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hydrometallurgy

ELSEVIER Hydrometallurgy 42 (1996) 377-386

Kinetics of pyrite dissolution by hydrogen peroxide


in perchloric acid
M. Dimitrijevic *, M.M. Antonijevic, Z. Jankovic
Technical Faculty Bor, University of Belgrade, P.O. Box SO, 19210 Bor, Yugoslavia

Received 4 May 1995; accepted 20 September 1995

Abstract

The kinetics of pyrite dissolution by hydrogen peroxide in perchloric acid were investigated.
The effects of stirring speed, temperature, hydrogen peroxide and perchloric acid concentrations
and particle size were examined. The activation energy was calculated to be 57 kJ/mol, indicating
that the dissolution of pyrite is chemically controlled. The order of the reaction with respect to
hydrogen peroxide was found to he approximately 1. The perchloric acid concentration had
practically no effect on the rate of pyrite dissolution. In addition, the effects of H+, ClO,, and
SOi- ions were examined.

1. Introduction

Complex ores of chalcopyrite, sphalerite and galena, which represent a potentially


important resource of copper, zinc, lead and other metals, are always associated with the
pyrite constituting the bulk of these ores. The ore minerals are intimately intergrown and
this restricts the use of conventional techniques of mineral separation to produce bulk
concentrates. In searching for a convenient hydrometallurgical method of processing
such concentrates, it is important to understand the behaviour of each of the minerals
mentioned.
The dissolution of pyrite has most often been investigated in the presence of oxygen
at elevated temperatures and pressures [l-5], as well as in the presence of iron(II1) [6,7],
chlorine [8], chromium(W) [9,101, hydrogen peroxide [l I], etc.
The use of hydrogen peroxide as the oxidizing agent for hydrometallurgical processes
has been increasingly studied. McKibben [ 11I studied the kinetics of aqueous oxidation
of pyrite by hydrogen peroxide at pH l-4 and 293-313 K. Vazarlis [12] leached a

* Corresponding author. E-mail: mile@nastava.tf.bor.ac.yu

0304386X/96/$15.00 Copyright 0 19% Elsevier Science B.V. All rights reserved.


SSDI 0304-386X(95)00094- 1
378 M. Dimitrijevic et al./ Hydrometallurgy 42 (1996) 377-386

zinc-lead bulk sulphide concentrate with H,O, at atmospheric pressure and 368 K.
Balaz and Ebert [13] studied the leaching of mechanically activated sphalerite with
H,O, at atmospheric pressure and at room temperature. Dechenes and Ghali [ 141 found
H,O, to be an appropriate oxidant for treating a gold-containing chalcopyrite concen-
trate. Hydrogen peroxide has also been used as the oxidizing agent for the in situ
leaching of uranium ores frequently associated with pyrite [15,16].
The dissolution of pyrite by hydrogen peroxide in acidic solutions is characterized by
the overall reaction [171:
FeS, + 7.5H,O, = Fe3++ 2SO42- + H++ 7H,O
and in highly acidic solutions by the reaction [l 11:
FeS, + 7.5H,O, + H+= Fe3++ 2HSO; + 7H,O
the products of both reactions being soluble. Also thermodynamically possible is
oxidation with sulphur formation:
FeS, + 1.5H,O, + 3Hf= Fe3+ + 2s” + 3H,O
The objective of this investigation was to study the kinetics and mechanism of pyrite
dissolution by hydrogen peroxide in perchloric acid solution.

2. Experimental

The experiments were carried out with a sample of pyrite concentrate from the Veliki
Krivelj copper mine (Serbia). The concentrate assayed 45.38% Fe, 52.17% S and 0.88%
SiO,. X-ray diffraction analysis revealed the presence of pyrite and a small amount of
quartz. The sample was sieved into several size fractions. All experiments were
performed with the 0.050-0.063 mm fraction unless otherwise stated.
The solution was investigated in a 500 ml glass reactor equipped with a glass stirrer.
The reactor was filled with 250 ml of acidic peroxide solution which was heated to the
desired temperature. When the desired temperature was attained, a charge of 0.500 g of
pyrite was added to the peroxide solution, stirring was started, and the temperature of
the reaction mixture was then maintained constant. The fraction of pyrite reacted was
followed over time; at definite time intervals 6 samples of 1 ml each were taken for the
determination of iron by AAS. The reaction residues after oxidation were washed with
distilled water, dried and examined by X-ray diffraction analysis. The sulphates were
determined gravimetrically as BaSO,.

3. Results and discussion

3.1. Effect of stirring

The effect of stirring on the rate of pyrite dissolution was investigated in 2.0 M
hydrogen peroxide in 0.50 M perchloric acid, at 303 K. The stirring speeds applied were
M. Dimitrijevic et al./ Hydrometallurgy 42 (1996) 377-386 379

- “0 StirrinQ

-E+ 1000Vmin

T = 303 K

0 50 100 150 200


Time, min

Fig. 1. Effect of stirring speed on pyrite dissolution.

400, 700 and 1000 min- ’. The results obtained (Fig. 1) show that the rate of pyrite
dissolution is independent of the stirring speed, which indicates that the reaction is not
controlled by diffusion. Slightly more rapid dissolution of pyrite in the absence of
mechanical stirring can be attributed to a somewhat higher hydrogen peroxide concentra-
tion, since stirring accelerates the decomposition of hydrogen peroxide, thus reducing
the available amount for the reaction. It should be noted that, in addition to mechanical
stirring, there was mixing caused by the bubbles of molecular oxygen produced by
hydrogen peroxide decomposition; it is known that hydrogen peroxide is subject to
spontaneous decomposition with the evolution of oxygen gas, which is more pronounced
in the presence of the Fe3+ ions that are produced by the dissolution of pyrite and act as
a catalyst for peroxide decomposition [16,18].
All subsequent experiments were carried out without mechanical stirring. Stirring was
only used prior to sampling in order to homogenize the solution.

3.2. EfSect of temperature

The dissolution of pyrite was carried out in the temperature range 293-323 K, with
an initial hydrogen peroxide concentration of 2.0 M in 0.50 M perchloric acid. The
dissolution curves are given in Fig. 2 and show an increase in the pyrite conversion with
increasing temperature.
As seen from Fig. 2, the dissolution of pyrite ceased after about 90 min at 318 and
323 K. The reason for this phenomenon was a rapid decomposition of hydrogen
peroxide, due to elevated temperatures.
On the basis of the Eh-pH diagrams for the systems H,O,-H20, FeS,-H,O and
S-H,O, the products of the reaction expected are Fe3+, SOi- and HSO; ions. X-ray
diffraction analyses of the solid residues after dissolution revealed the presence of pyrite,
quartz, and traces of elemental sulphur. The small amounts of elemental sulphur formed
380 M. Dimitrijevic et al./ Hydrometallurgy 42 (1996) 377-386

- 293 K + 298 K + 303 K 8 308 K

‘t * 313 K + 318K -A- 323 K

0
d

0 50 100 150 200


Time, min

Fig. 2. Effect of temperature on pyrite dissolution.

floated on the solution surface and adhered to the walls of the reaction vessel. A separate
experiment was carried out in order to determine the amount of sulphide sulphur
oxidized to the elemental form. For this, 1.000 g of pyrite was treated by 500 ml of
peroxide solution (2.0 M H,O,, 0.50 M HClO,) at room temperature until total
dissolution was achieved, and from the final solution the amount of sulphates was
determined gravimetrically. On the basis of the amount of sulphide sulphur in the
starting 1.000 g of pyrite and that of sulphur in the form of sulphate in the final solution,
the amount of elemental sulphur in the final solution was calculated. In this manner, it
was calculated that 3% and 97% of the sulphide sulphur from the pyrite was oxidized to
elemental sulphur and sulphate ion, respectively, under the conditions given.
The data given in Fig. 2 were analysed with the aid of the surface reaction control
shrinking core model [191:

1-(1-X)“3=k,t (4)
where: X is the fraction of pyrite reacted; k, is the apparent rate constant; and t is time.
The variation in 1 - (1 - X)‘13 with time for different temperatures is shown in Fig. 3.
The apparent rate constants obtained from the slopes of the lines in Fig. 3 were used to
determine an activation energy of 57 kJ/mol, as shown in Fig. 4. This magnitude of
activation energy confirms the proposed surface reaction control model. When leaching
pyrite with hydrogen peroxide, McKibben [ 111 found an activation energy of 33.3 rf: 12.5
kJ/mol. An activation energy of 50 kJ/mol was found in our recent study of the
leaching of pyrite by potassium dichromate [9].

3.3. Eflect of initial particle size

The effect of initial particle size on the rate of pyrite dissolution was studied by
treating four size fractions (0.040-0.050, 0.050-0.063, 0.063-0.080, and 0.080-0.100
M. Dimitrijevic et al./HydrometaNurgy 42 (1996) 377-386 381

l/3
1-(1-X)

0.6

0.5

0.4

0.3

0.2

0.1

C
50 100 150 200
Time, min

Fig. 3. The variation in 1 --cl -X)‘13 with time at various temperatures. Symbols as in Fig. 2.

mm) with 2.0 M hydrogen peroxide in 0.50 M perchloric acid, at 303 K. The results
obtained are shown in Fig. 5. As expected, the smaller the particle size, the faster the
dissolution of pyrite. The data from Fig. 5 were analysed according to the surface
reaction model, Eq. (41, and the calculated apparent rate constants are plotted versus the
reciprocal of the initial particle radius in Fig. 6. The linear relationship between k, and
l/r, again confirms the proposed surface reaction model.

3.4. Effect of initial hydrogen peroxide concentration

This effect on pyrite dissolution was examined by varying the initial hydrogen
peroxide concentration in the range 0.30-5.0 M in 0.50 M perchloric acid, at 303 K.
The results showed a linear dependence in the range 0.30-1.0 A4 as well as a parabolic

In ( kS. l/min 1

3 3.1 3.2 3.3 3.4 3.5


1000/T, l/K

Fig. 4. Anhenius plot for pyrite dissolution.


382 M. Dimitrijevic et al./Hydrometallurgy 42 (19%) 377-386

50 100 150
Time, min

Fig. 5. Effect of particle size on pyrite dissolution.

dependence in the range 2.0-5.0 M, thekinetic curves being more parabolic with higher
initial peroxide concentrations. The possible cause of this phenomenon was the oxygen
produced by hydrogen peroxide decomposition, which was adsorbed on the surface of
pyrite particles and retarded the adsorption of hydrogen peroxide on the same surface,
resulting in a decrease in the rate of pyrite dissolution; the higher the hydrogen peroxide
concentration, the larger was the amount of oxygen produced and the reaction rate
decreased more rapidly.
The data obtained were analysed according to Eq. (4) and the apparent rate constants
were determined (Fig. 7). For hydrogen peroxide concentrations of 4.0 M and 5.0 M the
last (180 min) and last two analyses (120 and 180 min), respectively, were not taken into
consideration when calculating the apparent rate constants because of a greatly de-

1000 kS j l/min

iH2021=20M

2- t HC’O4 ] = 05 M

T = 303 K

l/r0 I l/mm

Fig. 6. Plot of k, versus l/r,,.


M. Dimitrijevic et al./Hydrometallurgy42 (1996) 377-386 383

0 50 100 150 200


Time, min

Fig. 7. The variation of 1- (1 - X)‘13 with time for various hydrogen peroxide concentrations.

creased reaction rate, due to hydrogen peroxide decomposition. The rate constants were
used to make a plot of logarithm of k, versus the logarithm of hydrogen peroxide
concentration, from which a reaction order of 1.26 with respect to hydrogen peroxide
concentration was calculated. This result is in accordance with the first-order depen-
dence reported by McKibben [ 111.
3.5. Eflect of initial perchlotic acid concentration
This effect was examined in solutions containing different initial perchloric acid
concentrations (0.10-2.0 M) at 303 K in 2.0 M hydrogen peroxide. The kinetic curves
showed that the initial perchloric acid concentration has essentially no effect on the rate
of pyrite dissolution. Furthermore, in the absence of the acid the fraction of pyrite
reacted was very small and pyrite dissolution practically ceased after 90 min. There are
several reasons for this phenomenon. First, the acid inhibits the decomposition of
hydrogen peroxide; in the absence of the acid, peroxide decomposition was rapid from
the beginning and most of the peroxide was decomposed in a rather short time. Second,
the Fe3+ ions produced by the dissolution of pyrite hydrolyse to ferric hydroxide, which
also may retard the pyrite-peroxide contact by precipitating on the surface of pyrite
particles. Last, the oxidative action of hydrogen peroxide is more pronounced in acidic
solutions.
It was observed during the experiments that the amount of oxygen produced
decreased with increasing perchloric acid concentration from 0.10 M to 2.0 M whereas
the fraction of pyrite reacted remained almost unchanged. This indicates that the
molecular oxygen does not act as an oxidant.
The kinetic data were analysed using EQ. (4) and by plotting In k, versus In [HClO,]
the order of 0.10 with respect to perchloric acid was determined. These findings are in
agreement with the results of McKibben [l 11, who has established that the rate of pyrite
dissolution with hydrogen peroxide is independent of acidity below pH = 4.
384 M. Dimitrijevic et al./Hydrometallurgy 42 (19%) 377-386

T = 303 K

0 50 100 150 200


Time, min

Fig. 8. Effect of perchlorate ion concentration on pyrite dissolution.

3.6. Effect of hydrogen ion concentration

The effect of hydrogen ion concentration was studied with 2.0 M hydrogen peroxide
at 303 K. The investigation was carried out by adjusting solution ionic strength to a
constant value of 2.0 M using sodium perchlorate, and hydrogen ion concentration was
varied from 0.10 M to 2.0 M by adding perchloric acid. The kinetic data were analysed
according to Eq. (4). A plot of In k, versus In [H+] gave an reaction order of 0.10 with
respect to hydrogen ion. On the basis of the fact that the reaction order with respect to
hydrogen ion equals that with respect to perchloric acid, it may be concluded that the
effect of perchloric acid concentration is essentially the effect of the hydrogen ion
concentration.

3.7. Effect of perchlorate ion concentration

On the basis of the effect of hydrogen ion it can be concluded that the perchlorate ion
has no effect on pyrite dissolution; however, the experiments were performed in order to
confirm the conclusion. The experiments were carried out with 2.0 M hydrogen
peroxide at 303 K. The perchlorate ion was added in the form of sodium perchlorate in
the concentration range 0.10-2.0 M. The results are given in Fig. 8 and confirm that the
perchlorate ion has no effect on pyrite dissolution. This fact can be attributed to the high
stability of the per-chlorate ion in aqueous solutions.

3.8. Effect of sulphate ion concentration

It was of interest to examine the effect of sulphate ion concentration because the
sulphate ion is a product of pyrite dissolution. The experiments were performed with 2.0
M. Dimitrijevic et al./Hydrometallurgy 42 (1996) 377-386 385

M hydrogen peroxide in 0.50 M perchloric acid, at 303 K, by adding the sulphate ion as
sodium sulphate in the concentration range 0.02-0.20 M. The results showed that the
rate of pyrite dissolution decreases as sulphate ion concentration increases. The kinetic
curves were linearized by means of Eq. (4) and the reaction order with respect to
sulphate ion was determined as - 0.21. The cause for the inhibiting effect is possibly the
adsorption of sulphate ions on the pyrite surface, which retards the adsorption of
hydrogen peroxide on the same surface and therefore decreases the rate of pyrite
dissolution.

3.8.1. Reaction mechanism


Since the kinetics of pyrite dissolution by hydrogen peroxide in perchloric acid are
well described by Eq. (4), it can be assumed that the chemical reaction at the mineral
surface is rate-controlling. The results further supporting the assumption are the value of
the activation energy of 57 kJ/mol and a linear plot of k, versus l/r,.
On the basis of the results obtained, it can be assumed that the oxidation of pyrite by
hydrogen peroxide takes place through ‘thio’ intermediates such as S,Oi- and S,Oi-;
because of the fact that, in addition to sulphate ions, small amounts of elemental sulphur
were generated in the leaching solution. Thiosulphate is either further oxidized to
sulphate or decomposes to produce elemental sulphur and bisulphite, according to the
following reaction scheme [20]:

4. Conclusion

From the results of this investigation, the following conclusions can be drawn:
1. The kinetics of pyrite dissolution may be described by the surface reaction model
1 - (1 - X)“3 = k, . t. Th e magnitude of the activation energy of 57 kJ/mol and the
linear relationship between k, and l/r,, both confirm the proposed surface reaction
model.
2. The order of the reaction is approximately 1 with respect to hydrogen peroxide
concentration, which indicates that the peroxide concentration considerably affects
the rate of pyrite dissolution.
3. Perchloric acid (i.e., hydrogen ion) has practically no effect on pyrite dissolution.
4. Perchlorate ions have no effect on the rate of pyrite dissolution.
5. Sulphate ions have very little effect on the rate of pyrite dissolution.
386 M. Dimitrijevic et al./Hydrometallurgy 42 (1996) 377-386

References

[l] Bailey, L.K. and Peters, E., Can. Metall. Q., 15 (1976): 333-344.
[2] Gerlach, J., Hahne, H. and Pawlek, F., Erzmetall, 19 (1%6): 66-74.
[3] McKay, D.R. and Halpem, J., Trans. Metall. Sot. AIME, 6 (1958): 301-309.
[4] Vracar, R., Zh. Prikl. Khim., 60 (1987): 1458-1465.
[5] Papangelakis, V.G. and Demopoulos, G.P., Hydrometallurgy, 26 (1991): 309-325.
[6] Kawakami, K., Sato, I., Kusunoki, K., Kusukabe, K. and Morooka, Sh., Ind. Eng. Chem. Res., 27 (1988):
571-576.
[7] Sakai, N., Ishizaki, Ch., Chida, T. and Shimoiizaka, J., I. Min. Metah. (Jpn.), 103 (1987): 395-m.
[8] Lotens, J.P. and Wesker, E., The behaviour of sulphur in the oxidative leaching of sulphidic minerals.
Hydrometallurgy, 18 ( 1987): 39-54.
[9] Antonijevic, M.M., Dimitrijevic, M. and Jankovic, Z., Hydrometallurgy, 32 (1993): 61-72.
[lo] Antonijevic, M.M., Dimitrijevic, M. and Jankovic, Z., J. Serb. Chem. Sot., 60 (1995): 241-249.
[l 11 McKibben, M.A., Ph.D. Thesis, Pennsylvania State Univ. (1984).
[12] Vazarlis, H.G., Hydrochloric acid-hydrogen peroxide leaching and metal recovery from a Greek
zinc-lead bulk sulphide concentrate. Hydrometallurgy, 19 (1987): 243-251.
[13] Balaz, P. and Ebert, I., Hydrometallurgy, 27 (1991): 141-150.
[14] Deschenes, G. and Ghali, E., Leaching of gold from a chalcopyrite concentrate by thiourea. Hydrometal-
lurgy, 20 (1988): 179-202.
[15] Hiskey, J.B., Trans. Inst. Min. Metal]., C 89 (1980): 145-152.
[16] Eary, L.E., Barnes, H.L. and Cathles, M., Metall. Trans., 17B (1986): 405-413.
[17] Eary, L.E., Metall. Trans., 16B (1985): 181-186.
[18] Kanungo, S.B., Parida, K.M. and Sam, B.R., Electrochim. Acta, 26 (1981): 1157-1167.
[19] Sohn, H.Y. and Wadsworth, M.E., Rate Processes of Extractive Metallurgy. Plenum Press, New York
(19791, pp. 133-186.
[20] Mishra, K.K. and Osseo-Assare, K., J. Electochem. Sot., 135 (1988): 2502-2509.