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Redox potential control during flotation of sulphide minerals

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 Redox potential control during flotation of sulphide minerals
Wonder Chimonyo, Kirsten Corin, Jenny Wiese and Cyril O’Connor
Centre for Minerals Research, Department of Chemical Engineering, University of Cape Town

Abstract

Redox potential (Eh) control plays a critical role during sulphide mineral flotation by influencing the
reactions on the surface of the minerals and consequently the flotation behaviour. Batch flotation tests
using sodium hypochlorite (NaCIO), as an oxidant were conducted to show the effect of oxidation on
the metallurgical performance of a typical Merensky PGM ore. A change of pH from 9 to 11 lowered
the Eh to values between 0 and 100 mV and resulted in a decrease in the amount of solids recovered. It
was observed that for copper there was no significant change in recovery for all of the conditions
investigated in this study. Nickel had the lowest recovery of 7 % in collectorless flotation and the highest
recovery of 76% in the presence of collector and without NaCIO.

Key Words: flotation recovery, grade, redox potential

1. Introduction

Literature is generally in agreement that base metal sulphide (BMS) minerals are commonly associated
with PGMs within the Merensky Reef and this has an effect on the way in which these minerals can be
concentrated by flotation (Vermaak et al. 2004; Wiese et al. 2005; Mphela 2010; Miller et al. 2005;
Schouwstra et al. 2000). Furthermore it has been suggested by Shackleton, (2007) that PGMs behave in
the same way as sulphides during flotation. A major problem stemming from this association has been
reported to be losses of valuable minerals (PGMs) associated with the loss of BMS (Wiese et al. 2005),
during flotation. In order to float the PGMs the base metals are targeted. Therefore, there is a need to
investigate ways to improve the flotation performance of the sulphide minerals. The study of the
electrochemistry of flotation of sulphide minerals has been ongoing for over half a century. There has
been consensus that sulphide minerals float only under a suitable redox environment (Heyes & Trahar
1979). This implies that reducing and oxidizing conditions during flotation of ores such as the Merensky
Reef can be manipulated/varied to achieve an optimum flotation response.

During flotation, sulphide minerals interact with thiol collectors in an electrochemical reaction to form
hydrophobic entities at the mineral surface (Finkelstein & Goold 1972; Rand & Woods 1984). The
sulphide minerals are semiconductors and their interaction with collectors involves transfer of electrons.
As such, a potential difference is formed and this is responsible for driving electrons between reacting
species (Fuerstenau et al. 2007). The magnitude of the potential difference affects the relative energies
of charge carriers (electrons) at the mineral/solution interface hence controlling the direction and rate
of charge transfer or rate of reaction (Bard et al. 2001). In a mixed mineral system the mineral/solution
interface potentials account for the mixed potential which is critical to the process of flotation (Chander
2003; Sun & Wang 2009; Woods 2003).

The use of potential as a parameter to control flotation has been widely proposed in literature (Leppinen
& Hintikka 1995; Woods 2003; Smith et al. 2012; Chander 2003; Goktepe 2001; Rao 2004; Khan et al.
2004; Javadi 2013; Ross & Van Deventer 1985; Allison et al. 1972; Sun & Wang 2009; Gardner &
Woods 1979). There have, however, been significant contradictions and inconsistencies in potential
range values where flotation recovery can be maximised (Guo & Yen 2003; Goktepe 2001). In addition,
there are uncertainties around parameters like oxidation-reduction potential (Eh), dissolved oxygen
(DO) and pH during flotation of mixed sulphide mineral systems (Heyes & Trahar 1979). It has been
noted that it is difficult to accurately predict the effect on recovery of changing these parameters. These
parameters affect the nature of oxidation-reduction reactions, the stability of the collector and the
processes of precipitation and dissolution at either the mineral surface or in the pulp (Abramov &
Avdohin 1998). The following reaction depicts the reduction of hypochlorite under the conditions
investigated in this study, where the natural pH of the ore is generally around 9.

CIO- + H 2 O + 2e- → CI- + 2OH – Eo (V) = 0.89 V (1)

Eo (V) is the standard potential.

Reaction (1) is stable around pH 9 judging by the positivity of its standard potential, Eo (V) of 0.89 V.
The more positive the potential the higher the likelihood of the reaction to be thermodynamically stable.
The value of the potential in a system can be calculated using the Nernst Equation shown below and
depends on the activity of the available species (Mendiratta 2000)

(2)

The investigations conducted in this study were on a Merensky ore using a chemical oxidizing reagent,
sodium hypochlorite (NaCIO), to control the redox potential. NaCIO has been proposed to be a suitable
redox agent for potential control by various authors (Woods 2003; Guo & Yen 2005; Smith et al. 2012;
Plackowski et al. 2013). This study investigates how NaCIO affects metallurgical performance. Little
information is available on how NaCIO performs during bulk sulphide flotation. Plackowski et al.
(2014) investigated the effect of increasing potential to +500 mV, using NaCIO, on the flotation of
enargite (Cu 3 AsS 4 ). They found a high recovery of 82 % at +500 mV compared to recoveries of 52%
at a potential of +100 mV. It was also found by Woods (2003) that it is possible to float chalcopyrite
(CuFeS 2 ) from galena (PbS) by control of the redox potential measured. High recoveries of chalcopyrite
at a potential of 450 mV and low recovery of galena at the same potential were observed. Conversely
galena was found to float effectively at a potential of -150 mV.

There is no demonstrated evidence in literature on potential control for a real ore, like the Merensky
Reef using an oxidizing agent. The objective of this study, is to understand how changes to redox
potential can affect overall flotation recovery in a complex sulphide ore, by the use of a chemical reagent
(sodium hypochlorite) under changing pH conditions.

2. Experimental Details
2.1 Reagents

0.1 M sodium hydroxide (NaOH) solution was used to adjust the pH in the flotation cell. 1% solution
of Sodium Ethyl Xanthate (SEX) was used as collector at a dosage of 100 g/t. Collector was prepared
fresh each day. The collector was supplied by Senmin. DOW 200, supplied by BetaChem, at a dosage
of 40 g/t was used as the frother. Sodium hypochlorite (NaCIO), supplied by Kimix, was used for
oxidation-reduction potential (Eh) control. A 1% solution was prepared from a 12% commercial
solution using distilled water and was added at a dosage of 500 g/t.

2.2 Flotation Experiments

A 1 kg sample of Merensky ore (±1 mm) was milled in a laboratory scale rod mill to the required particle
size of 60% passing 75 µm. After milling, the slurry was transferred to a 3L batch flotation cell and
made up to a pulp density of 33% solids by addition of synthetic plant water (SPW). Depending on the
required conditions for experiments, the oxidant was added for conditioning either in the mill or into
the flotation cell, however, the collector was always added to the mill. A YSI probe was used for
measurement of Eh, and pH during the conditioning stage.

The impeller speed of the flotation cell was set to 1200 rpm and the airflow rate was 7 L/min. A 50 ml
feed sample was collected before each experiment. A total of four concentrates (C1, C2, C3, and C4)
were collected by scraping froth off manually every 15 seconds, into pre-weighed dishes. A froth height
of 2 cm was maintained manually by constantly adding SPW. The total time for each flotation test was
20 minutes. At the end of flotation two 50 ml tailings samples were collected. The feed, concentrates
and tails samples were filtered, dried and weighed before being assayed for copper and nickel using a
Bruker XRF. All experiments were performed in duplicate for reproducibility. All Eh values are
reported versus the standard hydrogen electrode (SHE).

3. Results and Discussion

Figure 1 shows the control of Eh using NaCIO as a function of pH for a Merensky ore pulp. At pH 9,
the natural Eh of the slurry was between 100 - 200 mV. The addition of NaCIO resulted in an increase
in the Eh to 500-600 mV, as shown by the triangles in Figure 1. This increase resulted in an insignificant
change of pH as shown in Figure 1.
 E X - /X2

Figure 1: Control of Eh using NaCIO as a function of pH in a flotation cell for a Merensky ore pulp.

When the pH was adjusted to pH 11 by the addition of NaOH the natural Eh was found to have decreased
to a region between 0 – (-100 mV). When NaCIO was added at pH 11 the Eh increased to 250 mV on
average, as shown by the squares in Figure 1. From the findings in Figure 1, it can be deduced that Eh
is independent of pH under the conditions tested. This was considered as crucial to reduce the number
of variables allowing the effects of changing Eh to be analysed. The dashed line represents the Eh above
which xanthate will form dixanthogen.

Figure 2: Final solids and water recoveries at pH 9 and 11.

Figure 2 shows the final solids and water recoveries obtained for tests at pH 9 and pH 11. The figure
also shows the baseline data for comparison, i.e. the results without any reagent addition at both pH
values. (The collector, SEX is represented in Figure 2 as X). At pH 9 there was a slight increase in solids
recovery with increasing potential due to the addition of an oxidizing reagent (NaCIO). Under all other
pH 9 conditions the amount of water recovered was very similar, except in the presence of both NaCIO
and a collector when the highest amount of water was recovered at pH 9.

As can be seen from Figure 2 the amount of water recovered at pH 11 was high as compared to pH 9. It
is also interesting to note that at pH 11, the addition of a collector tends to have stabilised the froth
resulting in high solids recoveries under the conditions where a collector was present. However, at pH
9 far more total solids per unit water were recovered than at pH 11. This observation is consistent with
literature (Corin et al. 2012) in that at high pH less solids are recovered than at a lower pH. This can be
attributed to an increased rate of formation of hydrophilic species due to an increase in concentration of
hydroxide ions at higher pH. The hydrophilic species might include ferric hydroxides and these can be
present at the mineral surface making it less hydrophobic and subsequently less floatable (Corin et al.
2013).

Solids and water recovery can be used to understand the effects of various reagents on froth stability.
An increase in solids recovery can be due to either true flotation or entrainment or both (Harris 2009).
It is also possible that the use of NaCIO may have activated the flotation of gangue minerals and thereby
increasing the amount of solids that were recovered. It has been reported in literature that the effects of
flotation reagents on froth stability can be either direct or indirect (Wiese et al. 2011). This statement
supports the findings from this study where the influence of flotation reagents on froth stability was not
observed from the baseline data. When the solids and water recoveries are high the froth is more stable
(Ekmekçi et al. 2005). Tests conducted when there were no reagents showed the lowest recoveries in
terms of solids and water at both pH values. The amount of solids and water recovered increased when
a collector was added over both Eh and pH ranges
Figure 3: Final recovery and final grade for copper and nickel at pH 9 in the absence and presence of a collector and NaCIO

Figure 3 shows the recovery and grade of copper and nickel at pH 9. The results generally show higher
recoveries of copper than nickel under all the conditions shown. The highest recovery for copper was
84% in the presence of a collector and NaCIO at pH 9. The grades of copper were not significantly
affected by a change of conditions. In the absence of collector the recovery of nickel was 13% and the
control of Eh to between 500 - 600 mV slightly increased the recovery of nickel to 32%. The highest
recovery and grade for nickel was achieved in collector induced flotation.

Figure 4: Final recovery and final grade for copper and nickel at pH 11 in the absence and presence of a collector and NaCIO

Figure 4 shows the recovery and grade of copper and nickel at pH 11. The results obtained show high
recoveries of copper compared to nickel. In the absence of a collector the recovery of copper was 69%
and the presence of NaCIO resulted in a recovery of 74%. It can also be observed that in the presence
of a collector the recovery for copper was 80% and when both a collector and NaCIO were present the
final recovery was marginally affected. This shows that the change in recovery for copper was only
marginal at pH 11. On the other hand, results in Figure 4 show that nickel recoveries and grades were
low in the absence of a collector. In the presence of NaCIO a final recovery of 7% and final grade of
0.4% was achieved. The presence of collector significantly improved the recoveries and grades for
nickel.

When comparing Figures 3 and 4, it can be concluded that copper flotation performance was not
significantly affected by the changes in either Eh or pH. The flotation behaviour of copper in
collectorless flotation is consistent with findings of other authors (Ross & Van Deventer 1985; Hayes
et al. 1987) who noted high recoveries of copper in the absence of a collector. The insignificant
difference in the recovery of copper in the absence and presence of the NaCIO, can be explained by the
fact that chalcopyrite is fast floating and has a stronger catalytic effect towards the reduction of oxygen
and mineral surface oxidation to elemental sulphur formation. It is common knowledge that oxygen
reduction shown in reaction 2 is a prerequisite for electrochemical reactions which result in mineral
floatability (Sun & Wang 2009). According to Eliseev (2012) and Gardner & Woods (1979) elemental
sulphur can be formed when a sulphide mineral undergoes oxidation. The elemental sulphur is the
hydrophobic species responsible for flotation in the absence of collectors (Hayes & Ralston 1988).
Recovery of an average of 70% for copper, could also be attributed to the molecular absorption of
oxygen which dehydrates the mineral surface even in collectorless flotation (Smart et al. 1998). This is
important to promote the interaction between the particles and air bubbles at the solid/air interface under
the typical flotation conditions of open air.

The presence of a collector increased the grade and recovery for nickel at both pH values, whereas in
the absence of a collector very low recoveries (less than 35%) were achieved. This behaviour can be
attributed to the electrochemical reactivity of the minerals containing nickel and copper in a typical
aerated flotation system. Nickel contained within pentlandite has a lower rest potential of 250 mV
compared to 300 mV of copper within chalcopyrite. These rest potentials were obtained from studies
conducted elsewhere in this project. It is understood that the rest potentials for each system can be
different. According to measurements in literature by Buswell et al. (2002), they showed that pentlandite
has a lower rest potential than chalcopyrite. The difference in rest potentials imply that nickel can easily
undergo oxidation and the reactions can be presented as follows (Khan et al. 2004);

Pn[(Ni 4.5 Fe 4.5 )S 8 ] + 22.5OH- →Pn[4.5Fe (OH) 3 + (4.5-x)Ni(OH) 2 +8S] + xNi(OH) 2 + 22.5e- (3)

Pn[(Ni 4.5 Fe 4.5 )S 8 ]+ 54.5OH- →Pn[4.5Fe (OH) 3 + (4.5-x)Ni(OH) 2 +8S]+ xNi(OH) 2 + 8SO 4 2- + 38.5e-
(4)

Reactions (3) and (4) show the possible formation of sulphate, ferric and nickel hydroxides at the
mineral surface. These oxidation products are hydrophilic and are responsible for the low recovery of
nickel in collectorless flotation. The mechanism of interaction is chemisorption which is the most
thermodynamically feasible and occurs as the first step. It results in formation of nickel xanthate and in
the second stage transformation of the chemisorbed xanthate to dixanthogen can occur (Khan et al.
2004; Kelebek & Nanthakumar 2007). Through the formation of these species the mineral can exhibit
hydrophobicity as shown by the high recoveries obtained in the presence of collector, and both
collector/NaClO at pH values of 9 and 11. Xanthate can remove any hydrophilic oxidation products as
shown in reactions (3) and (4) from the mineral surface depending on their solubility products.
(Chanturiya & Vigdergauz 2009) This serves as confirmation that more effective flotation of nickel can
be achieved in the presence of a collector. According to Bozkurt & Xu (1998) even under oxidizing
potentials nickel requires a collector to undergo significant flotation. The recovery for nickel obtained
at pH 9 in collector-induced flotation was 76% and when both the collector and NaClO were added the
recovery was hardly affected.

An increase in the oxidizing potential further above that of dixanthogen formation to a region of 500 –
600 mV (using NaCIO) was expected to increase the recovery. It was hypothesised that raising potential
can increase relative energy of charge carriers. Subsequently this can increase the oxidation rates of the
collector to dixanthogen. Dixanthogen is the most preferred species which is a well-known product
responsible for improving recovery (Khan & Kelebek 2004). Furthermore, the thermodynamics of
electrochemical reactions support the fact that an increase in potential results in a reaction occurring at
a faster rate. At pH 11 the potential was 0 – 100 mV, which is below the dixanthogen formation potential
of 150 mV. There was little effect on recovery of the valuable minerals, which exhibited recoveries of
80% for copper and 60% for nickel in the presence of a collector. The recoveries can be attributed to
the presence of the hydrophobic metal xanthate species at the mineral surface.

In describing the action of NaCIO as a potential modifier, potential control by use of NaCIO is intended
to causes dixanthogen formation by ensuring that the mixed potential of the system is in the right region.
Plackowski et al. (2014), confirmed the presence of dixanthogen in the same potential range as
investigated in this study. According to Chanturiya & Vigdergauz (2009), the detailed mechanism of
action of potential modifiers is not clearly understood in a typical flotation system. Most studies
available have been either single mineral studies or mixtures of two minerals. It is difficult therefore to
make concrete conclusions from such studies when considering a real ore system. Fuerstenau et al.
(2007) agreed that there is limited discussion of modifiers in literature. The results of this study have
contributed towards an increased understanding on the effects of controlling Eh in a real ore system by
chemical means (using NaCIO).

3.1 Flotation kinetics

Flotation kinetics can be used to analyse the flotation performance under the selected conditions
investigated in this study. The Classical model has been used to analyse flotation rates and establish the
flotation performance. The model can be represented as shown:

𝑅𝑅 = 𝑅𝑅 𝑚𝑚𝑎𝑎x (1 − 𝑒𝑒−𝑘𝑘𝑡𝑡)
Where R is the recovery, R max is maximum possible recovery, k is the flotation rate constant and t is
flotation time.

Figure 5 shows the rate of recovery for copper under selected reagent conditions at pH 9.

pH 9

Figure 5: Flotation rate of copper at pH 9

In Table 1 the flotation rate constants and maximum possible recovery for copper at pH 9 are shown

Table 1: The rate of flotation (k) and maximum recovery (R max ) for copper at pH 9 at shown conditions
Conditions Classical model constants

k(min-1) R max (%)

No reagent 0.79 69

X 1.01 83

NaCIO 0.70 74

X, NaCIO 1.10 84

It can be observed in Figure 5, that in the presence of a collector, the highest rate constants were
achieved. These correspond to the high maximum possible recovery obtained, with the highest being
84% in the presence of NaCIO. In the absence of a collector the rate constants were low.
Figure 6 shows the rate of recovery of nickel under selected reagent conditions at pH 9.

pH 9.2

Figure 6: Flotation rate of nickel at pH 9

In Table 2 the flotation rate constants and maximum possible recovery for nickel at pH 9 are shown. As
was also the case for copper, the highest flotation rate constants for nickel were achieved in the presence
of a collector.

Table 2: The rate of flotation (k) and maximum recovery (R max ) for nickel at pH 9 at shown conditions
Conditions Classical model constants

k(min-1) R max (%)

No reagent 0.17 13

X 0.53 76

NaCIO 0.14 34

X, NaCIO 0.53 72

The results in Figure 5 and 6 show the flotation kinetics of copper and nickel at one of the pH values
investigated in this study, i.e. 9. It is clear that copper is fast floating in comparison to nickel. The results
are consistent to what is already available in literature regarding the flotation rates. It is again interesting
to note the need for a collector to induce flotation.

4. Conclusions

The addition of a chemical oxidant (NaCIO) was used to determine the effects of potential (Eh) control
on the flotation performance of a Merensky ore. It was observed that NaCIO did not cause any
substantial changes to pH during conditioning. However, increasing Eh generally caused an increase in
the amount of solids and water recovered at both the pH values investigated. There was no significant
change to recovery of copper and nickel when changing Eh to a higher potential. It was established that
copper was essentially independent of changes to both Eh and the pH. However, notable changes were
observed on the grade of nickel which was more dependent on the presence of a collector and the pH
of the system.

Eh control is dependent on the sulphide ore content and the type of ore investigated. The Merensky ore
has a very low sulphide content and this might had a bearing on the results obtained in this study. The
application of an oxidant in a bulk sulphide process had not been established quantitatively in literature
and this has proved to be elusive. At this stage, it is sensible to recommend investigation into the
concentration-dependent effect of potential modifiers on bulk sulphide recovery. There is a need for
understanding the optimum potential range for significant recovery in mineral processing, which is
inherently ore dependent.

5. Acknowledgements

The authors wish to acknowledge funding from University of Cape Town (UCT), South African
Minerals to Metals Research Institute (SAMMRI), Department of Science and Technology (DST). This
work is also based on the research supported in part by the National Research Foundation (NRF) of
South Africa (Grant Number 92782/85540)

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