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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 process would release SO2 and As2O3 and pollute the environment.
Pressure oxidation processes are difcult to be carried out, because
The resources of high-sulphur and high-arsenic refractory gold they require high-pressure and high temperature equipments. Bio-
concentrate (HGC) are abundant and can be found in many areas oxidation process requires long time for pretreatment (Ramon
in China, such as Guizhou, Guangxi, Jiangxi and Yunnan provinces. et al., 2004). Therefore, a new process is necessary to be developed.
Because air and water was introduced into the stratum, HGC was Nitric acid has a strong oxidation potential relative to refractory
oxidized spontaneously and released acids and many heavy metals sulphide ores and several processes have been reported in the lit-
such as As, Pb, Zn and so on. Meanwhile, the obtained acids can erature for nitric or nitrous acid leaching of complex sulphide ores
accelerate the dissolution of the minerals around them and lead (Posel, 1976a,b; Kunda, 1982; Raudsepp and Beattie, 1989). We
many chemicals into water. Therefore, HGC leads to regional eco- have also done much work on catalytic oxidation by nitric acid.
logical damage. On the other hand, it contains a lot of valuable ele- For example, we chose nitric acid as an oxidant to dispose cyanided
ments, such as Au, Ag. So utilization of it can bring economical and tailings and have obtained good prots (Li, 2003a,b; Li et al., 2006)
environmental benets. However, to date, there is not much research on the kinetics of
The gold in HGC is encapsulated as ne grained particles in the HGC oxidation by dilute nitric acid under mild conditions. It was
crystal structure of the mineral matrix, which renders the metal expected to gain a clear understanding of the behavior of HGC oxi-
inaccessible to the leaching agent (Abrantes and Costa, 1996; Ubal- dation under mild conditions for a successful process design. The
dini et al., 1997; Karamanev et al., 2001). To achieve a satisfactory purpose of our work was to investigate the kinetics of HGC oxida-
recovery, an oxidative pretreatment stage is required to break tion by dilute nitric acid under various reaction conditions at ambi-
down or at least to modify the sulphide matrix and release the pre- ent pressure and lay a good foundation for developing a new
cious and base metals before applying any conventional treatment process.
(Climo et al., 2000). These pretreatment methods include roasting
(Dunn and Chamberlain, 1997), pressure oxidation (Gudyanga 2. Experimental
et al., 1999), bio-oxidation (Gonzalez et al., 1999; Deng and Liao,
2002; Miller and Brown, 2005) for high leaching rate of HGC. The 2.1. Materials
contents of sulphur and arsenic are high, so traditional roasting
The HGC used in this study were obtained from Penglai Gold
* Corresponding author. Tel.: +86 21 677 92541; fax: +86 21 677 92522. Smelting Plant in Shandong Province, China. It was washed to re-
E-mail address: lidengxin@dhu.edu.cn (D. Li). 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- drawn, Xi the concentration of iron in sample i (mg/L), m the initial
ature. It was then crushed and screened to produce the 50335 lm mass of the HGC (g) (on a dried basis) added into the reactor and X
particle size fraction. Table 1 shows the element composition of the concentration of iron in the initial HGC (wt.% dried solids).
the raw materials used for the experiment. All solutions were pre-
pared with analytical grade chemicals and deionized water. 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- To study the effect of particle size on Cr, a series of experiments
neck round bottom ask immersed in a thermostatically controlled were performed with the particle size ranging from 50 to 335 lm.
water bath. A thermometer, a condenser, and a mechanical agitator Other experimental parameters are listed in Table 2 (case 1). As
were tted into the glass reactor through three of its openings. The illustrated in Fig. 1, the decrease in particle size enhanced the iron
fourth opening was used to feed reactants and withdraw samples. dissolution, but it can be seen that particle size has little effect on
For each run, original total quality of the solution was 500 g and the kinetics in the leaching process. The small difference observed
the quality of HGC was 25 g. Firstly, a given amount of nitric acid of is probably due to that the chemical reaction occurs on the surface
pre-determined molarity was charged into the reactor and heated of HGC particles. The particle size decreases and surface area in-
to the desired temperature, and then HGC was added to the reac- creases, which help accelerate the leaching process.
tion vessel while the contents of the reactor were stirred at a cer-
tain speed. The temperature of the reaction mixture was then 3.2. Effect of initial nitric acid concentration on Cr
maintained constant. This time was marked as the beginning of
the experiment. The NOx generated can be absorpted by the subse- To investigate the effect of nitric acid concentration on Cr,
quent NaOH adsorption bottle to make NaNO2 and NaNO3. The experiments were carried out with varying initial concentrations
reaction liquid and oxidation tailings in the reactor can be used of nitric acid (from 10% to 30%). Other experimental parameters
to prepare iron red pigment and leach valuable metals, are listed in Table 2 (case 2). As shown in Fig. 2, it is obvious that
respectively. nitric acid concentration has a signicant effect on Cr. Cr increases
At selected time intervals during a run, solution samples of one with the rise of nitric acid concentration in the range being as-
milliliter were withdrawn from the reactor with a pipette to mea- sessed in this study. About 80% of iron present in the gold concen-
sure the iron extracted rate. The sample slurry was ltered and trate is extracted using 30% nitric acid solution after 90 min.
washed before determined by complexometry with EDTA using
5-sulfosalicylic acid as indicator. The reaction kinetics were deter- 3.3. Effect of temperature on Cr
mined by measuring the total iron dissolved in the solution as a
function of time. Table 2 shows the experimental parameters for To study the effect of temperature on Cr, experiments were car-
different cases. ried out with the temperature ranging from 25 to 85 C. Other
experimental parameters are listed in Table 2 (case 3). Fig. 3 shows
2.3. Chemical analysis the effect of reaction temperature on Cr at two different initial ni-
tric acid concentration of 10% and 25%.
Iron content in the ltrate was analyzed by complexometry From Fig. 3a, it can be seen that Cr is low in 10% HNO3, even at
with EDTA using 5-sulfosalicylic acid as indicator. Iron extraction 85 C. From Fig. 3b, it can be concluded that reaction temperature
rate (Cr) was chose to represent the oxidation degree of HGC. For has a major role on the iron dissolution. Cr is relatively lower in the
the calculation of Cr, a correction formula was used (Georgiou experiment carried out at 25 C (28%) but signicant increases as
and Papangelakis, 1998), which includes in itself correction factors the reaction temperature rises and a high Cr was observed at
to account for the volume and mass losses due to sampling. Cr was 85 C (99%). Similar results were observed by Kadioglu et al.
calculated by dividing the amount of solubilized iron in the mo- (1995).
ment of sampling by the amount of iron contained in the HGC at
the beginning of the reaction.
Pi1 Pi1 1.0
V  i1 vi X i
i1 vi X i
C ri 1
mX=100
where Cri is the iron extracted rate of the sample i, V the initial vol- 0.8 154-335 um
ume (mL) of the solution, Vi the volume (mL) of the sample i with- 74-154 um
50-74 um
Table 1
0.6
Chemical composition of the gold concentrate (wt.%)
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


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