ECS Transactions, 2 (3) 3-8 (2006)

10.1149/1.2195993, copyright The Electrochemical Society

Electrochemical Studies on Heazelwoodite Flotation from Inco Matte

S. R. Rao and J. A. Finch

Department of Mining, Metals and Materials Engineering, McGill University,

Montreal, Quebec, Canada H3A 2B2

Electrochemical and flotation studies were conducted on Inco

matte, which is composed of. chalcocite (Cc), heazelwoodite (Hz)
and Ni-Cu alloy. After magnetic removal of the alloy, chalcocite is
floated using diphenyl guanidne (DPG). There is some flotation of
heazelwoodite, possibly due to inadvertent activation by Cu ions.
This was investigated by: rest potential measurements on matte
components and the mild steel grinding medium, detection of Cu
ions by EDTA extraction, and flotation tests. Rest potentials at the
grinding pH (11.9) showed that the order was: Cc > mild steel >
Cu-Ni alloy > Hz. Along with Cc which oxidizes readily, the Cu-
Ni alloy is potentially galvanically active, releasing Cu ions.
Sodium dithionite proved the most effective, reducing the rest
potential by ca. 100 mV and Cu ion release by nearly 80 %.
Subsequent flotation, however, required aeration to restore Cc
floatability. The combination of dithionite and aeration yielded
superior Cu-Ni separation. The need for aeration is compatible
with the proposed surface product formed by reaction between Cu
and DPG.

Introduction

The Sudbury area Cu-Ni ores comprise the pay minerals pentlandite and chalcopyrite
hosted in pyrrhotite and non-sulfide gangue (rock). In the Inco process, a bulk Cu-Ni
concentrate is produced which is smelted to matte (Inco matte) comprising chalcocite (Cc,
Cu2S), heazelwoodite (Hz, Ni3S2) and a copper-nickel alloy. The matte is caste, cooled,
then crushed and ground. The alloy is recovered by magnetic separation. The chalcocite
is selectively floated from heazelwoodite using diphenyl guanidine (DPG) as both
collector and frother at pH ~12 set by lime (1). The DPG is selective for Cc, but
maximum separation efficiency (difference in Cu-Ni recovery) is limited by some non-
selective flotation of Hz.

A possible cause of Hz flotation is accidental activation by Cu ions released from

matte components. The presence of Cc which readily produces Cu ions is one source (2).
Another could be galvanic interactions in grinding. Two observations reported from the
matte separation plant (M. Xu, Inco Technical Services, Mississauga, Ontario, Canada,
private communication) stimulated this line of thinking: 1, the mild steel grinding media
(balls) remained untarnished (‘shiny’) which is not usually the case when ore is ground,
and 2, cupric ions are detected (by Tof-SIMS) on mineral surfaces. Investigations were
conducted to test for galvanic effects and release of Cu ions.

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Experimental

Samples and Reagents

Samples of matte, heazelwoodite, grinding media and diphenyl guanidine were

obtained from Inco Technical Services, Mississauga, Ontario and chalcocite from Ward’s
Natural Science. The magnetic fraction (mags) was separated by a hand magnet. The
original sample, mags and non-mags fractions were analyzed (atomic absorption
spectroscopy, Perkin Elmer model 3110) (Table I).

The mild steel grinding medium was electrolytically reduced by applying a potential
of –0.6V to remove any oxide film.

Chemicals other than DPG, sulfite, dithionite and ethylene diamine tetra-acetic acid
(EDTA) (sodium salts), were Fisher reagent grade.

TABLE I. Composition of Matte Derived Samples

Sample Cu (%) Ni (%) Fe (%)*
Original 36.8 45.7 2.1
Non-mags 48.5 31.0 1.7
Mags 22.1 58.1 5.2
*The Fe is assumed to be as FeS, the remainder Cu2S and Ni3S2.

Procedures

Potentials were measured with an ORP gold electrode (Cole-Palmer), connected to a

pH-ORP meter (Hanna Manufacture). The electrode was contacted with the specimen
under water at the set conditions. In this study, the term rest potential is employed for the
matte components and pulp potential for the flotation slurry. The pH was measured with
a glass electrode (Fisher Scientific).

Grinding was conducted in a porcelain mini-mill (250 mL) using 0.62 mm (1/4 in)
diameter mild steel balls. The matte was -14 mesh (crushed product). The conditions for
the Cu release (EDTA extraction) study and flotation tests are given in Table II. The long
grind times were required to approach the target for flotation (95 % - 74 µm).

TABLE II. Grinding Conditions

Study Media Matte Water (mL) DPG (mg) pH Time
(g) (g) (hr)
Cu release 200 140 58 0; 10 11.9 4
Flotation 100 50 100 32.5 11.9 6

In the Cu release study, after grinding, the balls were separated from the matte, which
was filtered and dried under vacuum at room temperature. Two to five grams of ground
matte was agitated with 50 mL of 0.2 % EDTA solution for 20 min, the EDTA extract
was separated and analyzed for Cu and Ni. The impact of adding 10 mg of each reducing
agent was tested.

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For flotation, the base line conditions (Table IV) were based on Tipman et al. (1976).
The tests were conducted in a 1 L Denver flotation machine (self-aspirated) at 1200 rpm.
Flotation time was 3 min at which point the froth was barren. The tests were done in
duplicate. From the Cu release results, dithionite (1 g/kg = 50mg) was selected for a
comparative test. This gave very poor flotation. To restore, the pulp was aerated for 20
min, which markedly improved flotation. Again, flotation time was 3 min and tests done
in duplicate.

Results

Rest Potentials

The rest potential of the mild steel and the components of the matte as a function of
pH are shown in Figure 1. The Hz and Cc data are similar to those reported in a previous
study (where both Hz and Cc were synthetic samples provided by Inco) (3). At the
grinding pH the order is: Cc > mild steel > Cu-Ni alloy > Hz.

Figure 1.Rest potentials of mild steel and components of Inco Matte as a function of pH

EDTA Extraction

The grinding experiments confirmed one observation from the plant: the mild steel
balls remained untarnished (whether DPG was present (10 mg) or not). The results of
EDTA extraction from the matte ground in the presence of the three reducing agents (10
mg = 0.71 g/kg) and DPG (10 mg) are shown in Table .III

Flotation

The conditions and results of flotation are shown in Tables IV and V, respectively.
Each test was done in duplicate and the average values are recorded. Average variation in
grade assay was +2 %.

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TABLE III. Effect of Reducing Agents on Pulp Potential and Metal Ion Release (EDTA
Extraction)
Reducing Pulp Potential Metal Ions Released
Agent (mV vs. SHE) (mg/g)
Initial* Final* Cu Ni Fe
None +6 +16 13.5 0.6 0.12
Sulfite -58 +10 13.1 2.3 0.07
Metabisulfite -72 +10 5.2 8.0 0.13
Dithionite -120 -55 2.2 3.6 0.02
* Initial = before grinding; Final = after grinding

The release of Cu ions decreased most notably when ground in the presence of
dithionite.

TABLE IV. Grinding and Flotation Conditions

Test In Grinding In Flotation
Type pH ORP (mV) pH ORP
Initial Final Initial Final Initial Final Initial Final
Baseline 11.9 11.6 -18 -5 11.9 11.7 +20 +45
Dithionite* 11.8 11.6 -110 -115 11.9 11.5 -20 +15
* grinding with 1g/kg sodium dithionite + 20 min aeration prior to flotation

TABLE V. Flotation Results

Product / Mass (%) Grade (%) Recovery (%)
Test Type
Cu Ni Cu Ni
Float
Baseline 49.5 55.9 23.2 82.7 27.4
Dithionite 45.3 65.4 14.6 87.2 15.6
Non-float
Baseline 50.5 11.5 60.2 17.3 72.6
Dithionite 54.7 7.8 65.5 12.8 84.4

As a single measure of separation efficiency, the difference in recovery of Cu and Ni

to the float product (Cu concentrate) increases from 55.3 % for the baseline test to 71.6 %
for the test with dithionite.

Discussion

Grinding Medium Reactions

The pertinent observations from the matte plant experience are that the mild steel
grinding balls remain untarnished (no apparent oxidation at the surface), some
heazelwoodite is non-selectively floated, and Cu ions have been detected on the mineral
surface (by ToF-SIMS). These observations may be related: copper-bearing phases in the
matte are preferentially oxidized which ‘protects’ the mild steel and releases Cu ions,
which activate the heazelwoodite. The present work supports this connection.

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At the grinding pH, the grinding medium has a similar rest potential to Cc and a
higher rest potential than the other two of the matte components. This is unusual in terms
of sulfide grinding experience where usually the mild steel has the lowest rest potential
and oxidizes readily through galvanic interactions (4). To satisfy on this aspect, grinding
separately with pyrite (Py) and chalcocite confirmed the expected tarnished state of the
mild steel with Py but not with Cc (even though the latter’s rest potential is apparently
slightly higher than the mild steel). The mild steel is the electron acceptor (i.e., is
galvanically protected) when in contact with the matte, supporting the plant observation.

The order of rest potentials introduces an initially unexpected source of Cu ions:

generation from the Cu-Ni alloy by galvanic interaction. From electrochemical potential
data on the elements individually (5) this low rest potential of the alloy is ‘unexpected’.
Combined with their ready release from Cc (2) this provides the source of Cu detected on
the mineral surfaces. There would seem little that can be done to alter this situation other
than by adding a reducing agent: removing the alloy from the grind feed is not an option
as it is not liberated and in any event the Cc would likely remain a potent source of Cu
ions.

There was an additional observation of note with regard the mild steel. At low pH the
surface had greenish patches suggestive of ferrous hydroxide, which turned reddish
(ferric hydroxide) with time. This introduces some mixed potential concerns in
interpreting the data. The film may initially passivate the iron leading to a low rest
potential at low pH.

Action of Reducing Agents

Oxidation and galvanic reactions can be suppressed by lowering the oxygen activity,
in this case achieved by introducing reducing agents. Three reducing agents were
evaluated, sulfite, metabisulfite and dithionite. The pulp potential is lowered by about 60
mV with first two, which did not significantly reduce Cu ion production. Sodium
dithionite lowered the potential by nearly –110 mV (to -115 mV) and did hinder Cu ion
production.

It was evident, however, that the low pulp potential reached by grinding in the
presence of dithionite also hindered flotation requiring a judicious level of aeration to
restore Cc floatability. Since the action of DPG does not follow a charge transfer
(electrochemical) mechanism the presence of oxygen is not needed on that score.
However, the requirement is consistent with recent studies by Hart et al. (6) who showed
that some oxidation of Cc to form CuOH (cuprous hydroxide) on the surface is necessary
for DPG complexation. Tipman et al. (1) also showed some oxidation was necessary and,
on the basis of infrared spectroscopy, suggested the surface complex was
Cu(DPG)2SO4.Cu(DPG)2(OH)2, i.e., Cu in the cupric state. The three studies agree in
general for the need of some oxidation, therefore, but the oxidation state of Cu
appropriate to reaction with DPG remains to be resolved.

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Conclusions

This study of Inco matte has shown the following:

1. At the flotation pH, mild steel has a high rest potential compared to the matte
components, i.e., is an electron acceptor, which accounts for the lack of tarnishing
reported from the plant.
2. The mild steel could galvanically interact with Cu-Ni alloy to release Cu ions,
contributing to the Cu ions detected on mineral surfaces (by ToF-SIMS) and
possibly accidentally activating heazelwoodite.
3. The reducing agent dithionite added to grinding lowered the pulp potential and
restricted Cu release but also hindered flotation.
4. Flotation was restored by aeration and the Cu-Ni separation efficiency increased
from ca. 55 to 70 %.

Acknowledgments

The Natural Sciences and Engineering Research Council of Canada (NSERC) under the
Collaborative Research and Development Program provided the funding for this work
with industrial support from Teck Cominco, Falconbridge, Inco, Noranda, COREM and
SGS Lakefield.

References

1. N. R. Tipman, G. E. Agar and L. Pare, in Flotation (A. M. Gaudin Memorial

Volume), volume 1, pp. 528-548, M. C. Fuerstenau, Editor; AIME, New York
(1976).
2. D. Lascalles and J. A. Finch, Minerals Eng. 15, 567-571 (2002).
3. V. Bozkurt, S. R. Rao and J. A. Finch, Can. Met. Quart. 33, 175-183 (1994).
4. R. L. Pozzo, A. S. Malicsi and I. Iwasaki, Minerals Metallurg. Process. 7, 16-21
(1990).
5. G. M. Barrow, Physical Chemistry, 4th edition, p. 626, McGraw-Hill, New York,
(1979).
6. B. Hart, M. Biesinger and R. St C Smart, Centenary of Flotation Symposium, pp.
457-464, Australasian Institute of Mining and Metallurgy, Carlton South, Victoria,
Australia (2005).

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