same time the sulphide particles surfaces are coated with oxides layers. The sulphide minerals ground under these conditions do not present self-induced oatability and their otation response in the presence of xanthate is usually poor (Heyes and Trahar, 1979). When two sulphides presenting large dierences between their rest potentials are in contact or are ground in a porcelain mill, the sulphide with lower rest potential will act as anode while the other will act as cathode. The anodic mineral will exhibit enhanced otation performance due to the fact that a surface under oxidised state favours xanthate oxidation and adsorption. On the other hand, oxygen reduction occurs on the most noble sulphide (usually pyrite). Its surface presents, then, very low anity towards xanthate due to its reduced condition (Xiang and Yen, 1998). This behaviour explains the

0892-6875/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.mineng.2003.05.006


K.L.C. Gon calves et al. / Minerals Engineering 16 (2003) 12131216

enhanced otation selectivity in the separation between chalcopyrite, galena, and sphalerite from pyrite, when the ore is ground in porcelain or stainless steel mills as compared with iron or carbon steel mills. Salobos deposit, located in the Caraj as area, is the largest Brazilian copper reserve (geological reserves of approximately 1 billion tonnes of ore, copper grade 0.86%, and open pit mineable reserve of 255 million tonnes of ore averaging 1.11% Cu). Results of extensive on site pilot plant scale testwork, performed in the 80s, were reported by Pereira et al. (1991). This stage included a demonstration run lasting 210 h and treating 380 tonnes of ore. The major conclusions were that Salobos copper ore is hard to treat mainly due to its high Bond work index, its liberation in a ne size range, its complex mineralogy and uncommon mineralogical associations, and its need of high otation retention times and high collector consumption. The importance of controlling the electrochemical conditions of the pulp was stressed in the report, despite the fact that this control was not performed due to technical diculties related to time and geographical constraints. CVRD decided to concentrate the eorts on process development of smaller deposits presenting higher grade and easier concentration conditions. Serra do Sossego project start up is predicted for 2004. In the mean time, Salobos ore should be submitted to further investigation, especially concerning the correlation between grinding conditions and otation performance (Gonc alves, 2002). The eects of sodium sulphide additions and of using nitrogen as gas phase in otation will be presented in other publications.

and sodium dithiophosphate (25 g/t) were utilised as collectors and a polyglycol alcohol (60 g/t) was employed as frother. Flotation kinetics was evaluated by means of froth collection at the following time conditions: 1.5, 3, 5, 10, 15 and 20 min. Froths collected in the rst three otation stages were designated as rougher #1 and the other three froths constituted rougher #2, #3, and #4. Reagents were dosed in all four steps, prior to each otation stage, 40% of each reagent being dosed prior to rougher #1 and 20% prior to each other stage, namely rougher #2, #3, and #4. A combined platinum electrode was utilised for rest potential determinations. An increment of 197 mV was added to the gure read in the equipment in order to convert it to the normal hydrogen electrode standard. Slurry potentials were recorded after grinding and also after each reagents addition stage and rougher otation stage.

3. Results The chemical analysis showed 1.35% Cu, 0.55% S, and 0.99 g/t Au. The copper sulphides present in the ore are bornite (4%), chalcopyrite, covellite, and chalcocite/ digenite (1% each). Pyrite content is 0.5%. The predominance of bornite is conrmed by the Cu/S ratio approximately 2.5. The sulphide particles are present in the ne size range. Associations with magnetite and with silicates, as inclusions, are common. Fig. 1 illustrates the size distribution of the sample after grinding under dierent conditions. The coincidence of the curves was achieved by using dierent grinding times for each grinding condition: (i) (ii) (iii) (iv) rubber lined jar mill, stainless steel rods: 16 min; rubber lined jar mill, carbon steel balls: 15 min; unlined jar mill, carbon steel rods: 09 min; ceramic mill, ceramic balls: 29 min.

2. Materials and methods The ROM copper ore sample was crushed in a roll crusher, in closed circuit with screening, to produce 100% passing 1 mm with minimal ultranes production. This sample was homogenised and then cone and quartered to produce 1100 g fractions for the otation experiments. Grinding was performed in the absence of reagents, at 60% solids: (i) (ii) (iii) (iv) rubber lined jar mill, stainless steel rods; rubber lined jar mill, carbon steel balls; unlined jar mill, carbon steel rods; ceramic mill, ceramic balls.

100 90 lined; stainless steel rods unlined; carbon steel rods ceramic; ceramic balls lined; carbon steel balls 60 50 40 30 20 10 0 1 10 100 1000

cumulative percentage passing

80 70

The grinding time was determined based on the requirement of achieving 90% < 100# (150 lm). Rougher otation experiments were performed with 1100 g ore samples, at 35% solids, in a 2.5 L Denver laboratory machine. Potassium amyl xanthate (100 g/t)

particle size ( m)

Fig. 1. Size distributions after grinding under dierent conditions.

K.L.C. Gon calves et al. / Minerals Engineering 16 (2003) 12131216

100 90




100 Eh (mV)

copper recovery %

70 60 50 40 30 20 10 0

lined; stainless steel rods unlined; carbon steel rods


lined; stainless steel rods ceramic; ceramic balls lined; carbon steel balls unlined; carbon steel rods
0 5 10 15 20 25 30 35 40 45


ceramic; ceramic balls lined; carbon steel balls

-300 1 2 3 4 5 6 7 8 stages 9

copper grade (%)

1 - after grinding 2 - after reagents 3 - after rougher 1

4 - after reagents 5 - after rougher 2 6 - after reagents

7 - after rougher 3 8 - after reagents 9 - after rougher 4

Fig. 3. Copper recovery as a function of copper grade for dierent grinding conditions.

Fig. 2. Slurry potential variation along rougher otation of the copper ore.

The condition of eliminating the otation feed size distribution as a variable was attained, as illustrated in Fig. 1. Fig. 2 illustrates the slurry potential variation along rougher otation, after grinding under dierent conditions. Table 1 and Fig. 3 show copper otation recovery for grinding under dierent conditions.

4. Discussion The similarity among the curves plotted in Fig. 1 shows that the dierent grinding conditions utilised did not produce samples with signicantly dierent size distributions. The results of rest potential variation along rougher otation are discussed at the light of Fig. 2. Grinding in ceramic mill (ceramic balls) and lined steel mill (stainless steel rods) yielded positive values of the pulp rest potential, approximately +200 mV, the oxidising environment being caused dissolved oxygen. This condition is ideal to promote the oxidation of xanthate to dixanthogen as well as to oxidise moderately the surface of copper sulphides present in the slurry

(bornite, chalcocite/digenite, and chalcopyrite). A layer of metal sulphide decient in the metal is formed at the surface of the minerals, favouring the adsorption of xanthate oxidised species and also enhancing the selfinduced oatability of the copper minerals. Grinding in lined steel mill (carbon steel balls) and unlined steel mill (carbon steel rods) yielded negative values of the pulp rest potential, approximately )50 and )150 mV, respectively, the reducing environment being caused by the availability of ferrous ions in the system. The co-existence of ferrous ions and sulphide minerals in the system causes a galvanic current that induces the oxidation of species presenting lower redox potential (ferrous ions) and oxygen reduction on the surface of the sulphide minerals, resulting in a strongly reducing environment. Iron oxides and hydroxides tend to precipitate on the surface of the sulphide particles. Sulphide minerals ground under this condition do not present self-induced oatability and their otation response with xanthate is normally poor. The high copper recovery in the rst minute of otation after grinding in a lined mill and stainless steel grinding media, shown in Table 1, conrms the hypothesis that the existence of an oxidising environment during grinding enhances the oatability of copper minerals. Grinding conditions that generated a reducing environment yielded low copper recoveries in the rst

Table 1 Copper otation recovery after grinding under dierent conditions Time (min) Lined-stainless steel rods Cu (%) 1.5 3 5 10 15 20 26.4 18.4 15.4 10.0 8.5 7.6 Cu recovery (%) 58.8 73.7 79.9 89.5 92.1 93.5 Ceramicceramic balls Cu (%) 34.4 21.9 17.6 10.5 8.6 7.8 Cu recovery (%) 41.0 64.0 73.0 87.5 91.0 92.5 Lined-carbon steel balls Cu (%) 34.5 26.0 21.5 9.6 8.0 7.1 Cu recovery (%) 36.5 52.5 61.8 87.7 91.8 93.8 Unlined-carbon steel rods Cu (%) 38.4 26.3 20.9 8.8 7.2 6.5 Cu recovery (%) 21.1 42.1 53.2 86.8 91.9 93.7


K.L.C. Gon calves et al. / Minerals Engineering 16 (2003) 12131216

minute of otation. A gradual decrease in the oatability of the sulphide minerals is observed for pulp rest potentials reaching less positive and then negative values. More positive potential values represent a larger availability of iron ions in the system, and consequently a larger amount of oxidised iron species (oxides and hydroxides) are present on the surface of the sulphide minerals. The expectation that grinding in a ceramic mill would yield otation results similar to those produced by grinding in a lined mill (with stainless steel rods) was not conrmed, despite the fact that the pulp rest potential was practically identical for both conditions (see Fig. 1). The impaired otation performance of the ore ground in the ceramic mill may be attributed to the morphology of the particles, submitted to longer abrasion action (29 min in the ceramic mill 16 min in the lined mill with high chromium rods). Another explanation could be the precipitation of oxidised copper and iron species on the sulphides surfaces. The extension of this phenomenon was larger for grinding in the ceramic mill due to the longer residence time. Data presented in Table 1 and Fig. 3 show that the highest selectivity (higher grade for the same copper recovery) was achieved for grinding in a lined mill with stainless steel rods, following ceramic mill with ceramic balls, then lined mill with carbon steel balls, and nally unlined mill with carbon steel rods. The direct contact between the carbon steel rods and the mill shell causes enhanced wear of the shell and grinding media, liberating ultrane iron particles into the pulp. The rate of the oxidation of iron particles reaction is accelerated, with consequent precipitation of larger amounts of iron oxides and hydroxides on the surface of the sulphide minerals, explaining the impaired selectivity and the slower otation rate up to the 10th minute of the test. The high dosage of reagents necessary for the otation of Salobos ore is responsible for the high nal copper recovery even for grinding conditions less ade-

quate for otation. Very high collector dosages are necessary to provide the adhesion of the oxidised copper sulphide particles to air bubbles. Nevertheless, improved otation selectivity is achieved only for grinding conditions providing an oxidising environment.

5. Conclusions The grinding conditions aect signicantly the subsequent otation stage of this sulphide copper ore. The presence of iron ions in the slurry is deleterious to the otation of copper minerals and may be avoided by the utilisation of lined mills and non-ferrous or corrosion resistant grinding media, such as stainless steel or pebbles. Monitoring the slurry rest potential provides an indication of the otation performance. Mild oxidising potentials (positive rest potentials) are adequate for enhanced copper recoveries for favouring xanthate oxidation and adsorption onto the minerals surface. References
Gonc alves, K.L.C., 2002. Eect of surface oxidation on the otation of Salobos copper and gold ore, M.Sc. thesis, CPGEM-UFMG, p. 138 (in Portuguese). Heyes, G.W., Trahar, W.J., 1979. Oxidationreduction eects in the otation of chalcocite and cuprite. International Journal of Mineral Processing 6, 229252. Pereira, C.E., Peres, A.E.C., Bandeira, R.L., 1991. Salobo copper ore process development. In: Proceedings of COPPER 91, Ottawa, Canada, pp. 133144. Rao, S.R., Moon, K.S., Leja, J., 1976. Eect of grinding media on the surface reactions and otation of heavy metal sulphides. In: Fuerstenau, M.C. (Ed.), Flotation A.M. Gaudin Memorial Volume, vol. 1. AIME, New York, pp. 509527. Xiang, H.W., Yen, X., 1998. The eect of grinding media and environment on the surface properties and otation behaviour of sulde minerals. International Journal of Mineral Processing 7, 4979.