Ind. Eng. Chem. Res.

1995,34, 3995-4002 3995

Solubility of Stibnite Ore in HCl Solutions

Mehmet Copur,"Sabri Colak, and Sinan Yapici
Atatiirk tiniversitesi, Miihendislik Fakiiltesi, Kimya Miihendisligi Boliimii, 25240 Erzurum, Turkey

In this study, the dissolution of stibnite, Sb2S3, which is an antimony ore, in HCl solutions was
investigated, taking into consideration the effect of particle size, acid concentration, stirring
speed, solid-to-liquid ratio, and temperature. It was observed that the dissolution rate increased
with increasing temperature and with decreasing particle size and solid-to-liquid ratio, while
no pronounced effect of stirring speed was observed. Using the experimental data, we attempted
to establish a kinetic model for the dissolution of the ore in HC1 solutions. Employing graphical
and statistical methods, the following kinetic model including the effect of the above choosen
parameters was established to represent the dissolution process -ln(l - X ) = 9.79 x 10-lo-
t , where X is the conversion fraction of the mineral, D is the
(D)-0.908(C)10~600(S/L)-0.321e-6244/T
particle size, C the acid concentration in weight percent, and S/L is the solid-to-liquid ratio in
grams per milliliter. The activation energy for this dissolution process was calculated as 52 kJ
mol-l .

1. Introduction reaction as the process progressed. No study for the

Antimony trioxide (Sb203) is widely used as a fire-
resistant material in plastic, cable, and latex production
(Morizot et al., 1980; Robert and Weast, 1986). Manda-
tory use of fire-resistant materials in the automobile
industry by law in the United States has substantially
increased the consumption of Sb2O3. The use of anti-
mony in the production of fire-resistant materials in the
United States is about 57 % of the total antimony
consumption (MTA Bulletin, 1985).
Stibnite has an orthorhombic crystal system and is
available in nature in the color of lead-grey, sometimes
tarnished and iridescent; it is opaque. It melts readily,
even in a match flame. Stibnite, the most common
antimony mineral, is commonly found with quartz in
hydrothermal veins, as replacement bodies in limestone,
and in hot spring deposits (Hamilton et al., 1987).
The production of SbzO3 in high purity requires the
production of SbC13 in high purity (Morizot et al., 1980).
SbCl3 is also used for the production of other antimony
compounds, in antimony electroplating, for coloring iron
and zinc metals, and as a catalyst in organic chlorina-
tion and polymerization processes. The most common
method for the production of SbCl3 is a dissolution
process of stibnite, Sb2S3, in HC1 solutions followed by
separation by a distillation process (Kirk and Othmer,
1952).
Carrying out a reactor design for a technological
process requires the knowledge of the kinetic behavior
of the occurring process. Some studies were found in
the literature t o enlighten the kinetic process for the
dissolutin of stibnite in different solutions. In a study
carried out by Shestiko et al. (19751, it was found that
the leaching kinetics of stibnite in Na2S was controlled
by diffusion through the fluid layer, and the activation
energy of the process was calculated as 16.72 kJ mol-l.
In the dissolution process of stibnite in NaOH solutions,
KOet al. (1981) determined that the dissolution process
was controlled by diffusion for the solution of 0.5 M
NaOH concentration and by chemical reaction for that
of 0.05 M NaOH. For the dissolution process of stibnite
in acidic FeCl3 solutions, KOet al. (1981) found that the
process was controlled by diffusion of the reactant Fe3+
through the sulfur layer for particle sizes smaller than
270 mesh, while for particle sizes larger than 270 mesh,
the process was controlled by chemical reaction in the
beginning of the dissolution and then by chemical
0888-588519512634-3995$09.0010
leaching of stibnite with HC1 solutions could be detected
in the literature.
There are also some studies for the production of
SbCl3. Khundar et al. (1967) produced SbC13 by the
effect of CC4 on stibnite in the temperature range 200-
500 "C. In another study carried out by Grossman
(19761, SbC13 was obtained by the contact of HC1 gas
with stibnite at temperatures above 80 "C. SbC13
obtained by the contact of an antimony ore with Clz gas
was separated from S or H2S by distillation (Stewart
and McKinley, 1976).
The aim of this study is to investigate the dissolution
kinetics of stibnite in HC1 solutions in a stirred batch
reactor, using some kinetic data. As mentioned above,
although the process is used to produce SbCl3 industri-
ally, no study was found in the literature on the kinetic
investigation of the dissolution of stibnite in HC1 solu-
tions.
2. Experimental Section
The antimony ore used in the experiments was
provided from the region of Nigde in Turkey. After
crushing and grinding the ore, it was sieved by a wet
method using ASTM standard Sieves and separated into
fractions of 0.5958, 0.4213, 0.2979, 0.2121, 0.1500, and
0.0822 mm. It was determined that the ore contains
mainly Sb& and Si02 by X-ray diffraction; and X-ray
diffractogram is given in Figure 1. The chemical
analysis of the ore by volumetric and gravimetric
methods and by atomic absorption spectrophotometry
for trace elements is given in Table 1.
For the kinetic study, the parameters were chosen to
be temperature, HC1 concentration, particle size, stir-
ring speed, and solid-to-liquid ratio. The ranges of these
parameters and their values are given in Table 2.
The dissolution experiments were carried out in a 250
mL glass reactor equipped with a mechanical stirrer
with a digital control unit and a timer, a thermostate,
and a back cooler. The temperature of the reaction
medium could be controlled within f0.5 "C. First, 200
mL of an HC1 solution at a given concentration was put
into the reactor, and after getting to a desired temper-
ature of the reactor contents, a certain amount of the
ore was added into the solution while stirring the
contents of the vessel at a certain stirring speed during
the reaction. At the end of the reaction period, the
0 1995 American Chemical Society
3996 Ind. Eng. Chem. Res., Vol. 34, No. 11, 1995

u 44 40 36 32 28 2L to 16 12 8

Figure 1. X-ray diffractogram of stibnite mineral.

Table 1. The Chemical Analysis of Stibnite Used in the Table 2. Parameters and Their Ranges and Values
Studs Employed in the Experiments
element % (by weight) element % (by weight) parameter range
Sb 60.560 Ag 0.005 temperature ("C) 12, 18, 25, 32,40,60
Ca 2.210 CU 0.014 acid concentration (% wt) 23.72,27.20, 30.58,33.84
Pb 0.029 Zn 0.022 particle size (mm) 0.5958, 0.423, 0.2979,0.2121,
co 0.013 As 0.010 0.1500,0.0822
Fe 0.091 S 23.118 stirring speed (rpm) 100,200,300,500,700,900
Mn 0.008 Si02 13.920 solid-to-liquid (g/mL) 0.5/100, 1/100,2/100,4/100

contents of the vessel were filtered for 15 s and Sb3+in
the filtered solution was then analyzed volumetrically
(Furman, 1963). Each experiment was repeated twice
within a deviation of approximately 1.5%, and the
average values were used in the kinetic analysis. The
number of experiments within the parameter ranges is
enough for a kinetic analysis of this type.
3. Results and Discussions
3.1. Dissolution Reactions. Stibnite gives the
following equilibrium reaction in HC1 solutions (Gil-
reath, 1954)
+
Sb2S3(s) 6HCUaq) 2SbC13(aq)+ 3H2S(g) (1)
Depending upon the HC1 concentration, the following
reactions take place in the system
+
Sb2S3(s) 8HCUaq)
B[SbCl,l-(aq) + 3H2S(g)+ 2Ht(aq)
Sb2S,(s) + 12HCKaq) =
2[SbC1J3(aq) + 3H2S(g)+ 6Hf(aq) (3)
The complexing reactions 2 and 3 result in a shift of
the dissolution process to the right, hence increasing
the dissolution process.
3.2. Effect of Parameters. The effect of the pa-
rameters on the dissolution process was investigated for
each parameter using the values given in Table 2. In
the experiments, while the effect of one parameter was
studied, the value of other parameters was kept con-
stant: the constant values were chosen as 25 "C for
temperature, 500 rpm for stirring speed, 0.2121 mm for
particle size, 30.58 % for acid concentration, and 11200
(g/mL)for solid-to-liquidratio. The data obtained from
the experiments were plotted in time versus conversion,
described as (percentage of dissolved antimony from the
ore)/(percentage of antimony in original ore).
The effect of the stirring speed on the dissolution was
investigated for the range of 100-900 rpm. The results
are exhibited in Figure 2. As seen from this figure,
increasing the stirring speed increased the dissolution
rate up to 300 rpm, and no effect of the stirring speed
on the dissolution could be observed by further increas-
ing the stirring speed. This behavior can be explained
by the higher density of stibnite (4649 kg mW3for pure
stibnite (Perry, 1984)); for a good distribution of solid
particles in the solution, a certain value of the stirring
speed is necessary. It was also observed that some part
of the solid settled down in the reactor at lower stirring
speeds. This settling of the particles decreased with
increasing stirring speed, and a good distribution was
(2) obtained after 300 rpm.
The fact that stirring speeds above 300 rpm have no
effect on the dissolution rate can mean that the process
is not diffusion controlled through the film layer around
the solid particle. For other solid-to-liquidratios, it was
observed that this limit value of the stirring speed for
complete suspension of solid particles in the reaction
medium remained almost approximately at the same
value, 300 rpm, thus the stirring speed value was chosen
as 500 rpm to make sure of a good suspension of the
particles in the solution while the effect of other
parameters was investigated.
The effect of the particle size on the dissolution was
investigated for the particle size range 0.0822-0.5958
mm. The results obtained from these experiments are
 Ind. Eng. Chem. Res., Vol. 34, No. 11, 1995 3997
I . 00

0.80

0.60

n
v,
X

0,40

0.20

A A A A ~0
oe0.0 IS "
....I 2 1 "

Stirring speed / r p m
Figure 2. Effect of stirring speed on dissolution of stibnite.

1. 00

0 .BO

0.60

n
ln
X
0,10

0.20

0 00
0 10 20
Figure 3. Effect of particle size on dissolution of stibnite.
shown in Figure 3. This figure shows that the dissolu-
tion rate decreases as the particle size increases; a
behavior which can be attributed to the increase of
surface with the decrease of particle size per amount of
the solid.
The experiments to observe the effect of the HC1
concentration on the dissolution process, carried out in
30 LO 50 60 70
time/ min
the concentration range 20.11-33.84 %, showed that the
dissolution rate increases with increasing acid concen-
tration, as seen in Figure 4. This increase in the
dissolution with acid concentration can be explained by
(a) the increase of the number of H+ ions per volume
with the increase of HC1 concentration and therefore
the shift of equilibrium reactions 1-3 to the right, (b)
3998 Ind. Eng. Chem. Res., Vol. 34, No. 11, 1995

0 40 EO 160 200 260

t i me / m'i n
Figure 4. Effect of HCl concentration (wt %) on dissolution of stibnite.

I. 00 I-

/
0.8 0

0.60

0
v,
X

0,h0

00000 12OC
00000 l8OC
0.20

0.00 '
0
I 1

10
1 1

20
1

30 40 50
I

60 70
t i m e / min
Figure 6. Effect of temperature on dissolution of stibnite.

the increase of the dissolution rate due to the removal
of HzS because of decreasing solubility of HzS with
increasing acidity, and (c) the increase of the dissolution
due to complex formation throughout reactions 2 and
3.
The effect of temperature on the dissolution process
was investigated in the temperature range 12-60 "C.
The results plotted in Figure 5 shows that the increase
in the temperature substantially increases the dissolu-
tion rate. This behavior can be explained by the
increase of the reaction rate constant with temperature
expressed by the Arrhenius Law. Moreover, since the
solubility of gases decreases with temperature, the
removal of HzS formed through the dissolution reactions
 Ind. Eng. Chem. Res., Vol. 34,No. 11, 1995 3999

"0° k
0.8 0

0.6 0 -
n
In
X
0,40 -

.....
oaaao 0.51100
0 20 oooou 11 100
AAAAa 2 1 100
4 1 100

0 00
0 5 10 I5 20 25
t imelmin
Figure 6. Effect of solid-to-liquid ratio in g/mL on dissolution process.

from the reaction medium will shift the occurrence of
the reactions 1-3 t o the right side increasing the
dissolution process.
The investigation of solid-to-liquid ratio on the dis-
solution was carried out for the solid-to-liquid range
0.005-0.040. The results exhibited in Figure 6 show
that decreasing solid-to-liquid ratios are in favor of the
the dissolution process, which can be explained by the
decrease of solid amount per amount of reagent in the
suspension.
3.3. Kinetic Analysis. The experimental results
were analyzed by computer with statistical and graphi-
cal methods, applying fluid-solid reaction models (Lev-
enspiel, 1.9721, and it was determined that the dissolu-
tion kinetics cannot be expressed by any of the fluid-
solid reaction models. Therefore, the experimental data
were analyzed using pseudo-homogeneous reaction mod-
els and it was found that this dissolution process can
be expressed by a first-order pseudo-homogeneous reac-
tion model in the form of
dx
-=I41 -x)
dt
Integrating this equation gives
-ln(l - X ) = kt
The plots of -ln(l - X) vs t for various temperature
and acid concentration ranges given in Figures 7 and
8, respectively, show the agreement of the experimental
results with the model. To express the effect of the
parameters it can be assumed that the rate constant of
the dissolution process depends on the parameters as
follows
Then, eq 5 can be written as
where D = particle size, mm; C = acid concentration,
w t %; S/L = solid-to-liquidratio, g mL-l; X = conversion
fraction; EA = activation energy, J mol-l; t = time, min;
and a , b, d = constants. Statistical calculations by
simultaneous multiple regression gave the following
results for the constants in eq 7
ho = 9.790 x 10-l'
a = -0.908
b = 10.600
d = -0.321
E, = 51919.766 J mol-'
Inserting the estimated values into eq 7 gives the
(4) following kinetic model
-ln(l - x)=
9,790 ~ ~ - 1 0 ~ ~ ~ - 0 . 9 0 8 ~ ~ ~ 1 0 . 6 0 0 ~ ~ ~ ~ - 0 . 3 2 1 e - 6 2 4 4 / ~
t (8)
(5)
As seen from the kinetic model for the dissolution
process, eq 8, the most effective parameter is the acid
concentration, and then reaction temperature follows
it. Since there is no effect of the stirring speed on the
dissolution, it was not included in the kinetic model. The
particle size is more effective than the solid-to-liquid
ratio. The fact that the stirring speed has no effect on
the process and that activation energy is higher than
28 000 J mol-l (Jackson, 1986) supports the idea that
the process is not controlled by diffusion through the
fluid layer around the solid particle. Since the purity
4000 Ind. Eng. Chem. Res., Vol. 34,No. 11, 1995

4. 5

4.0

3.5

3.0

-T 2.5

--
c

c
I 2. 0

1. 5

I. 0

0.5

0.0
U 10 20 30 40 50 60 70
time / m i n
Figure 7. Plot of -ln(l - X ) vs t for different temperatures.

3.0

2.5

2. 0

-
X
c

-c
I

1. 5
I

1 0

os

0.o
0 25 50 75 100 12 5 150 175 200 225
time /min
Figure 8. Plot of -ln(l - X ) vs t for different acid concentration values.

of the ore is very high, approximately 83 % by weight, an ash layer around the particle is out of the question,
and it was observed by microscope that silica particles so it is being controlled by diffusion through the ash
separated from stibnite by grinding, the formation of layer. The statistical calculations showed that the
 Ind. Eng. Chem. Res., Vol. 34, No. 11, 1995 4001
I. 0

0.8

0.6

a
L

E
.-
L 0. 4
P,
a
0,
x

0.2

0. 0
0.0 0.4 0.6 0.8 1.0

x p r e d i c t i on
Figure 9. The agreement between experimental conversion values and those predicted from the empirical expression.

process data fits t o a first-order pseudo-homogeneous 4. Conclusions

reaction model, not a fluid-solid reaction model con-
trolled by surface reaction, with regression coefficients
of 0.9977 vs 0.9874 for the two models, respectively. In
some studies of fluid-solid systems on mineral leaching
(Ekmekyapar et al., 1993; Kum et al., 1994, Yartagi et
al., 1994) the kinetic model was also found to fit to the
pseudo-homogeneous models.
To test the agreement between the experimental
conversion values and the values calculated from the
empirical equation, the plot of X e x p vs X p r d was drawn
as seen in Figure 9. The agreement between the
experimental and calculated values is very good, with
a relative mean square of errors of 0.0627 calculated
by the equation
where X p r d is the calculated value, xexp
the experimental
value, and N the number of experimental data, which
is 76 for the present case.
This empirical model can be applicable for the ex-
perimental condition ranges and reactor geometry used
in the present study. The study can be extended to a
pilot scale work with higher solid-to-liquid ratios and
to production of antimony components from the Sb3+-
containing solution.
A kinetic study of the dissolution of stibnite with HC1
solutions was performed in a stirred semibatch reactor.
The parameters were chosen t o be temperature, acid
concentration, solid-to-liquid ratio, particle size, and
sitrring speed. The results showed that the most
effective parameter is the acid concentration followed
by the temperature. The particle size is more effective
than the solid-to-liquid ratio while no effect of stirring
speed on the dissolution process was observed, after
complete suspension at a critical stirring speed of 300
rpm. The kinetic analysis using fluid-solid reaction
models and homogeneous reaction models incorporating
graphical and statistical methods proved that the
kinetic model best representing the process was a first-
order pseudo-homogeneous reaction model. A n empiri-
cal kinetic expression including the parameters used in
the study was developed, and this expression can
estimate the conversion fraction with a relative mean
square of errors 0.0627. The activation energy for the
process 51919.77 J mol-I.
Nomenclature
a: a constant in eq 6
aq: aqueous
b: a constant in eq 6
C: acid concentration, w t %
D: particle size, mm
d : a constant in eq 6
EA: activation energy, J/mol
4002 Ind. Eng. Chem. Res., Vol. 34, No. 11, 1995
g: gas
S L : solid-to-liquid ratio, g/mL
- Ferric Chloride Solution. On the Leaching Behavior of Stibnite.
s: solid
ko: a constant in eq 6
T temperature, K
t: time, m i n
X: conversion fraction
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Received for review December 13, 1994
Revised manuscript received May 25, 1995
Accepted May 25, 1995@
I39407363
@Abstract published in Advance A C S Abstracts, August 1,
1995.