Int. J. Miner. Process. 72 (2003) 151 162 www.elsevier.

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Electrochemical potential controlling flotation

R. Woods *
School of Science, Griffith University, Nathan Campus, Nathan, Queensland 4111, Australia Received 18 June 2002; received in revised form 20 June 2003; accepted 30 June 2003

Abstract The development of the understanding of flotation systems based on electrochemical concepts and techniques is reviewed. An improvement in devising flotation strategies has been achieved through the consideration of electrochemical potential as one of the parameters to be monitored and controlled in the laboratory. The progress that has been made in applying potential measurements in flotation plants is also examined. D 2003 Elsevier B.V. All rights reserved.
Keywords: electrochemistry; monitoring potential; potential control; self-induced flotation

1. Electrochemistry of flotation It is now more than four decades since Nixon proposed an electrochemical mechanism to explain the interaction of thiol flotation collectors with sulfide mineral surfaces and provide a means of reconciling the different theories that had previously been resolutely advanced (Woods, 1996). The electrochemical approach considers a surface species to be formed by an anodic oxidation reaction involving the collector occurring simultaneously with a cathodic process which is usually the reduction of oxygen. Thus, adsorption of the collector, the key chemical step in the flotation process, is amenable to investigation using electrochemical techniques and the component anodic and cathodic processes can be studied separately at sulfide mineral electrodes. Doug Fuerstenau was a pioneer in the study of sulfide flotation systems under potential control. The
* Tel.: +61-7-38757550; fax: +61-7-38756572. E-mail address: ronwoods@sct.gu.edu.au (R. Woods). 0301-7516/$ - see front matter D 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0301-7516(03)00095-4

first studies of the interaction of flotation collectors with sulfide mineral electrodes were made by Woods (1971) (galena/ethyl xanthate), Kowal and Pomianowski (1973) (chalcocite/ethyl xanthate), and Chander and Fuerstenau (1974) (chalcocite/diethyldithiophosphate). Electrochemical techniques were applied by a number of authors to the investigation of sulfide flotation systems, particularly during the late 1970s and the 1980s (Woods, 1996). These studies have identified potential regions in which (i) the thiol chemisorbs, (ii) a thiol compound is formed with a metal component of the mineral, and (iii) the dithiolate is produced. Chemisorption is generally the thermodynamically favoured process and occurs at potentials below the reversible value for the formation of the metal thiolate. The potential dependence of equilibrium chemisorption coverage for a number of mineral/collector systems has been found to obey the Frumkin adsorption isotherm (Woods, 1996). This isotherm is a phenomenological equation based on macroscopic considerations and has been shown to apply to a range of systems in which species are

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chemisorbed on solid surfaces from the gas phase or from solution. The Frumkin isotherm has been explained in terms of molecular-model theories in which the free energy of adsorption varies with coverage, through either heterogeneity of surface sites or interactions between adsorbed molecules. Chemisorption offers the most effective utilization of the collector because a monolayer forms before the nucleation and growth of the bulk phase. Metal thiolate phases usually develop on the chemisorbed monolayer. Dithiolates may form in addition to the metal thiolate, the dominant bulk reaction depending on which of the two redox potentials is the most negative. By using particle bed electrodes, or controlling the potential of mineral pulps through the addition of redox reagents, the potential dependence of flotation recovery has been determined for a number of sulfide mineral/thiol collector systems. The potential dependence of flotation for three sulfide mineral/thiol collector systems is compared to the corresponding adsorption isotherms in Fig. 1.

Clearly, if there is a difference in the potential at which different minerals float with a particular collector, then control of the potential should allow flotation separation. For example, Chander and Fuerstenau (1983) showed that chalcocite could be separated from molybdenite through appropriate choice of the potential of flotation. The early work on the potential dependence of flotation led researchers to assume that it would be possible to develop separation strategies from differences in recovery/potential relationships established experimentally for individual minerals. Progress in this endeavour became constrained, however, by the finding (Guy and Trahar, 1985; Gebhardt et al., 1985; Gebhardt and Richardson, 1987) that the behaviour of mixtures could not be predicted accurately from single mineral studies. The behaviour of simple mixtures compared with those of the individual minerals is shown in Figs. 2 and 3. Fig. 2 shows the results reported by Guy and Trahar (1985) for mixtures of galena and chalcopyrite

Fig. 1. Comparison of potential dependence of flotation recovery with the corresponding adsorption isotherm for (A) galena/ethyl xanthate, (B) chalcocite/ethyl xanthate, and (C) chalcocite diethyldithiophosphate (from Woods, 1996).

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Fig. 2. Floatabilities under reducing and oxidizing conditions for chalcopyrite (Cp) and galena (Gn) from quartz (Q) and from chalcopyrite, galena, quartz mixtures with ethyl xanthate as collector (from Guy and Trahar, 1985).

with ethyl xanthate as collector compared with those for the individual minerals. These authors noted that, from single mineral studies, it should be possible to float chalcopyrite from galena at oxidizing potentials, while the converse flotation separation of galena from chalcopyrite should be possible at low potentials. As Fig. 2 shows, chalcopyrite was found to float effectively at the oxidizing potential of 0.45 V whereas galena recovery is small and conversely, galena to float efficiently at the reducing potential of 0.15 V whereas chalcopyrite recovery is small. However, it can be seen that the minerals interact with each other when they are present together in such a manner that the inherent differences between their recoveries are diminished. Thus, at 0.45 V, chalcopyrite recovery is reduced by a factor of f 4 when galena is present while galena recovery is approximately doubled in the presence of chalcopyrite. At the reducing potential of 0.15 V, galena flotation is diminished by f 40% whereas chalcopyrite recovery is enhanced by a factor of f 5 when the minerals are present together. The influence of each mineral on the flotation response of the other was explained (Guy and Trahar, 1985) by a modification in the flotation response of galena (towards that of chalcopyrite) by incorporation of copper ions derived by oxidation of chalcopyrite and a modification in the response of chalcopyrite

Fig. 3. Floatabilities with ethyl xanthate as collector of chalcocite (Co) and pyrite (Py) alone and from mixtures of the two minerals which were prereduced at 0.36 V or preoxidized at open circuit (0.2 V) prior to flotation (from Gebhardt and Richardson, 1987).

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(towards that of galena) by replacement of iron in chalcopyrite by lead ions from galena. A similar loss in selectivity in a pyrite chalcocite mixture was reported by Gebhardt and Richardson (1987) and this is illustrated in Fig. 3. This figure shows that, with single minerals, chalcocite floats efficiently with ethyl xanthate at potentials above 0.15 V, while pyrite does not begin to float until f 0.05 V. This indicates that there should be a potential window of f 0.2 V in which chalcocite could be readily floated away from pyrite. But the difference between the potential dependence of flotation of the two sulfide minerals is diminished considerably in the mixture, ease of separation depending on mode of pretreatment. Thus, Fig. 3 shows that the presence of pyrite significantly depresses chalcocite while chalcocite activates pyrite when the minerals are present in a mixture. It is clear from these studies that flotation recovery of sulfide minerals from mixtures is still a function of potential, even though it is not readily predictable from single mineral studies. Electrochemical techniques have provided valuable information on the kinetics and mechanisms of processes occurring at the solid/solution interface, but electrochemical characterizations lacks the molecular specificity required to give unequivocal identification of species formed at electrode surfaces. For this reason, a number of in situ and ex situ spectroscopies have been applied to augment electrochemical approaches and provide information on the elemental and molecular composition, the atomic geometry, and the electronic structure of the interface. Spectroelectrochemical studies of mineral flotation have been reviewed recently by Buckley et al. (2002). The importance in flotation of the effects of galvanic interaction between sulfide minerals and grinding media was highlighted by Iwasaki et al. (e.g., Adam et al., 1984; Pozzo and Iwasaki, 1989). These authors demonstrated in laboratory studies the electrochemical nature of such interaction, which adversely affects the floatability of sulfide minerals. Later studies at Virginia Polytechnic Institute and State University have sought to minimize wear and corrosion of grinding media in ball mills through cathodic protection. Pazhianur et al. (1997) employed impressed current to cathodically protect grinding media and reported that this procedure reduced wear by 30 60%.

2. Self-induced flotation A few sulfide minerals are naturally floatable as a result of preferential cleavage along planes of sulfur atoms that have all chemical bonds satisfied. Other sulfides have been found to float under oxidizing but not reducing conditions. As with collector-induced flotation, the process responsible for rendering the mineral floatable is electrochemical in nature. In the self-induced flotation case, the anodic reaction is oxidation of the surface to a sulfur species. Fig. 4 shows a comparison of the potential dependence of floatability of chalcopyrite at pH 11 as determined by Heyes and Trahar (1977), Luttrell and Yoon (1984), and Gardner and Woods (1979), with the anodic current on a voltammogram at this pH reported by Gardner and Woods (solid line). It can be seen that there is a good correlation between the potential of onset of flotation and the commencement of the anodic current. The electrochemical mechanism of self-induced flotation is further supported by the observation (Woods, 1991) that the potential of onset of flotation correlates with the reversible potentials for sulfide mineral oxidation. The open circles in Fig. 5A show the potential for 50% recovery reported by Healy and Trahar (1989) plotted against the standard potentials of the reactions forming S0 plus M(OH)2 for the binary sulfides and S0 plus Fe(OH)2 plus

Fig. 4. Anodic current and flotation response of chalcopyrite in the absence of collectors (from Woods, 1996).

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3. Practical application of self-induced flotation The self-induced flotation of a range of sulfide minerals has been well established in laboratory studies. However, this phenomenon has yet to be applied effectively in practice. Two problems are encountered that are difficult to overcome. Firstly, the self-induced flotation of related minerals of the same metal can be quite different. For example, chalcopyrite can float most effectively in the absence of collectors whereas chalcocite displays negligible floatability in similar environments. These minerals occur together in many copper ores and hence the different responses of these related minerals raise serious problems. Secondly, self-induced flotation is sensitive to inhibition from metal hydroxides (Senior and Trahar, 1991; Grano et al., 1997). The development of metal hydroxides will depend on the grinding media and will vary with ore type and water source. The inhibition by metal oxides can readily be avoided under laboratory conditions but is difficult to control on the industrial scale. The effect of hydroxides can be reduced or eliminated by complexing the depressant ions but this is unlikely to be economically favourable with respect to the addition of collectors. The addition of collectors, even at low levels, can counter the effect of hydroxides and establish efficient flotation. It is often difficult to ascertain to what extent this amounts to collector-induced flotation or to countering the inhibition by hydroxides of self-induced flotation (Senior and Trahar, 1991). Attempts were made by Control International to exploit the phenomenon commercially in Arizona copper mines in the late 1980s (Arbiter and Gebhardt, 1992). Flotation recoveries in the complete absence of collector failed to match that achieved in conventional practice. The conclusions reached in these studies are best expressed in the words of Arbiter and Gebhardt (1992) when they reviewed the work carried out by Arbiter and Vargas in the southwest US copper mines, In view of the low collector requirements and cost for the copper ores tested, the present practicality of collectorless flotation on an industrial scale is questionable. Based on cost of collector alone, it would not appear practical that one could achieve sufficient control of the electrochemical environment at similar cost. However, if one can offset, by better control of

Fig. 5. Potential of onset of flotation compared with standard and reversible values (from Woods, 1991).

copper or nickel sulfide for the ternary sulfides. The solid line is drawn at a 45j slope that corresponds to an exact correlation between the two parameters. The standard potential refers to each component in its standard state and hence to pH 0, since H+ ions are released in the oxidation reaction. The dashed line in Fig. 5A corresponds to the reversible potentials at a pH value of 8.5, which is close to that corresponding to the flotation measurements. It can be seen that a good correlation exists with the observed flotation edges. The important reaction could be the formation of the M2 + ion rather than M(OH)2. The flotation potentials of Healy and Trahar are plotted in Fig. 5B (open circles) against the standard potentials of the MS/M2 +, S0 couples, again assuming that only iron is removed from the ternary sulfides. It is apparent that a good correlation exists for this reaction as well as for the formation of the metal hydroxides. The standard potential relates to 10 5 mol dm 3 M2 + for each mineral (dashed line), which is a realistic value for flotation systems.

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the electrochemical conditions, the extensive use of lime as a modifier for flotation and corrosion control and achieve similar or improved metallurgy, then it may be practical to pursue this goal. Other costs associated with controlling the system environment need to be considered, including those for replacing or purifying system water, or using complexants to nullify ionic depressant effects, and the probable costs of additional equipment for these purposes. The combination of control of the electrochemical environment with judicious use of reagents may offer the best approach to optimizing metal recovery at minimal costs. Although it has not proved possible to date to exploit flotation without collectors, it should be pointed out that self-induced flotation can occur whenever the potential is in the region of surface oxidation. Thus, self-induced flotation acts as a complication in collector-induced flotation. An interesting approach to inhibiting the collectorless flotation of pyrite in coal flotation was adopted by Yoon et al. (1996). It was shown that pyrite rejection can be improved by galvanic coupling the pulp with active metals such as zinc, manganese, and aluminium. These metals act as sacrificial anodes and maintain the potential of the pulp below the region in which superficial oxidation of pyrite occurs to form a hydrophobic surface layer.

the plant. As pointed out by Hintikka and Leppinen (1995) monitoring of potential with noble metal electrodes is now almost routinely carried out in laboratory testwork and full-scale processes. Early examples of the application of potential measurements in developing flotation strategies are those of Johnson (1988) at Mt. Isa Mines in Queensland. The aim in laboratory studies is to establish the same Eh at the commencement of flotation as occurs in the plant. The scale-up factor from laboratory to plant mill, together with aeration during cyclone classification, is such that the Eh profile in the process will differ between the laboratory and the plant situation. One approach to simulating the plant was adopted by Arbiter and Vargas (private communication), who found that grinding in a mill charged with 80 85% stainless steel and 15 20% mild steel resulted in flotation behaviour in the laboratory analogous to that in the plant. 4.1. Outokumpu Oy Outokumpu Oy promotional literature, Turning theory into profit, states that, in flow sheet development, special attention is paid to electrochemical measurements and that Eh data, in conjunction with other metallurgical information, can lead to significant improvements in existing processing strategies. Rounala et al. (1997) reported laboratory investigations on the influence of grinding media and flotation gas composition on flotation efficiency of sulfide ores. Studies on Outokumpu ores have also been made by VTT Chemical Technology laboratories (Hintikka and Leppinen, 1995) in which the flotation gas composition was varied for potential-controlled flotation. Following grinding, air was used in the flotation cell until the potential of noble metal and mineral electrode probes inserted in the pulp reached a selected value and then a mixture of nitrogen and air was used to maintain the potential of a mineral electrode to within 2 5 mV of this value throughout the flotation stage. Fig. 6 shows the results obtained for a complex copper zinc lead ore using a chalcopyrite electrode to monitor potential. It can be seen that the optimum potential for separation of the chalcopyrite from the other two sulfides is f 0 V. The authors reported that the selectivity in the flotation process was signifi-

4. Monitoring potential in developing flotation strategies Electrochemical studies of sulfide flotation systems have clearly shown that flotation recovery is a function of the potential across the mineral/solution interface. The possibility of using measurements of potential, commonly known as the Eh, to monitor or control flotation has been considered by many groups throughout the world since the pioneering measurements of Eh in Australian flotation plants made by Jones and Woodcock (1971). For example, Ralston (1991) reviewed Eh and its consequences in sulphide mineral flotation more than a decade ago and pointed out that Eh is a very useful diagnostic parameter, whether it is used in the plant or the laboratory. Now, most laboratories apply potential measurement to derive optimum flotation strategies for operation in

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Fig. 6. Effect of potential on the recovery of elements from a complex Cu Zn Pb ore. Potassium amyl xanthate 150 g/t, SO2 400 g/t, pH 11.5, flotation time 10 min (from Hintikka and Leppinen, 1995).

cantly improved under conditions of controlled potential compared to open potential conditions. 4.2. Original potential flotation The Central South University of Technology in Changsha, China has utilized electrochemical studies

in the laboratory to develop their Original Potential Flotation (OPF) technology. This group studied the electrochemistry of galena flotation and, from these studies, advanced a modified, conventional flotation procedure for the treatment of lead zinc ores using different collectors from those in previous practice and floating at different pH. This group reported (Guohua et al., 2000) that the OPF technology has been applied successfully in galena flotation of complex lead zinc iron sulfide minerals in China. The flotation flow sheet is simpler than that used previously due to the lead flotation rate being accelerated. For example, in the Nanjing lead zinc mine of Jiangshu Province, the number of flotation machines needed was decreased to one half without cutting down the production capacity. Other ores investigated were from the Fankou and Lechang lead zinc mines of Guangdong Province and the Beishan lead zinc mine of Guangxi Province. The main minerals present in the four ores were galena, sphalerite and pyrite, but their content and the degree of oxidation, were different. The most effective collector identified in OPF studies was diethyldithiocarbamate and this compound was applied at a dosage below 70 g/t, and lime was

Fig. 7. Effects of pulp pH and Eop on lead zinc iron sulfide minerals flotation (from Guohua et al., 2000).

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used to modify pH and Eop. Their test results are given in Fig. 7. Although the ores were obtained from different mines, the relationship between pH and Eop was found to be the same. Thus, they were able to translate their findings to the plant situation by simply monitoring pH. It can be seen from Fig. 7 that, at pH >12.5, the Eop is < 0.17 V and, under these conditions, the recovery of galena is the optimum and the content of sphalerite and pyrite in the lead rougher concentrate is least. The improvements achieved by the adoption of the OPF flotation strategy, compared to that using the previous approach, are reported to be substantial as can be seen from Table 1 (Guohua et al., 2000). 4.3. SIPSA Pen oles, Mexico Uribe-Salas et al. (2000a,b) recently reported that significant metallurgical improvement was achieved in the flotation of galena and chalcopyrite from a finegrain, complex pyritic ore as a result of adjusting the pulp potential to around 0.3 V by the addition of hydrogen peroxide. The collector used in this study was a mixture of Aeroflot 404 (sec-butyl dithiophosphate and mercaptobenzothiazole), Aerophine 3418A (diisobutyl dithiophosphinate), and amyl xanthate. Noble metal electrodes were used to monitor the pulp potential. Fig. 8 shows the improvement achieved by changing the pulp potential from the value reached in the plant under the prevailing conditions. The authors reported that a potential control system, equivalent to the one described in their paper,

Fig. 8. Grade vs. recovery curve for lead indicating the effect of changes in the pulp potential from the value occurring in the plant and of amyl xanthate additions (from Uribe-Salas et al., 2000b).

had been adopted for industrial operation and good results were obtained.

5. Potential monitoring and control of flotation 5.1. Copper molybdenum flotation The use of nitrogen to replace air in the flotation stage of plants in which molybdenite is separated from copper sulfides was introduced in the mid-1980s in North and South American to minimize oxidation of the NaHS used to depress copper sulfides. At the same time, sulfide additions were monitored and controlled by the use of noble metal electrodes inserted in the pulp. Aravena (1987) reported that NaHS consumption was reduced by 48% with the introduction of nitrogen at the Chuquicamata mine in Chile and a further saving of 21% achieved when depressant additions were controlled by electrode measurements. 5.2. Controlled potential sulfidization Jones and Woodcock (1978) proposed that sulfidization of oxidized lead and copper ores should be carried out under potential control to improve performance. Controlling the potential during sulfidization ensures that the oxide component of the ore is sufficiently converted to sulfide for it to float while the sulfide ions remaining in solution are insufficient

Table 1 Flotation performance before and after adoption of the OPF flotation strategy (Guohua et al., 2000) Mine Flotation technology OPF traditional OPF traditional OPF traditional OPF traditional Lead concentrate Grade 62.61 58.02 57.20 56.47 58.28 55.05 55.45 51.57 Recovery 85.40 82.40 82.35 80.11 75.19 70.01 90.06 86.17 Zinc concentrate Grade 55.11 53.03 51.05 50.70 54.91 54.67 53.62 51.49 Recovery 95.51 92.27 91.65 87.02 92.86 88.87 91.52 87.00

Fankou Lechang Beishan Nanjing

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to depress subsequent flotation. In both controlled potential sulfidization (CPS) and copper/moly separation, the electrode responds to solution species, although the solution species are responsible for control of the potential of the mineral/solution interface. Woodcock and Jones suggested that silver sulfide ion selective electrodes be applied but this proved inappropriate in plant practice and were replaced by noble metal electrodes (Jones, 1991). The improvement in performance resulting from the use of CPS compared with that obtained with slug addition of NaHS is shown in Fig. 9. In Australasia, CPS, marketed through AMDEL laboratories, is being, or has been, applied at the Boddington, Cadia, Horseshoe, Mineral Hill, North Parkes, Ok Tedi, Red Dome, Selwyn, and Telfer mines for the treatment of copper/gold ores containing reactive sulfides or mixed oxides and sulfides (Jones, 1991; Woodcock and Hamilton, 1993; Woodcock, private communication). Mekhanobr in St Petersburg, Russia has also marketed a CPS system (Mashevsky, private communica-

tion) and it has been applied in mines in Europe and Asia for the separation of molybdenite from copper sulfides and the flotation of oxidized lead zinc and copper ores. Herrera-Urbina et al. (1999) have also concluded that the xanthate flotation of sulfidized, mixed oxide sulfide ores may be controlled by monitoring pulp potential. Outokumpu recently suggested (Heimala and Jounela, 2000) that djurleite (Cu1.96S) electrodes should be used for CPS flotation of oxidized copper and cobalt ores with the potential controlled between 600 and 300 mV vs. SCE, the optimum value depending on mineral composition. It was found that effective mixing of NaHS additions was important in achieving good grades and recoveries. 5.3. Sulfide mineral flotation More challenging for the flotation engineer than controlling sulfide additions is the monitoring and control of the potential of the mineral/solution interface across the full range of flotation situations in order to enhance performance and maintain it at a high level. A number of groups throughout the world have researched the concept of controlling flotation plants through continuous measurement of potential in the pulp. The questions to be answered before a control system can be made effective are:
 

how should the potential be measured, and how should the potential be adjusted.

Fig. 9. Comparison of slug vs. CPS sodium sulfide additions for flotation of a mixed oxide sulfide copper ore (from Ashton, 1984).

As pointed out above, noble metal electrodes are appropriate for determining potential in systems in which a dominant redox couple determines the potential, such as in monitoring NaHS additions. Such electrodes can also be used in conventional flotation pulps for monitoring pulp potential; for example, Hecker et al. (1999) applied platinum electrodes for potential monitoring in the El Teniente Colon concentrators SAG line feeding the copper flotation rougher circuit. However, potential measured by a noble metal electrode in a conventional pulp may not be that corresponding to a mineral/ solution interface of interest. Rand and Woods (1984) demonstrated that a platinum or gold elec-

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trode could express a potential close to that of a galena electrode inserted into the same pulp due to continued collision between the noble metal surface and galena particles. However, this does not apply to complex ores because different sulfide minerals in a pulp can be at different potentials (Rounala et al., 1997). Also, noble metal electrodes do not correspond to sulfide mineral potentials in dilute pulps, such as in the flotation of platinum group metal ores (Buswell et al., 2002). It would appear that the most appropriate method of determining the potential of each sulfide mineral in the flotation of complex ores is to use electrodes composed of the individual minerals being floated or depressed. However, the surface of the mineral electrodes will continuously react with the collector and other constituents of the pulp and hence will not continue to respond in the same manner as the freshly ground mineral particles of the same composition in the flotation pulp. Outokumpu has addressed this problem (Rounala et al., 1997) by regenerating sulfide mineral electrodes by electricity or ultrasound as well as by mechanical cleaning. It is difficult to know to what extent these treatments alleviate the problem, or if better techniques are required to maintain the activity of sulfide mineral electrodes and ensure that the potential expressed is the same as that of the particular mineral in the flotation pulp being monitored. Adjustment of potential can be achieved by modifying the conditioning time or by changing the composition of the pulp or flotation gas. It is interesting to note that Newmont Technologies has developed a process, N2TecR, for the flotation of refractory gold ores that employs nitrogen as the carrier gas. This process is being employed at the Lone Tree mine and at the Tonkin Springs gold project (Symmons et al., 1999). Presumably, the use of nitrogen inhibits the oxidation of auriferous sulfide mineral fines. Measuring pulp potential would appear to be a useful method of monitoring such a process. In most cases, the pulp chemistry that gives good flotation recovery has been established by conventional methods, and only small changes in potential are required to maintain flotation efficiency at the optimum level. A recent paper (Panayatov et al., 2000) described technology for direct potential control using electrodes inserted in the pulp but regulating

pulp chemistry offers a simpler and more economic approach. 5.3.1. Control International Control International adopted an electrochemical monitoring procedure for sulfide flotation plants (ECON) that was claimed to establish the relationship between ore mineralogy and electrochemical variables. It was reported (Suttill, 1990; Herbst et al., 1994) that application in a major lead zinc plant resulted in a reduction in overall processing costs as a result of improved metallurgical performance and lower reagent consumption. In particular, flotation could be accomplished at much lower pH values than those that were used in plant practice. Control International promoted E-CON as a control method, in particular, to regulate conditions in grinding that influence subsequent flotation. No details of the electrodes were announced in the Companys promotional documentation but it is likely that a noble metal electrode was employed. Apparently, the announcement in 1990 of this control system being available on the market was premature and the Company did not proceed with its development. 5.3.2. Outokumpu Oy Outokumpu Oy in Finland has progressed further than any other Company in the application of potential measurement for flotation control and has introduced its OK-PCF potential monitoring system in a number of its flotation plants. The system has been in operation at the Hitura nickel mine since 1984, at the Vammala nickel and Vihanti Cu/Zn/Pb mines since 1988 and was installed at the Pyhasalmi Cu/Pb/Zn/ FeS2 mine in the early 1990s. At Hitura, the replacement of pH control by potential control resulted in an improvement in nickel recovery by up to 2% depending on ore type (Rounala et al., 1997). At Vihanti, it is claimed that lime and collector consumption has been decreased to one third of the values experienced prior to the installation of the OK-PCF system. It is claimed that profitability has increased by 10 20% since potentials have been monitored. Outokumpu use electrodes composed of synthetic or natural sulfide minerals, usually of the composition being floated. For each valuable mineral, it is claimed (Rounala et al., 1997) that there may be one or more combinations of variables for the most economic

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processing, and this requires integration of on-stream X-ray analysis, electrochemical potential measurements, and collector concentrations. Despite a number of years of experience in the application of electrode measurements in flotation plants, Outokumpu has yet to market a potential monitoring or control system.

6. Concluding remarks Considerable advances have been made in understanding sulfide mineral flotation from an electrochemical viewpoint. This review seeks to highlight how this knowledge has been used to identify and solve problems in flotation plants and to develop improved flotation strategies. The use of Eh measurements to achieve more effective flotation in laboratory and plant studies is now common practice. Continuous monitoring of electrode potential is well established practice in flotation plants in situations where the potential is determined by a strong redox couple, such as in chalcopyrite molybdenite separation or the sulfide activation of oxidized ores. The ultimate aim of controlling potential in sulfide flotation plants in the usual situation in which the potential is determined by a balance between two or more electrochemical processes has, however, proved elusive. It would be incorrect to conclude that this means of potential is not a realizable control parameter in such situations. Maintaining electrode probes so that they respond appropriately in these plants is difficult to achieve, and the choice of materials for electrode probes and methods to activate or regenerate surfaces have, most likely, yet to be optimized. Clearly, this is an area for further research.

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