Alkaline Sulfide Recovery of Gold
Alkaline Sulfide Recovery of Gold
Alkaline Sulfide Recovery of Gold
Abstract
Over the past 15 years, numerous pressure oxidation plants for pretreatment of gold ores and
concentrates have been installed throughout the world. While this technology is now
established, it suffers in terms of the complex engineering and operational characteristics
inherent in utilization of high temperatures (i.e. up to 225oC) and high pressures (i.e. > 3000
kPag). This paper outlines the application of an industrially proven pressure leaching
methodology utilizing nitrogen species catalyzed pressure leaching and alkaline sulfide gold
leaching. As such, it stands as an economic and engineering advancement in pressure leaching
and non-cyanide treatment of gold ores and concentrates. In particular, the technology offers
significant technical and economic advantages over traditional pressure oxidation and cyanide
gold recovery in the treatment of gold bearing chalcopyrite ores and concentrates. An example
of this will application will be delineated in this paper.
Introduction
The use of nitric acid in metal sulfide oxidation is not new. Many derivations of the technology
have been researched and piloted [1,2,3,4]. However, as noted in Table I only the nitrogen
species catalyzed (NSC) acid pressure leach has ever been built and operated successfully on an
industrial scale [3]. Table II illustrates the comparative operating criteria for these technologies
as well as some selected conventional pressure oxidation gold plants. As seen, NSC is
advantageous over that others in that it is faster, uses lower temperatures, uses lower pressures,
uses a small amount of nitrogen species regenerated in-situ and uses unlined 316L stainless
steel autoclave.
NSC 125-170o C 625-975 kPag 2-3 g/L In-situ 15-45 Stainless steel
REDOX 85-95o C Atmospheric 140-180 g/L External 60 Titanium
REDOX 195-210o C 1950 kPag 70-110 g/L External 15 Titanium
NITROX 85-95o C Atmospheric 100-150 g/L External 60 Stainless steel
McGlaughlin 180o C 2200 kPag None just O2 None just O2 90 Lead/ acid brick
Sao Bento 190o C 1600 kPag None just O2 None just O2 120 Lead/ acid brick
Goldstrike 225o C 3000 kPag None just O2 None just O2 75 Lead/ acid brick
Getchell 210o C 3200 kPag None just O2 None just O2 90 Lead/ acid brick
In order to understand the advantages of NSC pressure leaching, it is important to review the
principles behind it. The commonly reported leach reaction of a sulfide mineral with nitric acid
in conjunction with sulfuric acid is shown below:
However, it is postulated that the actual reaction species is NO+ and not NO3- .The addition of,
or presence of, NO2- instead of NO3- accelerates the formation of NO+ [4-6]. As seen in Table
III [7], the NO+/NO couple is capable of an extremely high redox potential of about 1.45 V
relative to hydrogen. The NO+ then reacts with the mineral and oxidizes the sulfide to sulfur.
2 MeS (S) + 4NO+ (Aq) 2Me+2 (Aq) + 2So + 4NO (G) (2)
Since the nitrosyl ion is continuously regenerated, its role in the overall reaction as the actual
oxidizer is not obvious. The net overall reaction has the sulfide mineral reacting with the acid
solution and oxygen to solubilize the metal value into the sulfate solution and form elemental
sulfur (at low temperatures and/or low nitrogen species concentrations):
E0H
Oxidant Redox Equation (pH = 0, H2 ref.)
Fe+3 Fe+3 + e- Fe+2 0.770 V
HNO3 NO3- + 4H+ +3e- NO(g) + 2H2O 0.957 V
HNO2 NO2 - + 2H+ + e- NO(g) + H2O 1.202 V
O2 (g) O2 + 4H+ + 4e- 2H2O 1.230 V
Cl2 (g) Cl2 (g) + 2e - 2 Cl- 1.358 V
NO+ NO+ + e- NO(g) 1.450 V
As can be seen, nitric oxide gas, NO, is produced from the oxidation of sulfides. As this gas
has a limited solubility in aqueous solutions, it tends to transfer out of solution. The nitric oxide
gas emanating from the leach slurry accumulates in the headspace of the reactor where it reacts
with the supplied oxygen to form nitrogen dioxide gas, which reacts further to regenerate.
Overall, the nitrogen intermediates serve as an expedient means to transport oxygen to the
surface of the solid particle and allow the resulting reaction to take place at a heightened redox
potential. Complete oxidation of sulfide to sulfate can be achieved without the excessive
conditions found in other pressure leach systems.
An example of the NSC complete sulfide oxidation process application to gold is listed in
Tables IV, V and VI. In this case, the sulfides are completely oxidized to sulfate due to high
temperatures and long leaching times used. The gold is recovered via conventional carbon in
leach cyanidation of the leached solids.
Table IV.-Assay of Gold Concentrate Treated With Complete NSC Sulfide Oxidation
Another potential methodology with this technology is the partial oxidation of the sulfide to
elemental sulfur instead of sulfate. In this case, a lower temperature is used and subsequently
less oxygen is consumed. As currently experienced in other industrial systems, the majority of
the gold tends to accumulate in the elemental sulfur that is produced [8-10]. As practiced in
industry, this product can be readily screened or floated away from the other leached solids.
Then, the gold can be leached via alkaline sulfide lixiviation whereby the sulfur containing the
gold is dissolved in an alkaline solution. To better illustrate this, Figure 1 [11] shows the
equilibrium sulfur system while Figure 2 [12] shows the meta stable species sulfur system. In
reality, the species shown in Figure 2. dominate as the alkaline sulfide system is slow to reach
equilibrium .
The combination of sodium hydroxide and elemental sulfur results in the formation of species
other than just sulfide (S-2). Both sodium polysulfide (Na2SX) and sodium thiosulfate (Na2S2O3)
are created along with sulfide. This illustrated simplistically in the following scenario:
Initially gold lixiviation was thought to be the result of leaching by polysulfides and
thiosulfates:
25
50 g L-1 sulfide
20
I / A m -2
Current
15
50 g L-1 bisulfide
10
5
50 g L-1 polysulfide
0
-600 -500 -400 -300 -200 -100 0
Potential
E / mV
Figure 3: REQCM Reverse potential sweeps and calculated current for potential lixiviants at a
concentration of 50 g L-1 and at a temperature of 30°C
Figure 3 shows a comparison of sulfide, bisulfide and polysulfide as potential lixiviants for the
alkaline sulfide system. The large calculated current for sulfide in comparison to those of
bisulfide and polysulfide, suggests that sulfide is the dominant lixiviant of the system, and that
bisulfide and polysulfide are poor lixiviants. The actual leaching occurring in the polysulfide
and bisulfide system may be attributable to the presence of some sulfide in equilibrium with the
bisulfide and polysulfide. A number of ligands form stable compound with the aurous cations,
including sulfide and bisulfide. From the data below it can be seen that sulfide forms a more
stable complex with gold than bisulfide as shown by the larger stability constant, confirming
what was seen experimentally.
Thus, the reduction of polysulfide when acting as an oxidizer may be represented by the below
half reaction:
SX2- + 2(x-1)e- xS2- (12)
For a polysulfide with x equals 2:
S22- + 2e- 2S2- (13)
Thus, assuming that sulfide is the complexing lixiviant and polysulfide (S22-) the oxidant, the
overall reaction can be written as:
Further, a novel gold recovery method has been adopted to quantitatively and selectively
recover leached gold from complex alkaline sulfide solutions. This is illustrated by selectively
removing gold from an alkaline sulfide leach solution containing impurities such as Hg, As, Sb
and Sn, which are the only other possible elements soluble in this lixiviant. The assay of the
solution tested is shown in Table IX and the assays of the final products are shown in Table X.
The overall results are presented in Table XI.
Volume L Au Sb As Hg Sn
0.5 88.7 ppm 21.0 g/L 5.31 g/L 274 ppm 1.84 g/L
Volume, L Au Sb As Hg Sn
0.5 1.5 ppm 21.1 g/L 5.21 g/L 274 ppm 1.89 g/L
Liquid Solid
Gold 1.7% 98.3%
Antimony 100.0% 0.0%
Arsenic 100.0% 0.0%
Tin 100.0% 0.0%
Mercury 100.0% 0.0%
Finally the alkaline sulfide solutions, which are barren of gold, can be recycled for further gold
leaching or further processed with low temperature oxidation to sodium sulfate, Na2SO4. This
has been routinely practiced in industry [16]. The resultant sodium sulfate is further treated by
purification and crystallization to produce high grade, marketable sodium sulfate. This process
is illustrated simplistically in the following scenario:
This versatile and environmentally benign chemical is then sold and utilized in industries such
as pulp and paper, glass, ceramics, detergents, mineral feed supplements, textile dyes, bleach
and photography. As such, there are no environmental or toxicological issues in the use of
alkaline sulfide gold recovery because the waste products become value-added, marketable by-
products.
Moreover, NSC partial sulfide oxidation pressure leaching followed by alkaline sulfide gold
leaching and recovery is an advantageous application for treatment of copper sulfide gold ores
and concentrates. First of all, primary sulfide copper ores and concentrates such as chalcopyrite
can be effectively treated at low temperatures and pressures. Then, the sulfur produced can be
used to directly leach and recover the gold. This is particularly advantageous in that it avoids
the large reagent consumptions found when treating copper ores and concentrates with cyanide.
The following example illustrates the treatment of a gold bearing chalcopyrite ore [17].
500 tonnes per day of a gold bearing chalcopyrite ore has been proposed to be treated by NSC
partial sulfide oxidation pressure leaching followed by SX-EW production of copper. The gold
will be recovered via alkaline sulfide leaching followed by electrowinning. Table XV illustrates
the plant conditions utilized while Table XVI shows result of NSC partial sulfide oxidation on
the chalcopyrite concentrate. Table XVII delineates the site-specific economics of the
application for treatment of the chalcopyrite ore. Figure 4 illustrates the proposed flowsheet. A
key aspect here is to minimize sulfide oxidation to elemental sulfur. This minimizes oxygen
consumption, reduces in-situ acid production and the closed circuit process causes in-situ iron
precipitation. This limits the amount of iron and acid build up in the process circuit thereby by
limiting amount of the circuit impurity bleed stream. As well, the elemental sulfur produced,
acts as a non-cyanide lixiviant for gold in the alkaline sulfide recovery system. Another key
aspect is that the solutions recycled do not buildup nitrates or nitrites, which could be damaging
to the solvent extraction reagents. Continuous closed circuit testing and analysis of the
flowsheet has consistently shown both nitrogen species solution concentrations of less than 0.1
ppm. Thus, by in-situ methods, the closed circuit NSC system does not allow any buildup of
nitrogen species in the recycled solutions, which may be harmful.
Both sulfuric acid generation and iron dissolution are minimized along with
production of elemental sulfur to be utilized in non-cyanide gold recovery.
NSC Chalcopyrite Partial Oxidation Operating Cost = $0.056 USD/lb Cu or $ 0.36 USD/g Au
Chalcopyrite ore.
3.2% Cu, 4.1% Fe, 5.7% Tot. S, 11g/T Au
Moreover, the relative economics of the NSC pressure oxidation methodologies are better than
that of conventional pressure leaching. This is illustrated by an order of magnitude economic
analysis of various pressure oxidation pretreatment options subject to the following:
Operating costs are expressed as dollars per % contained sulfide in the concentrate being
oxidized. Based on this, the order of magnitude capital and operating costs for NSC compared
to conventional pressure leaching are summarized in Tables XVIII and XIX.
USD/% Contained
Type of Process Sulfide Oxidized d
Finally, the relative reagent costs of sodium cyanide versus alkaline sulfide produced from
sulfur are illustrated in Table XX. This does not include the by-product revenues available
when using the alkaline sulfide system or the costs associated with destruction of waste
cyanide. Thus, as seen, there are significant economic incentives with the use of alkaline
sulfide leaching of gold instead of cyanide. This advantage was illustrated before in the
treatment of gold bearing chalcopyrite where conventional pressure leaching followed by
cyanidation is far more expensive.
In summation, the NSC pressure oxidation system offers several definitive and industrially
proven advantages. First it is the only proven industrial process for pressure leaching of
precious metal bearing sulfides. Second, the rate of reaction is much faster and the required
reactor volume is thus smaller. Third, the process does not require excessively high
temperatures or pressures. Fourth, the solution potential is extremely high so it oxidizes almost
any sulfide at low oxygen overpressures. Fifth, the materials of construction are readily
available stainless steels, so there is no need for titanium, cladding or brick with lead liners.
Thus, the capital and maintenance costs are less. Also, because of the simpler internal design,
direct heat exchange can be utilized in-situ for optimal temperature control. Further, in a
manner analogous to existing Ni/Co laterite HPAL systems, the energy from the in-situ heat
exchange can be readily utilized for optimizing the plant heat balance or co-generating
electrical power resulting in significant process operating cost savings. Sixth, there is no need
for a dip tube or special design radial agitators with cowlings. Oxygen transfer is innate with
the enhanced nitrogen species chemistry. So, with no titanium, and no titanium dip tube in
particular, there is much less oxygen fire danger. Seventh, the design of the feed pump system
is far less of a challenge as is the flash system and the choke system. Eighth, like a smelter,
precious metals recovery can be high and direct. Ninth, there are no sophisticated chloride
chemistries or resultant corrosion issues to deal with. Tenth, sulfur production and materials
handling is readily accomplished. Further, any elemental sulfur that is produced can be used as
a cost effective lixiviant for gold production and waste streams from this can be further
processed to produce value added by-product sodium sulfate. Finally, there is both a minor
amount of nitrogen species utilized, which can be controlled by commercially available systems
so there are no major economic or environmental issues.
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