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Minerals Engineering,

Vol. 14, No. 3, pp. 341-347.2001


8 2001 Published by Elsevier Science Ltd
All rights nserved
08926875(01)oooo5-x 0892-6875101/$ - see front matter

MECHANOCHEMKAL PROCESSING OF GOLD-BEARING SULPHIDES

N.J. WELHAM

Department of Electronic Materials Engineering and Department of Applied Mathematics,


Research School of Physical Sciences and Engineering, Australian National University,
Canberra, ACT 0200 Australia. Email: nicholas.welham@anu.edu.au
(Received 17 October 2000; accepted 4 January 2001)

ABSTRACT

Samples of pure pyrite and arsenopyrite and a gold-bearing pyrite /arsenopyrite concentrate have been
mechanically milled in inert and ox&sing atmospheres. Pyrite was found to be essentially inert with
only slight oxidation to FeSOd eviaknt only after 100 h milling in oxygen. Arsenopyrite completely
oxidised to As203 and FeSO* The milled concentrate was more complex and showed quartz pyrite and
an unidenti~ed phase as the products of milling in oxygen. Leaching of the milled concentrate in 3%
HCl showed 93% dissolution leaving quartz and pyrite as the only phases present. The gold, which was
present only in the arsenopyrite, remained in the solid residue which would be expected to be readily
treated by alkaline cyantdation. Thus, it appears that milling in oxygen allows selective oxidation of
arsenopytite over pyrite providing an alternative, low temperature process for extracting gold from
these types of ore. 0 2001 Published by Elsevier Science Ltd. All rights reserved.

Keywords
Gold ores; sulphide ores; grinding; oxidation

INTRODUCTION

Gold is present in a number of minerals but the most important associations are pyrite and. arsenopyrite. To
extract the gold the host minerals have to be completely destroyed, typically by oxidation using a range of
different techniques (La Brooy et aL, 1994). Roasting is becoming less acceptable and economic due to the
necessity to treat the offgas for SO8 and arsenic, bioleaching is becoming more common but the process has
inbuilt fragility and requires an extremely robust infrastructure for consistent operation (Linge and Welham,
1997b). Any simple process which can oxidise the sulphide without formation of SO2 may prove to be viable
on small deposits where it would be uneconomic to either construct a processing plant or to convey the
concentrate to another processing facility.

Almost all mineral processing plants use mills for the size reduction of particles prior to physical and chemical
processing. Continuation of milling beyond that required for size reduction leads to mechanical activation, the
energy causing a steady-state particle size due to breakage and realloying of particles. The deformation and
damage to the crystal structure leading to increased reactivity, which can be seen directly by reaction within the
mill, subsequent increased solubility, or indirectly, via a decrease in the subsequent temperature required for
reaction. It is a well known phenomenon that wet milling of pyrite in processing plants leads to slight
solubilisation of iron due to the formation of iron sulphate compounds. Thus even industrial milling performs
limited mechanical activation on what is often regarded as the most passive sulphide. It could be expected that
reactions may be induced more readily in more reactive sulphide minerals leading to alternative processing
possibilities.

341
342 N. J. Welham

Whilst much work has been reported on pure metal sulphide minerals, their structure and solubility (see (Balaz,
2000) and references therein) surprising little has been reported on multisulphide concentrates. The situation is
even more sparse when considering concentrates in which the major minerals are not intrinsically valuable but
host valuable metals, such as gold. This paper examines the oxidation during extended milling of pyrite,
arsenopyrite and a concentrate with both present. The subsequent solubility in a weak acid solution is used as
an indicator of the effectiveness of the conditions during milling.

THERMODYNAMIC ASSESSMENT

Figure 1 shows the equilibrium compositions for pyrite and arsenopyrite oxidation with varying oxygen input at
25C. The diagram represents the composition which has the free energy minimum of the system calculated
independently for each starting mixture (Roine, 1994).

2.5

0 10 20 30 40

0, in starting mixture I mol

Fig. 1 Thermodynamic equilibrium compositions at 25C for 10 mol of pyrite or arsenopyrite with
increasing oxygen content of the system.

The initial stage of pyrite oxidation is the formation of elemental sulphur and ferrous sulphate:

Fe& + 202 3 FeSO4 + S (1)

These are then concomitantly oxidised to ferric sulphate

2FeS04 + S + 202 j Fer(SO& (2)

Once this reaction is complete the remaining sulphur is oxidised to SOa.


Arsenopyrite oxidation is a more complex process with the initial oxidation forming As203 and two separate
iron phases, Fe& and FQO~.

8FeAsS + 902 3 4FeSz + 2Fe20s + 4Asz03 (3)

Once the arsenic has been oxidised the Fe& acts as a reductant for both Fez03 and 02 to form ferrous sulphate
which is subsequently reoxidised to ferric sulphate and FQO~.

4FeSz + 2Fez03 + 1302 3 8FeSO4 (4)


Mechanochemical processing of gold-bearing sulphides 343

6FeS04 + 1.502 2 2Fe@O& + Fez03 (5)

Sulphur dioxide is not predicted to occur during the oxidation of arsenopyrite and only occurs after the iron has
been completely oxidised to ferric in the pyrite system.

The same calculations were made at 100C to examine briefly the effect of having an elevated temperature in
the system. Industrial dry mills often operate above ambient temperature due to the high frictional losses
inducing heating, indeed tower mills are known to run at temperatures of up to 200C (Liddell, 2000). For
pyrite the major change was the oxidation of elemental sulphur to SO2 occurred prior to the formation of ferric
sulphate, indeed half of the sulphur dioxide had to be oxidised for this to occur:

2FeS04 + SOZ+ O2 =r Fe2(SO&

Oxidation of arsenopyrite at 100C was identical to that at 25C as shown in Figure 1.

EXPERIMENTAL TECHNIQUE

The pyrite sample used showed no impurity phases from XRD, the arsenopyrite contained small amounts of
quartz. Analysis of a concentrate obtained from a commercial plant showed that it consisted of 63%
arsenopyrite, 21% pyrite and 7% gersdorffite (NiAsS), the remaining 9% was silicate. The concentrate also
contained 128 g f gold.

Samples of each powder were milled for 100 h at room temperature using a laboratory ball mill, the atmosphere
in the mill was inert (argon), air or oxygen, in all cases the mill was evacuated prior to the working atmosphere
being added. Milled concentrate powders were subjected to an agitated leach for 18 h in 3 % HCI at room
temperature to determine whether solubilisation had occurred during milling.

The as-milled powders and the leaching residues were analysed by X-ray diffraction @RD) using
monochromatized Cok, radiation (h=1.78896 A) to give a profile of the phases present before and after
reaction.

RESULTS AND DISCUSSION

Pyrite

The XRD traces for pyrite milled under various atmospheres is shown in Figure 2, from which it is clear that
little reaction occurred with only the sample milled in oxygen showing peaks other than those for pyrite.

On opening this mill the distinct smell of SO;! was noted, chemical tests indicated that some oxidation of the
iron to the ferric state had occurred during milling. This is consistent with thermodynamic predictions shown in
Fig 1 which indicated that complete reaction with oxygen would form iron(m) sulphate and sulphur dioxide
by :

2FeSZ + 702 2 6Fez(SO& + SOz (7)

Monitoring of pressure within the mill indicated decreasing pressure with time which is as expected given the
small fraction of SO2 expected during reaction.
344 N. J. Welham

B FeAsS n As& AFe$,


0

oxygen
n

1.0 20 30 40 50 60 70

20/O

Fig.2 Pyrite milled for 100 h in argon, air or oxygen.

Arsenopyrite

Arsenopyrite was more reactive than pyrite with changes to the structure evident in all atmospheres, Figure 3.
In argon, the two main ueaks for arsenopyrite remain but are substantially broadened indicating crystallite size
refinement which is ty&al of extendA_milling (Welham, 1998a; Welham, 1998b; Welham-and Llewellyn,
1998).

10 20 30 40 50 60 70

20/O

Fig.3 Arsenopyrite milled for 100 h in argon, air or oxygen.


Mechanochemical pmcessing of gold-bearing sulphides 345

There are three new peaks evident (arrowed), however, the phase(s) responsible for these could not be
positively identified due to the breadth of the peaks making their position uncertain. It is, however, reasonable
to say that the peaks are due to decomposition of arsenopyrite. After milling in air, the main arsenopyrite peaks
remain but are substantially weaker and broader than those in the original material. Under an oxygen ambient
the reaction was dramatic with the powder changing colour from black to light grey and Asz03 and FQO~
confirmed as products, as predicted by the thermodynamics shown in Figure 1. No other phases could be
identified as present, although a single, weak peak remained unaccounted for. There was no evidence for
sulphur dioxide on opening the mill suggesting that the ratio of iron to sulphur (1: 1 for arsenopyrite and 1:2 for
pyrite) may play a role in the production of SO,.

It is clear that separation of pyrite and arsenopyrite is possible by milling in oxygen, the arsenopyrite
decomposing and the pyrite remaining essentially unreacted. This has great potential for processing gold
bearing pyritelarsenopyrite ores where selective oxidation of the gold bearing arsenopyrite would liberate the
gold for conventional cyanidation.

Gold-bearing amnopyritelpyrite concentrate

The gold-bearing pyrite - arsenopyrite concentrate was also milled for 100 h in argon, air and oxygen. The
XRD traces for the resultant powders are shown in Figure 4 and the phases identified as present in Table 1.
After milling in air or argon the only phases conclusively present were pyrite and quartz, peaks for other phases
are weak and confirmatory peaks were merged into the background. In oxygen, peaks for As203 were present in
addition to pyrite and quartz, this confirms the oxidation of arsenopyrite had occurred, as expected from the
data for pure arsenopyrite in Figure 3.

60

Fig.4 Concentrate milled for 100 h in argon, air or oxygen.

The remaining peaks for pyrite would suggest that it had not decomposed during milling, as was expected
from Figure 2. The peaks for quartz increased their intensity considerably compared with the other phases
present, eventually dominating the trace for the powder after milling in oxygen. It has been noted in many
systems (Weeber and Bakker, 1988; Gaffet and Harmelin, 1990; Koch, 1990; Shen et aZ., 1995; Welham,
1998b) that softer materials tend to amorphise more rapidly than harder components and the same would
seem to be the case here too.
346 N. J. Welham

TABLE 1 Solubility of gold concentrate powders milled for 100 h in 3 941HU, 18 h agitated leach in
closed vessels. Phases present after mWing and after leaching (qz - quartz, py - pyrite,
or - orthoclase, as - arsenopyrite, tc - talc, su - sulphur, fe - FeS04.6&0 ar -
As2031

Leaching

Table 1 shows that milling of the concentrate under argon for 100 h made a difference to the solubility of the
sulphide. This was presumably due, partially at least, to reduced particle size although some reaction may have
occurred (as for arsenopyrite, Figure 3). The XRD traces of the leached products are summansed in Table 1.
After milling in either argon or air the XRD traces contained a single peak corresponding to the main. peak of
elemental sulphur. The origin of this phase is uncertain with it being possible that it formed during milling, but
was too sparse to be detected by XRD or was a product of leaching, as has been observed elsewhere for
arsenopyrite (Fernandez et al., 1996; Linge and Welham, 1996; Linge and Welham, 1997a) and pyrite (Biegler
and Swift, 1979; Yin et&., 1999).

For the gold concentrate milled in oxygen the solubility was extremely high with only quartz and pyrite
detected by XRD in the leach product, Figure 4. The absence of arsenopyrite in the milled product implies that
liberation of gold had occurred. Furthermore, the absence of gold in the leach solution implies a fourteenfold
increase in gold concentration in the leached solids. The absence of metal sulphides from the system should
enable the liberated gold to be readily treatable by conventional alkaline cyanidation. However, the dissolution
of both sulphides indicates that the system may have been milled for too long and a shorter time may be
appropriate if selective oxidation of the arsenopyrite is sought.

Application

It is reasonable to assume that more reactive minerals will be preferentially oxidised during the early stages of
milling thereby making it feasible to solubilise some minerals but not others by varying the milling time, the
longer the time the more minerals are likely to oxidise. It is feasible that a shorter milling time than the 100 h
used here would give a better separation of pyrite and arsenopyrite. Simply by stopping the milling after the
arsenopyrite had oxidised would allow a simple leach to remove the oxidation products of the arsenopyrite
leaving (for this concentrate) a gold bearing pyrite which would be amenable to alkaline cyanidation. The leach
solution would be treated by oxidising the arsenic(III) to arsenic(V) and precipitating with iron to form ferric
arsenate. However, the apparent oxidation of pyrite in the presence of arsenopyrite under conditions where
alone it showed little reaction implies that there may be a synergistic process occurring in mixed mineral
concentrates. The high stability of pyrite towards mechanically induced oxidation has a potentially huge
application by allowing preferential oxidation of other, more valuable, minerals within a concentrate which
may not be readily treatable by conventional means.

It should be noted that the tumbling type of ball mill used in this investigation is extremely inefficient at energy
transfer and other types of mill (e.g. planetary, vibratory, stirrer ball) could be expected to produce the same
results in a shorter milling time. A model based on number of ball impacts per gramme of powder has indicated
a vibratory mill would be around 300 times faster (Welham, 2000) than the mill used here. A more exacting
model, accounting for differing ball masses and velocities, has indicated that vibratory mills may be -1000
times faster than ball mills (Maurice and Courtney, 19%), a further improvement has been reported for stirred
mills (Warris and McCormick, 1997).
Mechanochemicalprocessingof gold-bearingsulphides 347

CONCLUSIONS

The data presented here indicates that mechanical activation by milling can induce different reactions in
different sulphide minerals. These reactions which occur under ambient conditions lead to high solubilities of
some metal sulphide minerals but less solubility in others. In oxygen pure pyrite underwent only slight
oxidation whereas arsenopyrite was completely oxidised with no apparent evolution of SOZ. A gold-bearing
arsenopyrite / pyrite concentrate where the gold was entirely within the arsenopyrite was also processed. After
milling in oxygen, the gold content of the acid insoluble residue was approximately fourteenfold than the
starting concentrate. The residue consisted of quartz and pyrite, neither of which is a significant problem during
alkaline cyanidation. The absence of SO2 from the oxidation of sulphide minerals makes this processing route
of potential value in deposits which are conventionally treated by thermal processes.

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