Minerals Engineering 22 (2009) 111115

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Kinetics of high-sulphur and high-arsenic refractory gold concentrate oxidation

by dilute nitric acid under mild conditions
Guolong Gao a, Dengxin Li a,*, Yong Zhou a, Xianhao Sun b, Wen Sun c
a
College of Environmental Science and Engineering, Donghua University, 2999 North Renmin Road, Songjiang District, Shanghai 201620, China
b
Jining Institute of Architectural Design, Jining 272125, China
c
Jining Metrological Measuring Institute, Jining 272125, China

a r t i c l e i n f o a b s t r a c t

Article history: On one hand, high-sulphur and high-arsenic refractory gold concentrate (HGC) leads to regional ecolog-
Received 19 December 2007 ical damage. On the other hand, it contains a lot of valuable elements. So utilization of it can bring social
Accepted 8 May 2008 and environmental benets. In this paper, the kinetics of HGC oxidation by dilute nitric acid under mild
Available online 16 June 2008
conditions was investigated. The effects of particle size (50335 lm), reaction temperature (2585 C),
initial acid concentration (1030 wt.%) and stirring speed (400800 rpm) on the iron extraction rate
Keywords: (Cr) were determined. It is obvious that Cr increases with the rise of initial nitric acid concentration, reac-
Gold ores
tion time and stirring speed, but decreases with the increase of particle size. Oxidation kinetics indicates
Reaction kinetics
Oxidation
that the rate of reaction is diffusion controlled. The activation energies were determined to be 10.70 kJ/
Mineral processing mol in the 10% HNO3 and 12.25 kJ/mol in the 25% HNO3.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
The resources of high-sulphur and high-arsenic refractory gold
concentrate (HGC) are abundant and can be found in many areas
in China, such as Guizhou, Guangxi, Jiangxi and Yunnan provinces.
Because air and water was introduced into the stratum, HGC was
oxidized spontaneously and released acids and many heavy metals
such as As, Pb, Zn and so on. Meanwhile, the obtained acids can
accelerate the dissolution of the minerals around them and lead
many chemicals into water. Therefore, HGC leads to regional eco-
logical damage. On the other hand, it contains a lot of valuable ele-
ments, such as Au, Ag. So utilization of it can bring economical and
environmental benets.
The gold in HGC is encapsulated as ne grained particles in the
crystal structure of the mineral matrix, which renders the metal
inaccessible to the leaching agent (Abrantes and Costa, 1996; Ubal-
dini et al., 1997; Karamanev et al., 2001). To achieve a satisfactory
recovery, an oxidative pretreatment stage is required to break
down or at least to modify the sulphide matrix and release the pre-
cious and base metals before applying any conventional treatment
(Climo et al., 2000). These pretreatment methods include roasting
(Dunn and Chamberlain, 1997), pressure oxidation (Gudyanga
et al., 1999), bio-oxidation (Gonzalez et al., 1999; Deng and Liao,
2002; Miller and Brown, 2005) for high leaching rate of HGC. The
contents of sulphur and arsenic are high, so traditional roasting
* Corresponding author. Tel.: +86 21 677 92541; fax: +86 21 677 92522.
E-mail address: lidengxin@dhu.edu.cn (D. Li).
process would release SO2 and As2O3 and pollute the environment.
Pressure oxidation processes are difcult to be carried out, because
they require high-pressure and high temperature equipments. Bio-
oxidation process requires long time for pretreatment (Ramon
et al., 2004). Therefore, a new process is necessary to be developed.
Nitric acid has a strong oxidation potential relative to refractory
sulphide ores and several processes have been reported in the lit-
erature for nitric or nitrous acid leaching of complex sulphide ores
(Posel, 1976a,b; Kunda, 1982; Raudsepp and Beattie, 1989). We
have also done much work on catalytic oxidation by nitric acid.
For example, we chose nitric acid as an oxidant to dispose cyanided
tailings and have obtained good prots (Li, 2003a,b; Li et al., 2006)
However, to date, there is not much research on the kinetics of
HGC oxidation by dilute nitric acid under mild conditions. It was
expected to gain a clear understanding of the behavior of HGC oxi-
dation under mild conditions for a successful process design. The
purpose of our work was to investigate the kinetics of HGC oxida-
tion by dilute nitric acid under various reaction conditions at ambi-
ent pressure and lay a good foundation for developing a new
process.
2. Experimental
2.1. Materials
The HGC used in this study were obtained from Penglai Gold
Smelting Plant in Shandong Province, China. It was washed to re-
move any nes adhering to particle surfaces which might effect

0892-6875/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2008.05.001
112 G. Gao et al. / Minerals Engineering 22 (2009) 111115

the interpretation of the results, and air-dried at ambient temper-
ature. It was then crushed and screened to produce the 50335 lm
particle size fraction. Table 1 shows the element composition of
the raw materials used for the experiment. All solutions were pre-
pared with analytical grade chemicals and deionized water.
drawn, Xi the concentration of iron in sample i (mg/L), m the initial
mass of the HGC (g) (on a dried basis) added into the reactor and X
the concentration of iron in the initial HGC (wt.% dried solids).
3. Results and discussion

2.2. Experimental procedure 3.1. Effect of particle size on Cr

The oxidation experiments were carried out in a 1000 mL four-
neck round bottom ask immersed in a thermostatically controlled
water bath. A thermometer, a condenser, and a mechanical agitator
were tted into the glass reactor through three of its openings. The
fourth opening was used to feed reactants and withdraw samples.
For each run, original total quality of the solution was 500 g and
the quality of HGC was 25 g. Firstly, a given amount of nitric acid of
pre-determined molarity was charged into the reactor and heated
to the desired temperature, and then HGC was added to the reac-
tion vessel while the contents of the reactor were stirred at a cer-
tain speed. The temperature of the reaction mixture was then
maintained constant. This time was marked as the beginning of
the experiment. The NOx generated can be absorpted by the subse-
quent NaOH adsorption bottle to make NaNO2 and NaNO3. The
reaction liquid and oxidation tailings in the reactor can be used
to prepare iron red pigment and leach valuable metals,
respectively.
At selected time intervals during a run, solution samples of one
milliliter were withdrawn from the reactor with a pipette to mea-
sure the iron extracted rate. The sample slurry was ltered and
washed before determined by complexometry with EDTA using
5-sulfosalicylic acid as indicator. The reaction kinetics were deter-
mined by measuring the total iron dissolved in the solution as a
function of time. Table 2 shows the experimental parameters for
different cases.
2.3. Chemical analysis
Iron content in the ltrate was analyzed by complexometry
with EDTA using 5-sulfosalicylic acid as indicator. Iron extraction
rate (Cr) was chose to represent the oxidation degree of HGC. For
the calculation of Cr, a correction formula was used (Georgiou
and Papangelakis, 1998), which includes in itself correction factors
to account for the volume and mass losses due to sampling. Cr was
calculated by dividing the amount of solubilized iron in the mo-
ment of sampling by the amount of iron contained in the HGC at
the beginning of the reaction.
Pi1 Pi1
V  i1 vi X i
i1 vi X i
C ri
mX=100
where Cri is the iron extracted rate of the sample i, V the initial vol-
ume (mL) of the solution, Vi the volume (mL) of the sample i with-
Table 1
Chemical composition of the gold concentrate (wt.%)
To study the effect of particle size on Cr, a series of experiments
were performed with the particle size ranging from 50 to 335 lm.
Other experimental parameters are listed in Table 2 (case 1). As
illustrated in Fig. 1, the decrease in particle size enhanced the iron
dissolution, but it can be seen that particle size has little effect on
the kinetics in the leaching process. The small difference observed
is probably due to that the chemical reaction occurs on the surface
of HGC particles. The particle size decreases and surface area in-
creases, which help accelerate the leaching process.
3.2. Effect of initial nitric acid concentration on Cr
To investigate the effect of nitric acid concentration on Cr,
experiments were carried out with varying initial concentrations
of nitric acid (from 10% to 30%). Other experimental parameters
are listed in Table 2 (case 2). As shown in Fig. 2, it is obvious that
nitric acid concentration has a signicant effect on Cr. Cr increases
with the rise of nitric acid concentration in the range being as-
sessed in this study. About 80% of iron present in the gold concen-
trate is extracted using 30% nitric acid solution after 90 min.
3.3. Effect of temperature on Cr
To study the effect of temperature on Cr, experiments were car-
ried out with the temperature ranging from 25 to 85 C. Other
experimental parameters are listed in Table 2 (case 3). Fig. 3 shows
the effect of reaction temperature on Cr at two different initial ni-
tric acid concentration of 10% and 25%.
From Fig. 3a, it can be seen that Cr is low in 10% HNO3, even at
85 C. From Fig. 3b, it can be concluded that reaction temperature
has a major role on the iron dissolution. Cr is relatively lower in the
experiment carried out at 25 C (28%) but signicant increases as
the reaction temperature rises and a high Cr was observed at
85 C (99%). Similar results were observed by Kadioglu et al.
(1995).
1.0
1
0.8 154-335 um
74-154 um
50-74 um
0.6
Cr

Element Au Ag Cu Pb Zn S Fe As
Content 0.009 0.002 0.30 0.4 0.63 41 44.23 8.42
0.4

Table 2
Experimental parameters for different cases 0.2

Case Particle size Initial nitric acid Temperature Stirring speed

(lm) concentration (wt.%) (C) (rpm)
1 30 65 600 0.0
0 30 60 90
2 74154 65 600
3 74154 10, 25 600 Time (min)
4 74154 25 65
Fig. 1. Effect of particle size on iron extracted rate.
 G. Gao et al. / Minerals Engineering 22 (2009) 111115 113

3.4. Effect of stirring speed on Cr

0.8
10 % Stirring speed is often important in liquidsolid reactions, espe-
0.7 15 % cially those under diffusion control, so experiments were also con-
20 %
ducted to investigate the effect of stirring speed on Cr. The stirring
0.6 25 %
speeds were 400, 600 and 800 rpm, while other experimental
30 %
parameters are listed in Table 2 (case 4). As can be seen from
0.5
Fig. 4, Cr increases with an increase in stirring speed, indicating
that there is mass transfer resistance power in the liquid lm un-
Cr

0.4
der the selected conditions. With stirring speed increasing, liquid
turbulence intensity rises, diffusion layer thickness decreases,
0.3
mass transfer rate increases and reaction process speeds up. There-
0.2
fore, agitation affects positively the kinetics of HGC oxidation
process.
0.1
4. Process of HGC oxidation
0.0
0 30 60 90 4.1. Principles of oxidation by nitric acid
Time (min)

Fig. 2. Effect of initial nitric acid concentration on iron extracted rate. Nitric acid is an unstable strong acid and a strong oxidant. The
strong oxidizing power of the nitric acid can be explained from its
standard electrode potential. The standard electrode potential of
nitric acid is presented as follows:

NO3 2H e ! NO2 " H2 O E; 0:80 V 2

NO3
10H 8e ! NH4 ;
H2 O E 0:87 V 3
a NO3 4H 3e ! NO " 2H2 O E; 0:95 V 4

0.4 o These data suggest that nitric acid has a relatively high standard
25 C
o electrode potential, whether it is reduced into nitrogen dioxide,
35 C
o
ammonium ion or nitrogen monoxide.
45 C
0.3 o
When the acidity of solution is different, the oxidation potential
55 C of nitric acid is different. For example, the corresponding Nernst
o
65 C equation of Eq. (2) is as follows
o
75 C
Cr

0.2
85 C
o 0:0592 H 2 NO3 
E E; log 25  C 5
n PNO2

0.1
Supposing that the concentration of hydrogen ions is low at
107 mol/L, the concentration of nitrate ions is kept at 1.0 mol/L
and the partial pressure of nitrogen dioxide is 105 Pa, the half-reac-
tion potential is 0.03 V as shown in Eq. (6).
0.0
0 30 60 90
E E; 0:0592 logH 2 0:80 2  0:0592  7 0:03 V
Time (min)
6

b
1.0 o
25 C
o 0.8
35 C
o
0.8 45 C 400 rpm
o 600 rpm
55 C
o
0.6 800 rpm
65 C
o
0.6 75 C
o
85 C
Cr

Cr

0.4
0.4

0.2 0.2

0.0
0 30 60 90 0.0
Time (min) 0 30 60 90
Time (min)
Fig. 3. Effect of reaction temperature on iron extracted rate. (a) nitric acid: 10% and
(b) nitric acid: 25%. Fig. 4. Effect of stirring speed on iron extracted rate.
114 G. Gao et al. / Minerals Engineering 22 (2009) 111115

2
But when the concentration of hydrogen ions increases to 10 mol/L, 1  1  C r 3 kp t 12
the potential of the half-reaction is +0.92 V as shown in Eq. (7).
where kp = chemical rate constant (cm min1); t = time (min);
E E; 0:0592 logH 2 0:80 2  0:0592  1 0:92 V 7 Cr = iron extracted rate.
2

All these calculations imply that the higher concentration of nitric The variation of 1  1  C r 3 with time for the data in Fig. 3a
acid is, the stronger its oxidation ability is. In neutral solution and and b is shown in Figs. 5 and 6, respectively. It can be seen that
at extremely dilute nitric acid concentration, nitrate ions have no the experimental data were well correlated by the relationship as
oxidation ability at all. shown in Eq. (12), which indicates that the reaction follows the
shrinking particle model.
4.2. Chemical reaction The rate constants (Kp) were calculated from the slopes of each
straight line. The plots of lnKp versus 1/T for the data in Figs. 5
In the leaching studies, it was found that a little amount of ele- and 6 are shown in Figs. 7 and 8, respectively. According to the
mental sulfur formed and suspended in the solution. The propor- Arrhenius equation Eq. (13), the apparent activation energies (Ea)
tion of elemental sulfur formed increased rst with increasing for the process of HGC oxidation by nitric acid were found to be
leaching time, and then decreased. Because the amount of HNO3 10.70 kJ/mol in the 10% HNO3 and 12.25 kJ/mol in the 25% HNO3.
is excessive, all the elemental sulfur was oxidized to sulfate as According to Habashi (1969), the activation energy of a diffusion-
the reaction progressed to completion. Consequently, the elemen- controlled process is characterized to be from 4.18 to 12.54 kJ/
tal sulfur may be considered as an intermediate product. The reac- mol, while for a chemically controlled process, it is usually greater
tions between HNO3 and HGC are very complex and sensitive to than 41.8 kJ/mol. Therefore, the reaction is diffusion-controlled.
 
temperature and concentration. The oxidation and dissolution Ea
mechanisms of HGC by nitric acid still remain uncertain with a
K p A exp  13
RT
wide variety of possible mechanisms having been proposed in
the literature. So there are different forms of reaction equations ci-
ted in the literature for the nitric acid-ore system (Kadioglu et al., 0.32
1995). The following reaction equations account for the above
o
experimental kinetic data: 25 C
0.28 o
35 C
FeS2 4HNO3 ! FeNO3 3 2S NO " 2H2 O 8 o
0.24 45 C
2HNO3 S ! H2 SO4 2NO " 9 o
55 C
o
In addition, HGC could be oxidized by the nitric acid to produce 0.20 65 C
o
2/3

simultaneously both sulfur and sulfate by separate oxidation pro- 75 C

1-(1-Cr)

0.16 o
cesses according to Eqs. (8) and (10) depending on the leaching 85 C
conditions.
0.12
2FeS2 10HNO3 ! Fe2 SO4 3 H2 SO4 10NO " 4H2 O 10
0.08
4.3. Reaction kinetics
0.04

Fluid-solid heterogeneous reaction systems have many applica-

0.00
tions in chemical and hydrometallurgical processes. A number of 0 30 60 90
studies have been done on these types of reactions, and several Time (min)
mathematical models have been developed (Lapidus and De Lour-
des Mosqueira, 1988). Two of the most commonly used models are Fig. 5. 1  (1  Cr)2/3 vs. time at various temperatures (10% nitric acid).
described as follows: the shrinking particle model and the shrink-
ing core model.
During the experiments, it can be seen that only a little amount
of elemental sulphur suspended in the solution, that is, no solid 1.0
product layer formed. In order to determine the kinetic parameters
and rate-controlling step, the experimental data were tested on the o
25 C
basis of the shrinking particle model because HGC particles are 0.8 o
35 C
generally non-porous and there is no product layer in the process. o
45 C
According to this model, the reaction between a uid and a solid o
55 C
may be represented by:
2/3

0.6 o
65 C
1-(1-Cr)

o
Afluid Bsolid ! Cfluid 11 75 C
o
85 C
where A and B represent nitric acid and gold concentrate particles, 0.4
respectively. The reaction rate may be controlled by diffusion
through a uid boundary layer or the chemical reaction at the sur-
face of unreacted particle, that is, the rate-controlling step is either 0.2
the diffusion of NO 3 from liquid phase to HGC particle surface or the
chemical reaction between NO 3 and HGC particles on the shrinking
surface (Li et al., 2003). 0.0
0 30 60 90
When the rate of reaction is controlled by the diffusion of NO 3
Time (min)
from liquid phase to HGC particle surface, the kinetics may be cor-
related graphically using the following equation (Zhu, 2001): Fig. 6. 1  (1  Cr)2/3 vs. time at various temperatures (25% nitric acid).
 G. Gao et al. / Minerals Engineering 22 (2009) 111115 115

7.2 The kinetics study indicates that the rate of HGC oxidation by
dilute nitric acid under selected conditions is diffusion-controlled.
7.0 The activation energies were found to be 10.70 kJ/mol in the 10%
HNO3 and 12.25 kJ/mol in the 25% HNO3., which are consistent
6.8 with the values of activation energies reported for the diffusion-
controlled reactions.
6.6
Acknowledgements
-lnKp

6.4
The authors greatly acknowledge the Major project of Educa-
6.2 tional Ministry (No. 107124), National High Technology Research
and Development Program of China (863 Program, No.
6.0 2006AA06Z132), Shanghai Leading Academic Discipline Project
(No. B604) and Key Laboratory of Science and Technology of Eco-
5.8 Textile (Donghua University/Jiangnan University), Ministry of Edu-
cation, China (ECO-KF-2007-10) for nancial support of this study.
5.6

2.8 3.0 3.2 3.4

References
3 -1
10 /T (K ) Abrantes, L.M., Costa, M.C., 1996. Electro-oxidation as a pre-treatment for gold
recovery. Hydrometallurgy 40 (12), 99110.
Fig. 7. Arrhenius plot for the oxidation of gold concentrate (10% nitric acid). Climo, M., Watling, H.R., Bronswijk, W.V., 2000. Biooxidation as pre-treatment for a
telluride-rich refractory gold concentrate. Minerals Engineering 13 (12), 1219
1229.
Deng, T.L., Liao, M.X., 2002. Gold recovery enhancement from a refractory otation
concentrate by sequential bioleaching and thiourea leach. Hydrometallurgy 63
6.4
(3), 249255.
Dunn, J.G., Chamberlain, A.C., 1997. The recovery of gold from refractory
6.2 arsenopyrite concentrates by pyrolysisoxidation. Minerals Engineering 10
(9), 919928.
6.0 Georgiou, D., Papangelakis, V.G., 1998. Sulphuric acid pressure leaching of limonitic
laterite: chemistry and kinetics. Hydrometallurgy 49 (12), 2346.
5.8 Gonzalez, R., Gentina, J.C., Acevedo, F., 1999. Continuous biooxidation of a refractory
gold concentrate. Process Metallurgy 9 (1), 309317.
5.6 Gudyanga, F.P., Mahlangu, T., Roman, R.J., Mungoshi, J., 1999. An acidic pressure
oxidation pre-treatment of refractory gold concentrates from the KweKwe
-lnKp

5.4 roasting plant, Zimbabwe. Minerals Engineering 12 (8), 863875.

5.2
5.0
4.8
4.6
4.4
2.8 3.0 3.2
3 -1
10 /T (K )
Fig. 8. Arrhenius plot for the oxidation of gold concentrate (25% nitric acid).
where Kp is the reaction rate constant, A is the frequency factor, Ea is
the activation energy for the reaction, R is the universal gas con-
stant, and T is the absolute temperature.
The fact that the activation energies are different can probably
be attributed to the differences of the chemical reaction mecha-
nism in these media. However, at the present, it is not very clear
why different nitric acid concentrations give different values of
activation energy and it should be researched further in the future.
5. Conclusions
Kinetics of HGC oxidation by dilute nitric acid under mild con-
ditions was experimentally investigated. Cr increases with the rise
of temperature, time, initial nitric acid concentration, but de-
creases with the rise of particle size.
Habashi, F., 1969. Principles of Extractive Metallurgy, vol. 1. Gordon & Breach, New
York. pp. 153-163.
Kadioglu, Y.Y., Semra, K., Samih, B., 1995. Kinetics of pyrite oxidation in aqueous
suspension by nitric acid. Fuel Processing Technology 41 (3), 273287.
Karamanev, D., Margaritis, A., Chong, N., 2001. The application of ore
immobilization to the bioleaching of refractory gold concentrate.
International Journal of Mineral Processing 62 (14), 231241.
Kunda, W., 1982. Process for the recovery of silver values from silver-containing
material which also contains iron and arsenic. US Patent (4,331,469).
Lapidus, G., De Lourdes Mosqueira, M., 1988. The effect of product solubility on the
leaching kinetics of non-porous minerals. Hydrometallurgy 20 (1), 4964.
3.4 Li, D.X., 2003. One process of leach gold again from cyanided tailings technique.
Chinese Patent (ZL 01134737.6).
Li, D.X., 2003. One process of preparation iron oxide red from cyanided tailings.
Chinese Patent (ZL 01134738.7).
Li, D.X., Gao, J.S., Yue, G.X., 2003. Catalytic oxidation and kinetics of oxidation of coal
derived pyrite by electrolysis. Fuel Processing Technology 82 (1), 7585.
Li, Z.J., Li, D.X., Zhang, W.X., Hu, L., 2006. The research on preparation ferrous sulfate
from acid leaching tailings (in Chinese). Recycling Research 6, 3235.
Miller, P., Brown, A., 2005. Bacterial oxidation of refractory gold concentrates.
Developments in Mineral Processing 15, 371402.
Posel, J.G., 1976. Nitric acid leaching process for the recovery of copper, nickel, and
silver from polysulde ores of the same. Canadian Patent (992,749).
Posel, J.G., 1976. Recovery of nitric acid soluble transition metals from sulfur and
iron containing ores of the same. US Patent (3,965,239).
Ramon, G., Juan, C.G., Fernando, A., 2004. Biooxidation of a gold concentrate in a
continuous stirred tank reactor: mathematical model and optimal
conguration. Biochemical Engineering Journal 19 (1), 3342.
Raudsepp, R., Beattie, M.J.V., 1989. Recovery of precious metals from pyrite or
arsenopyrite via nitrate route. Australian Patent (582,961).
Ubaldini, S., Veglio, F., Toro, L., Abbruzzese, C., 1997. Biooxidation of arsennopyrite
to improve gold cyanidation: study of some parameters and comparison with
grinding. International Journal of Mineral Processing 52, 6580.
Zhu, B.C., 2001. Chemical Reaction Engineering. Chemical Industry Press, Beijing.