SULFIDE/BISULFIDE/SULFITE

LEACHING
Of these possible lixiviants only the bisulfide and bisulfite ions appear to
have any practical use under ambient conditions.
YES Technologies described a process using bisulfide generated from
sulfate reducing bacteria as a lixiviant for gold, although bisulfide ions
can readily be generated from hydrogen sulfide gas.

PROCESS CONDITIONS
The mechanism of gold dissolution and precipitation from aqueous sulfide
solutions under a range of conditions has received considerable attention in
the early geological literature (e.g. Hanninton and Scott, 1989; Seward,
1973; Tan and Bell, 1990). Neutral bisulfide solutions dissolve gold as follows:

Under weak acid conditions the gold complex, [Au(HS)] 0 forms, whilst under
strongly alkaline conditions, [Au2(HS)2S] 2- is formed (Seward, 1973).
Because of the similar stabilities of gold and silver bisulfide complexes,
bisulfide leaching may be suitable for leaching gold ores with a significant
silver content (Hunter et al., 1998).

PROCESS CONDITIONS

PROCESS CONDITIONS
Conventional bio-oxidation of ore particles is carried out to free the
precious metals dispersed or occluded within the ore. A portion of the
acidic, base metal sulfate leach solution produced from bio-oxidation is
introduced to an anaerobic reactor.
A non-toxic donor such as acetate or methanol (which does not bind to
activated carbon) is added to the anaerobic reactor to enrich within it a
mixed culture of sulfate-reducing bacteria.

PROCESS CONDITIONS
Bisulfide ions are generated biologically in the process with an electron
donor such as acetate by the following the reaction:

Additions of acidic sulfate solution may be required to maintain a neutral

pH in the reactor.
In a second process step, the oxidised ore (covered and submerged to
exclude oxygen) is leached by recirculating the neutral bisulfide lixiviant
saturated with H2S.
Precious metals are recovered from the pregnant bisulfide solution by
contact with activated carbon or other conventional techniques.

NITROGEN SPECIES CATALYSED

PRESSURE LEACHING PROCESS
Developed at Montana Tech, the sulfur residue is converted into a gold
extracting lixiviant (Anderson, 2003). The principles of the reaction of a
sulfide mineral with nitric acid in conjunction with sulfuric acid are shown
below. It is postulated that the actual reaction species is NO+, and not
NO3- which reacts with the mineral and oxidises the sulfide to sulfur at an
Eh of around 1.45V (vs SHE).

NITROGEN SPECIES CATALYSED

PRESSURE LEACHING PROCESS
By partially oxidising the sulfide to elemental sulfur instead of sulfate, the
gold can be accumulated in the elemental sulfur, recovered from the
other leached solids, and then leached via alkaline sulfide lixiviation
whereby the sulfur containing the gold is dissolved in an alkaline solution.
The combination of sodium hydroxide and elemental sulfur results in the
formation of sulfide (S2-), sodium polysulfide (Na2SX) and sodium
thiosulfate (Na2S2O3) as follows:

APPLICATIONS AND
LIMITATIONS
Bisulfide leaching is clearly more applicable to sulfidic ores rather than
oxidised ores.
The operating costs considering detoxification, however, would be very
high, because a high chemical oxygen demand would again be necessary.
One of the limitations would seem to be the sole suitability of this process
for bio-oxidised ore, because a sulfate ion source is required for bisulfide
regeneration. This process is recyclable, but theoretically an oxidation to
sulfate would also be possible, although this again would be expensive.

APPLICATIONS AND
LIMITATIONS
Compared to cyanide, bisulphide does not offer any major technical
advantages nor does it have such favourable lethal toxicity and
ecotoxicity data to warrant a more favourable classification with regard to
safe handling or environmental damage in the case of a spillage.

APPLICATIONS AND
LIMITATIONS
A major drawback is that H2S, which is also generated, has an
occupational health standard very similar to HCN. Extremely long
retention times and a closed system would be required. It would also lead
to the economic viability being much less favourable than that of cyanide.
This may be the main reason why no large scale application has ever
existed.
The nitrogen species catalysed pressure leach process is less hazardous
and has been successfully demonstrated at laboratory scale on silver
ores. Further investigations on treating gold ores are required. The
process is most probably better suited for the extraction of multielemental systems such as base and precious metals.

AMMONIA LEACHING
Ammonia is most commonly used as an additional reagent in cyanidation
for copper-containing ore bodies. However the laboratory use of ammonia
as a lixiviant for refractory gold ores athigh temperatures has been
reported.

PROCESS CONDITIONS
The use of ammonia is more commonly known as an additional reagent in
cyanidation for copper-containing orebodies.
Ammonia leaching of gold in the presence of an oxidant is carried out at
temperatures between 100 and 300 C and 600-1000 kPa of pressure using 5-10
g/L copper(II) as oxidant, 5.5M free ammonia and 0.5M ammonium sulfate.
Leaching times are short, around 1 to 4 hours. At ambient temperatures gold is
passivated and gold dissolution in ammonia solutions is observed only above
80C (Meng and Han, 1993). The most effective oxidant for gold dissolution
inammoniacal solutions is Cu(II) as represented in the following reaction (Guan
and Han, 1996):

PROCESS CONDITIONS
Alternative and less effective oxidants include oxygen,
hypochlorite, peroxide and Co(III). The oxidation of sulfides in the
ore produces some thiosulfate which complicates the leaching
process. The use of combined halogen and ammonia as a gold
leaching process has also been examined. High gold recoveries are
achieved at <100oC with iodine providing the best oxidant in terms
of the rate of dissolution of precious metals (Han, 2001).

PROCESS CONDITIONS
Iodine, I2 is a very effective oxidant (Peri et al., 2001) where gold can
react with ammonia in the presence of iodine as an oxidant to form goldammine.

One of the advantages of such a reaction is the ability to regenerate

iodine by reaction with oxygen. However no applications on the use of
iodine as an oxidant have been published.

APPLICATIONS
Sulfidic and carbonaceous refractory ores have been successfully treated
by the ammonia process (Han and Fuerstenau, 2000) with >95% gold
extraction achieved in 2 to 4 hours compared with <70% by conventional
cyanidation.
The availability of ammonia and its price, however, would not be a
restriction. Ammonia would have to be recycled and could not be
detoxified easily. This reagent may even be suitable for most ore types,
but not be selective with regard to leaching especially for copper-bearing
orebodies. This is due to the formation of copper tetraamine from most
copper minerals.

CURRENT STATUS
The capital and operating costs are the limiting factors in the
implementation of this process, since high pressures and temperatures
are required. Consequently it would only be viable in isolated cases (e.g.
spent catalysts or very high grade concentrates).
Ammonia may eventually be broken down to nitrate in the environment
by bacterial oxidation, but this is a slow process. However, the economic
viability seems to be the limiting factor in this process not having found
any large scale application to date.