A theoretical study of SART

precipitate generation:
Operational and safety impacts

SART (Sulphidization, Acidification, Recycling and Thickening) process is a Humberto Estay, Pablo Carvajal,
Karina González and Verónica
cyanide recovery technology currently installed in different gold cyanidation
Vásquez. Arcadis, Chile
plants around the world. This technology reduces the operational costs by
recovering cyanide and increases the income through the production of a
copper precipitate. The literature has reported that the precipitate is mainly
Cu2S and, consequently, the engineering design of SART plants have been
based on this fact. However, the experimental and operational results avail-
able, such as the required dosage of reagents and the observed copper grade
in the precipitates, introduce doubts about the correct characterization of the
copper precipitate. These results suggest the formation of other species
different from Cu2S, which then bias the true estimation of reagents dosage
and the selection of the safety criteria needed in the drying and storage
facilities. The present work applies thermodynamic modeling to identify
theoretically formation of the species CuS in the precipitate, as a function
of the operational conditions. This paper proposes the use of a 120% NaHS
stoichiometric addition based on Cu2S in order to obtain copper recoveries
around 90%; however, NaHS dosages above 120% stoichiometry increases the
NaHS consumption without increasing copper recovery. Furthermore, the
presence of oxidation reactions in the stored precipitate promotes the ability
to undergo spontaneous combustion under certain conditions. Therefore,
the inclusion of safety criteria in the storage facilities must be incorporated
in the design and operation of sart plants in order to minimize hazardous
situations in the facilities.

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INTRODUCTION

Description of SART Process

The SART process (Sulphidization, Acidification, Recycling, and Thickening), illustrated below in
Figure 1, is a technology currently incorporated in the cyanidation circuit by some gold mining
operations in order to reduce the cyanide consumption associated to the processing of ores with
high cyanide-soluble copper content.
The process begins with the Acidification and Sulphidization of the feed solution according to
equation (1) and (2) by adding sulphuric acid (H2SO4) and sulphide (in the form of NaHS or Na2S),
producing precipitation of copper sulphide (Cu2S) in the precipitation reactor, among that other
cations present in the solution (Estay et al., 2012). The hydrogen cyanide generated remains
dissolved in the solution (MacPhail, Fleming & Sarbutt, 1998).

Figure 1 Schematic block diagram of the SART process

2CN − + H 2 SO4 → 2 HCN (ac) + SO4−2 (1)

(2)
2Cu (CN ) 3−2 + S −2 + 6 H + → Cu 2 S ( s ) + 6 HCN (ac )

The solids formed in the precipitation reactor are removed from the process by sequential stages of
thickening, filtration, and drying, while the treated solution is neutralized by adding milk of lime
which produces the conversion of dissolved HCN into calcium cyanide (Ca(CN)2) and precipitation

154
of gypsum (CaSO4*2H2O) (Barter et al., 2001). Finally, the solution produced by the SART process is
put back into the leaching circuit, having all of its cyanide content as soluble Ca(CN)2, which is
equivalent to free cyanide for the purposes of gold dissolution in the cyanidation process
(MacPhail, Fleming and Sarbutt, 1998).

Precipitate characterization
The literature has reported that Cu2S is the main species formed in the precipitation stage of the
SART process (MacPhail, Fleming & Sarbutt, 1998; Barter et al., 2001; Estay, Arriagada & Bustos,
2010). However, the experimental and operational data suggest that other species may be the
reaction product. There are three issues which indicate the possible formation of others species, as
follows:
1. The typical copper grade in the SART precipitate is around 65% (Ford, Fleming & Henderson,
2008; Estay et al., 2012), almost 15% lower than the stoichiometric relation of Cu2S (79.9%). In
fact, the precipitation of other cations contained in solution such as zinc, nickel, and silver can
not explain the difference of copper grade between operational results and the expected value
given by the stoichiometric relation.
2. The operational data indicate that the copper recovery in the SART process varies between 90%
and 95% when the NaHS addition is 120% stoichiometric based on copper (Estay et al., 2012;
Estay, Arriagada & Bustos, 2010). Precipitation of Cu2S (equation 2) is very fast and determined
by thermodynamic equilibrium, therefore the excess of NaHS addition ought to be explained by
the generation of other species.
3. Finally, current SART operating plants have encountered exothermic reactions (T. Van Zeller,
2012, pers. comm., 04 November) that could promote spontaneous combustion of precipitate
bags, after a period of storage. The characterization of the precipitate in this connection is very
relevant since Cu2S has a self-ignition point higher than 400°C.
These results are taken to indicate that in the precipitate there are species not considered to date,
which could be formed in the precipitation stage, such as CuS or S. This study analysed the
thermodynamic equilibrium in the system to assess the generation of CuS and S species, in addition
to the main reactions occurring in the SART precipitation stage. Furthermore, the results of the
theoretical model are compared with the literature in order to identify the nature of these
spontaneous combustion events.

METHODOLOGY
The theoretical study for characterization of the precipitate in the SART process involved the
following steps:
1. Review of experimental and operational data to establish the facts about the true
characterization of the SART precipitates.
2. Establish the main chemical reactions that could be involved in the precipitation reactor of the
SART process.
3. Conduct a literature survey of equilibrium constants to build the thermodynamics model.
4. Construction and testing of the thermodynamics model.

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5. Conduct a literature study regarding the spontaneous combustion of sulphide concentrates.
6. Analyse the thermodynamics model results.

RESULTS AND DISCUSSION

Theoretical model
The theoretical model developed in this work is based on the following reactions, which could
occur during the precipitation stage:

+ ↔ ( ), (3)

( )+ ↔ ( ) , (4)

( ) + ↔ ( ) , (5)

( ) + ↔ ( ) , (6)

+ ↔ ( )+ + , (7)

2 + ↔ ( )+ , (8)

↔ ( )+ +2 , (9)

+ ↔ , (10)

+ ↔ , (11)

Thus, the solid species which could form in the precipitation stage are CuCN, CuS, Cu2S and S. The
feed solution could contain cations in low concentration (<10 mg/L) such as zinc, cadmium, nickel,
and silver, which can precipitate. These cations however have not been considered in this present
model.
The model relates the thermodynamic equilibrium equations of each chemical reaction and the
mass balance for cyanide, copper and sulphide to obtain a mathematical model describing the

156
speciation in the solid-liquid equilibrium, as a function of pH. The model has been constructed in
Matlab®. The equilibrium constants of equations (3-11) are presented in Table 1.

Table 1 Equilibrium constants values for Equations 3-11 at 25°C

logKi Value Source

logKCu1 20 Lu, Dreisinger & Cooper, 2002
logKCu2 3.94 Izzat et al., 1967
logKCu3 5.3 Izzat et al., 1967
logKCu4 1.5 Izzat et al., 1967
logKCuS 19.52 Zhang, Fang & Muhammed, 1997
logKCu2S 34.6 Zhang, Fang & Muhammed, 1997
logKS 2.2 Zhang, Fang & Muhammed, 1997
logKH2S 7.02 Zhang, Fang & Muhammed, 1997
logKHCN 9.21 Izzat et al., 1962

Simulations were conducted by considering a hypothetical cyanide solution containing 500 mg/L
Cu and 800 mg/L CN-, treated with NaHS dosages of 80, 100 and 120% stoichiometric based on
Cu2S during the precipitation stage, at different pH values. The copper species distribution results
obtained by the model are shown in Figures 2, 3 and 4 below.
The SART process operates in the pH range of 4 to 5. According to the results of the model, CuS
may be present in the precipitate at pH 5, which has 2, 15 and 36% of copper for 80, 100 and 120%
stoichiometric NaHS addition, respectively. That is, the increase in the sulphide/copper ratio
increases the stability range of CuS in the precipitate. On the other hand, a limited sulphide content
produces CuCN at pH lower than 4, increasing the stability of Cu(CN)2- species at pH 5, which
reduces copper recovery in the SART process. Elemental sulphur is not present for pH lower than 6,
and H2S is present for 120% stoichiometric NaHS addition at pH lower than 4. Hence, from the
thermodynamic standpoint, CuS could be present in the precipitate depending on the process
conditions (solution characterization, sulphide addition and pH).

100

90

80
%Cu Cu+
Cu distribution, %

70
%Cu CuCN
60 %Cu Cu(CN)2

50 %Cu Cu(CN)3
%Cu Cu(CN)4
40
%Cu CuS
30 %Cu Cu2S
20

10

0
0 2 4 6 pH 8 10 12 14

Figure 2 Copper species distribution for cyanide solution containing 500 mg/L Cu, 800 mg/L CN- and 80% of
NaHS stoichiometric addition (176.4 mg/L NaHS) based on Cu2S

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 100

90

80 %Cu Cu+

Cu distribution, %
70 %Cu CuCN

60 %Cu Cu(CN)2
%Cu Cu(CN)3
50
%Cu Cu(CN)4
40
%Cu CuS
30 %Cu Cu2S

20

10

0
0 2 4 6 pH 8 10 12 14

Figure 3 Copper species distribution for cyanide solution containing 500 mg/L Cu, 800 mg/L CN- and 100% of
NaHS stoichiometric addition (220.5 mg/L NaHS) based on Cu2S

100
90

80 %Cu Cu+
Cu distribution, %

70 %Cu CuCN

60 %Cu Cu(CN)2
%Cu Cu(CN)3
50
%Cu Cu(CN)4
40
%Cu CuS
30 %Cu Cu2S

20

10
0
0 2 4 6 pH 8 10 12 14

Figure 4 Copper species distribution for cyanide solution containing 500 mg/L Cu, 800 mg/L CN- and 120% of
NaHS stoichiometric addition (264.6 mg/L NaHS) based on Cu2S

The formation of CuS in the precipitate explains in part (0.5 to 5.5 points of % from the typical
difference of about 15%) the copper grade reported in the The remaining 10 points of % can be
explained by co-precipitation of zinc, nickel, silver o cadmium. It also explains the excess of NaHS
addition required to obtain copper recoveries higher than 90%. Actually, the effective stoichiometric
addition depends on the ratio of CuS and Cu2S generated; thus, when CuS formation is increased
the sulphide consumption increases. Hence, a 120% NaHS stoichiometric addition based on Cu2S
ensures copper recoveries higher than 90%, while NaHS dosages above 120% stoichiometric are not
recommended since the additional sulphide will be consumed to form CuS without increasing
copper recovery. This trend was confirmed by additional simulations conducted above 120% NaHS
stoichiometric (results not shown).

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The model can predict the copper recovery obtained in the precipitation stage, according to the
solution speciation and pH. Therefore, it can be a useful tool to predict the copper recovery as a
function of NaHS addition.

Spontaneous combustion risk

It is well known that spontaneous combustion of sulphide concentrate is a common phenomenon
under favourable conditions (Yang et al., 2011). The ability of sulphide concentrates to undergo
spontaneous combustion has been investigated (Yang et al., 2011; Yang, Wu & Li, 2011; Payant et
al., 2012; Yang & Wu, 2013). These authors studied the activation energy of spontaneous
combustion in storage yards for different sulphide concentrates, suggesting that the mechanisms
that can promote self-heating may be oxidation reactions, galvanic interactions, mechanical
activation, among others.
According to the results of the thermodynamics model, the characterization of the SART precipitate
is basically Cu2S with the presence of CuS, depending on the process conditions. Even when the
results of some researches indicate that copper sulphide concentrates are less susceptible to
spontaneous combustion at room temperature than iron sulphide concentrates or sulphur-rich
concentrates (Yang et al., 2011), there are experiences in current operating SART plants reporting
self-heating of precipitates in the storage area.
The occurrence of oxidation reactions can be expected when the sulphide concentrate is stored for a
period of time, releasing heat. If the rate of heat generation in the sulphide concentrate storage area
exceeds that of heat removal from the boundaries, the accumulated heat rises the temperature
producing the oxidizing reaction to accelerate up to the self-ignition point (Zarrouk & O’Sullivan,
2006).
Therefore, future studies should be focused on confirming the causes of spontaneous combustion,
i.e. CuS effect, energy activation, contact area of species, oxidation reactions, among others.
In summary, the SART precipitate as a sulphide concentrate can, under certain conditions, suffer
spontaneous combustion. This fact forces to include important safety criteria in the storage
facilities, such as to avoid large quantities of precipitate stored for extended periods, minimize air
contact, avoid the natural dried and to include the necessary installations to ensure a safety area,
such as fire protection system and a proper handling of the bags.

CONCLUSION
The precipitate formed in the SART process was characterized from a theoretical point of view. The
thermodynamics solid-liquid equilibrium suggested the formation of CuS in addition to Cu2S, its
content being dependent on the operational conditions. It is concluded that copper recoveries of
90% can be reached using 120% NaHS stoichiometric addition based on Cu2S; however, NaHS
dosages above 120% stoichiometric could only consume sulphide to form CuS without increasing
copper recovery.
There is no evidence in the literature about the effect of CuS on promoting self-heating. In this
context, future studies should be focused on confirming the causes of spontaneous combustion.
However, the fact of self-heating of SART precipitate forces the inclusion of safety criteria in the

159
storage facilities, which will be incorporated in the design and operation of SART plants, in order to
minimize the risk in the facilities as well as in personnel.

REFERENCES
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