Professional Documents
Culture Documents
To cite this article: P. A. Olubambi & J. H. Potgieter (2009) INVESTIGATIONS ON THE MECHANISMS OF SULFURIC ACID
LEACHING OF CHALCOPYRITE IN THE PRESENCE OF HYDROGEN PEROXIDE, Mineral Processing and Extractive Metallurgy
Review: An International Journal, 30:4, 327-345, DOI: 10.1080/08827500902958191
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
Mineral Processing & Extractive Metall. Rev., 30: 327–345, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 0882-7508 print/1547-7401 online
DOI: 10.1080/08827500902958191
INTRODUCTION
Hydrometallurgical processing has become an increasingly important
aspect in the recovery of base and precious metals from complex
sulfide ores. This is because it satisfies industrial requirements
in terms of technical effectiveness, flexibility, ease of operation,
cost-effectiveness, environmental friendliness, and the ability to be
expanded from a small scale. However, hydrometallurgical operations
do suffer some drawbacks, including low recovery of extracted metal,
difficulties in solid–liquid separation, and the effect of impurities
on the ease of purification. Another major problem confronting
hydrometallurgical processing of sulfide ore, especially chalcopyrite, is
low solubility in many leaching solutions. As a result of the diffi-
culty usually encountered in getting the desired metals into aqueous
solution, careful consideration must be given to selecting suitable
leaching reagents for the recovery of the constituent metals.
Among the several factors determining choice and effectiveness,
leaching reagents are usually assessed in terms of dissolution power,
price, and environmental friendliness. Several studies have been
reported on the effectiveness of different reagents for chalcopyrite
leaching. Halogen salts of chlorides and bromides (Stanley and Subra-
manian 1977), chlorine gas-saturated water (Ekinci et al. 1998), and
nitrogen dioxide (Frankiewicz and Lueders 1979a,b) have been used
for copper recovery from chalcopyrite. It should be noted, however,
that these reagents are, in general, very slow in the rate of metal
recovery, coupled with many problems associated with the removal
of iron and effective recovery of copper and zinc from the leach
THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 329
liquors. Prasad and Pandey (1998) reviewed and compared the effec-
tiveness of sulfuric acid, hydrochloric acid, nitric acid, ferric chloride,
and ferrous sulfate for sulfide ore leaching and found that nitric
and hydrochloric acids were comparatively and respectively the most
effective. Since nitric acid and hydrochloric acid usually induce a
very corrosive environment, and thus require very expensive corrosion-
resistant equipment, their industrial applications are limited. A number
of research articles have been focused on acid leaching of sulfide ores
in chloride and sulfate media (Al-Harahsheh et al. 2006; Buttinelli
Downloaded by [Erciyes University] at 13:24 23 December 2014
et al. 1992; Carneiro and Leão 2007; Hirato et al. 1987; Hiroyoshi
et al. 2001; Liddicoat and Dreisinger 2007; Lundström et al. 2005;
Souza et al. 2007). Despite the effectiveness of these reagents, they
suffer the major drawbacks of high corrosiveness and difficulties in
solution recoverability.
In the search for suitable and sustainable alternative leaching
reagents, attention has been refocused on the use of easily available
and cheap reagents like sulfuric acid. Sulfuric acid has been used for
a very long time for sulfide ore leaching, and means for improving
its effectiveness have been investigated by various researchers (Abdel-
Aal 2000; Antonijevic and Bogdanovic 2002, 2004; Havlik et al.
2005; Hiroyoshi et al. 2002; Ivascan and Roman 1975; Koch and
Grasselly 1952; Momade and Momade 1999; Padilla et al. 2003,
2005). Although, sulfuric acid is not as effective as stronger acids
like nitric acid and hydrochloric acid (Copur 2001, 2002; Prasad and
Pandey 1998), it is preferred over all other leaching reagents in terms
of cost, environmental friendliness, fewer corrosion problems, and
ease of its regeneration during electrowinning (Biswas and Davenport
1980).
As a means of optimizing the effectiveness of sulfuric acid
leaching, the possibility exists for using suitable oxidizing agents to aid
its dissolution kinetics. The use of oxygen as an oxidant for sulfuric
acid pressure leaching of chalcopyrite has been investigated under
conditions of varying stirring speed, concentration of sulfuric acid,
temperature, and partial pressure of oxygen (Padilla et al. 2007), and
it was observed that the oxygen partial pressure controlled the selec-
tivity of chalcopyrite dissolution. Several investigations have also been
reported on oxidative dissolution using hydrogen peroxide to aid and
promote the leaching potential of sulfuric acid (Antonijevic et al. 1997;
Eary and Cathles 1983; Jiagang et al. 2002; Olubambi et al. 2006).
330 P. A. OLUBAMBI AND J. H. POTGIETER
66 11 6.8 24 30 31
Leaching Experiments
Leaching experiments were initially carried out in 250 ml Erlenmeyer
flasks at room temperature to assess the amounts of copper and iron
leached. The flasks were placed in an incubator shaker to provide the
necessary stirring and to maintain a constant temperature of 25◦ C.
Analytical grade sulfuric acid (98 vol% H2 SO4 ), hydrogen peroxide (34
vol% H2 O2 ), and distilled water were used. Leaching experiments were
conducted in two stages: sulfuric acid leaching followed by sulfuric acid
leaching in conjunction with hydrogen peroxide.
Sulfuric Acid Leaching. Sulfuric acid solution (1.0 M, 200 ml) was
introduced into the reactor. At the desired temperature, 2 g of the
ore were added to the acid solution and the contents were stirred
at a constant speed of 160 rpm. Two milliliters of pregnant solution
were taken from the reactor every 60 minutes, filtered, and the filtrate
was analyzed for copper and total iron using atomic absorption
spectrometry (AAS).
Electrochemical Study
Electrochemical Cell and Electrodes. A 500 ml Pyrex glass electro-
chemical cell constructed for a conventional three-electrode system was
used for the electrochemical measurements. The counter electrodes
were made of graphite rods of 0.5 mm diameter, while silver/silver
chloride 3 M potassium chloride was used as the reference electrode.
The working electrode was a particulate electrode made from the
powdered sample. These electrodes were prepared similar to the
procedure described by Munoz et al. (1998) and Lu et al. (2000b).
A 0.7 g mass of the base conductor material (powdered graphite) was
mixed with 0.3 g of powdered sample and 0.6 ml silicon oil from Sigma
Aldrich and compressed under pressure using a carbon paste electrode
holder. Electrochemical tests were carried out using an Autolab poten-
tiostat (PGSTAT20 computer controlled) using the General Purpose,
Electrochemical Software (GPES, version 4.9).
The results of the dissolution in the shake flask carried out to asses
the amounts of copper and iron leached are presented in Figures 1
and 2. The results show that increasing the concentration of hydrogen
peroxide considerably accelerated the leaching of both copper and
iron. During sulfuric acid leaching without hydrogen peroxide addition,
very small amounts of copper were leached. Copper leaching rose from
4% within the first hour to a highest amount of 7% at the fifth hour of
leaching. However, when 1 M hydrogen peroxide solution was added,
copper leaching increased drastically from 46% during the first hour
of leaching to a highest amount of 52% in the sixth hour. In all the
concentrations of hydrogen peroxide studied, the highest copper disso-
lution of 87% was obtained at a hydrogen peroxide concentration of
Equation (5):
H2 O2 → HO∗ + OH− (5)
The reactive hydroxyl radical (HO∗ ) reacts with chalcopyrite to
form elemental sulfur (Equation (6)), which is oxidized to sulfate ions
(Equation (7)), and finally reacts with copper and iron ions to form an
aqueous solution of copper and ferrous sulfates (Equations (8) and (9)):
2HO∗ + 2S2− → 2S0 + H2 O + 05O2 (6)
+
2S0 + 3O2 + 2H2 O → 2SO2−
4 + 4H (7)
Cu2+ (aq) + SO2−
4 (aq) → CuSO4 (aq) (8)
Fe (aq) +
2+
SO2−
4 (aq) → FeSO4 (aq) (9)
The amounts of copper and iron dissolved as presented in Figures 1
and 2 revealed an increase in metal dissolution up to a maximum value,
after which there was a general decrease. Although the amounts of
copper and iron dissolved during sulfuric acid leaching were generally
small as compared with hydrogen peroxide additions, it was obvious
that the rate of decrease in dissolution after the maximum value was
reached was not pronounced during sulfuric acid leaching alone as
compared with hydrogen peroxide addition. The decrease in disso-
lution after the maximum value was reached could be attributed to a
decrease in the leaching strength of the media with time. The decrease
in leaching strength was more pronounced as the concentration of
hydrogen peroxide increased, due to its possible decomposition to water
(Equation (10)), which could be greater at higher concentrations:
H2 O2 → H2 O + 05O2 (10)
The further decrease in dissolution after the maximum value was
reached could also be due to cupric and ferrous ions precipitating
336 P. A. OLUBAMBI AND J. H. POTGIETER
from the leaching solution. Hiroyoshi et al. (2004) noted that the
presence of cupric and/or ferrous ions within the leaching system
causes activation (or depassivation) rather than passivation, and a lack
of these ions could lead to a high-resistance passive layer forming
on the chalcopyrite surface. The precipitated products could therefore
possibly hinder the transfer and transportation of both lixiviate to the
mineral’s surface and the solubilized species from the mineral’s surface
to the leaching solution.
Downloaded by [Erciyes University] at 13:24 23 December 2014
Figure 3. SEM micrographs of the residues after leaching in (A) 1 M sulfuric acid; (B) 1 M
sulfuric acid and 1 M hydrogen peroxide; (C) 1 M sulfuric acid and 2 M hydrogen peroxide;
(D) 1 M sulfuric acid and 3 M hydrogen peroxide. (Bar sizes 10 m.)
THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 337
will remain after the initial step as a result of the breaking of the Cu–S
bond. The unstable covellite formed could thus decompose to Cu2+
and promote complete dissolution of the chalcopyrite, as suggested by
Hiroyoshi et al. (2004).
Chalcopyrite oxidation observed during active dissolution was
suggested to be due to the presence of cupric and ferrous ions
(Elsherief 2002; Hiroyoshi et al. 2004; Nava and Gonzalez 2006).
On the other hand, its passivation could result from the presence
of several products including covellite, chalcocite, and sulfur (Arce
and Gonzalez 2002; Hackl et al. 1995; Klauber et al. 2001; Nava
and Gonzalez 2006). This observation was corroborated by the high
amounts of both copper and iron dissolved within the first 60 min
of dissolution in all the leaching media (Figures 1 and 2), which
could have resulted in the increased anodic currents. Elsherief (2002)
and Hiroyoshi et al. (2004) attributed the initial increase in the
anodic current that facilitated chalcopyrite dissolution observed during
active dissolution to the presence and coexistence of both cupric and
ferrous ions (Equation (1)) within the system. According to Nava and
Gonzalez (2006), the initial dissolution could occur when the nonstoi-
chiometric polysulfide (Cu1−x Fe1−y S2−z ) is formed.
The behavior of chalcopyrite observed within the passivity range
can be explained from a sulfur formation viewpoint. According to the
results of the X-ray analysis, elemental sulfur was the major product
formed on the surface of the solid residues after chalcopyrite leaching
in all the media. This is similar to the observation by Klauber et al.
(2001) that elemental sulfur, which can form a passive layer on the
chalcopyrite surface, is probably responsible for the passivation of
the chalcopyrite surface. Passivation could start when the amounts
of copper and iron on the surfaces of the chalcopyrite become very
minimal. According to Hiroyoshi et al. (2004), when the coexistence of
340 P. A. OLUBAMBI AND J. H. POTGIETER
CONCLUSION
Hydrogen peroxide accelerated the formation of elemental sulfur, which
probably passivated the chalcopyrite surface and thus reduced its initial
reactivity. Oxidation of the elemental sulfur to sulfates by hydrogen
peroxide accelerated chalcopyrite dissolution. The increase in the
porous and crystalline nature of the residues with increasing hydrogen
peroxide concentrations reduced the passive nature of chalcopyrite
and promoted dissolution. The presence of hydrogen peroxide can
be concluded to accelerate chalcopyrite leaching through the porous
and permeable nature of the dissolution products. The shape of the
THE MECHANISMS OF SULFURIC ACID LEACHING OF CHALCOPYRITE 343
current–time curves indicates that the controlling factor for the kinetics
in the presence of hydrogen peroxide is electron transfer.
REFERENCES
Abdel-Aal, E. A., 2000, ‘‘Kinetics of sulfuric acid leaching of low grade zinc
silicate ore.’’ Hydrometallurgy, 55, pp. 247–254.
Adebayo, A. O., Ipinmoroti, K. O., and Ajayi, O. O., 2003, ‘‘Dissolution kinetics
of chalcopyrite with hydrogen peroxide in sulphuric acid medium.’’ Chemical
and Biochemical Engineering Quarterly, 17, pp. 213–218.
Downloaded by [Erciyes University] at 13:24 23 December 2014
Al-Harahsheh, M., Kingman, S., and Bradshaw, S., 2006, ‘‘Scale-up possibil-
ities for microwave leaching of chalcopyrite in ferric sulphate.’’ Interna-
tional Journal of Mineral Processing, 80, pp. 198–204.
Antonijevic, M. M. and Bogdanovic, G. D., 2002, ‘‘Leaching of chalcopyrite
ore with sulphuric acid solution. 34th IOC on Mining and Metallurgy,
Bor Lake, Yugoslavia, Technical Faculty Bor, pp. 373–379.
Antonijevic, M. M. and Bogdanovic, G. D., 2004, ‘‘Investigation of the
leaching of chalcopyritic ore in acidic solutions.’’ Hydrometallurgy, 73,
pp. 245–256.
Antonijevic, M. M., Dimitrijevic, M., and Jankovic, Z. 1997, ‘‘Leaching of
pyrite with hydrogen peroxide in sulphuric acid.’’ Hydrometallurgy, 46,
pp. 71–83.
Antonijevic, M. M., Jankovic, Z. D., and Dimitrijevic, M. D., 2004, ‘‘Kinetics
of chalcopyrite dissolution by hydrogen peroxide in sulphuric acid.’’
Hydrometallurgy, 71, pp. 329–334.
Arce, E. M. and Gonzalez, I., 2002, ‘‘A comparative study of electrochemical
behavior of chalcopyrite, chalcocite and bornite in sulfuric acid solution.’’
International Journal of Minerals Processing, 67, pp. 17–28.
Biswas, A. K. and Davenport, W. G., 1980, Extractive Metallurgical of Copper,
Oxford, Pergamon Press, pp. 263–269.
Buttinelli, D., Lavecchia, R., Pochetti, F., Geveci, A., Guresin, N., and
Topkaya, Y., 1992, ‘‘Leaching by ferric sulphate of raw and concentrated
copper-zinc complex sulphide ores.’’ International Journal of Mineral
Processing, 36, pp. 245–257.
Carneiro, M. F. C. and Leão, V. A., 2007, ‘‘The role of sodium chloride on
surface properties of chalcopyrite leached with ferric sulphate.’’ Hydromet-
allurgy, 87, pp. 73–82.
Copur, M., 2001, ‘‘Solubility of ZnS concentrate containing pyrite and
chalcopyrite in HNO3 solutions.’’ Chemical and Biochemical Engineering
Quarterly, 15, pp. 181–184.
Copur, M., 2002, ‘‘An optimization study of dissolution of Zn and Cu in ZnS
concentrate with HNO3 solutions.’’ Chemical and Biochemical Engineering
Quarterly, 16, pp. 191–197.
Eary, L. E. and Cathles, L. M., 1983, ‘‘The kinetics of uranium dioxide disso-
lution in acidic hydrogen peroxide solutions.’’ Metallurgical Transactions,
14B, pp. 10, 325.
344 P. A. OLUBAMBI AND J. H. POTGIETER
Ekinci, Z., Colak, S., Cakici, A., and Sarac, H., 1998, ‘‘Leaching kinetics of
sphalerite with pyrite in chlorine saturated water.’’ Minerals Engineering,
11, pp. 279–283.
Elsherief, A. E., 2002, ‘‘The influence of cathodic reduction, Fe2+ and
Cu2+ ions on the electrochemical dissolution of chalcopyrite in acidic
solution.’’ Minerals Engineering, 15, pp. 215–223.
Frankiewicz, T. C. and Lueders, R. E., 1979a, ‘‘Copper leaching employing
nitrogen dioxide as oxidant.’’ U.S. Patent 4, 132, 758.
Frankiewicz, T. C. and Lueders, R. E., 1979b, ‘‘High slurry density mineral
leaching using nitrogen dioxide.’’ U.S. Patent 4, 144, 310.
Hackl, R. P., Dreisinger, D. B., Peres, E., and King, J. A., 1995, ‘‘Passivation
Downloaded by [Erciyes University] at 13:24 23 December 2014
Lu, Z. Y., Jeffrey, M. I., and Lawson, F., 2000a. ‘‘The effect of chloride ions
on the dissolution of chalcopyrite in acidic solutions.’’ Hydrometallurgy,
56, pp. 189–202.
Lu, Z. Y., Jeffrey, M. I., and Lawson, F., 2000b. ‘‘An electrochemical study
of the effect of chloride ions on the dissolution of chalcopyrite in acidic
solutions.’’ Hydrometallurgy, 56, pp. 145–155.
Lundström, M., Aromaa, J., Forsén, O., Hyvärinen, O., and Barker, M. H.,
2005, ‘‘Leaching of chalcopyrite in cupric chloride solution.’’ Hydromet-
allurgy, 77, pp. 89–95.
Mahajan, V., Misra, M., Zhong, K., and Fuerstenau, M. C., 2007, ‘‘Enhanced
leaching of copper from chalcopyrite in hydrogen peroxide–glycol
Downloaded by [Erciyes University] at 13:24 23 December 2014