Hydrometallurgy 119-120 (2012) 4046

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Hydrometallurgy
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Leaching of copper and zinc from copper converter slag otation tailings using H2SO4
and biologically generated Fe2(SO4)3
Maxim I. Muravyov a,, Natalya V. Fomchenko a, Alexey V. Usoltsev b,
Evgeniy A. Vasilyev b, Tamara F. Kondrat'eva a
a
Laboratory of Chemolitothrophic Microorganisms, Winogradsky Institute of Microbiology, Russian Academy of Sciences, 117312 Moscow, Russia
b
Laboratory of Hydrometallurgy and Dressing, Research Center, Uralelectromed, 624091 Verkhnyaya Pyshma, Russia

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

Article history: Leaching of converter slag otation tailings from the Svyatogor copper smeltery (Sverdlovsk region, Russia)
Received 6 July 2011 by sulfuric acid solutions containing ferric ions was investigated. The solutions were obtained using oxidation
Received in revised form 27 February 2012 of ferrous sulfate by a consortium of moderately thermophilic acidophilic chemolithotrophic microorgan-
Accepted 4 March 2012
isms, including Sulfobacillus species. Flotation tailings contained 0.56% Cu and 4.74% Zn. Copper was present
Available online 10 March 2012
mostly as digenite, bornite, and free metal. Zinc was present as a ferrite (franklinite) ZnFe2O4 and, to a lesser
Keywords:
degree, as silicate. The effects of pH, pulp density, temperature, initial Fe 3 + concentration, and the presence
Copper converter slag of oxygen in the leaching solution on the leaching dynamics of copper, zinc, and iron were investigated. In-
Flotation tailings creasing Fe 3 + concentrations was found to have an inhibitory effect on zinc and iron leaching, but not on
Zinc ferrite copper leaching. Temperature had the most pronounced effect on the kinetics of copper and zinc leaching.
Ferric sulfate leaching Kinetic analysis was carried out, and the calculated activation energies for copper and zinc leaching were
Sulfuric acid dissolution 51.3 and 53.8 kJ/mol, indicating control of this process by a chemical reaction on the particle surface. The
recommended technological parameters for leaching of copper (the most important component) from con-
verter slag otation tailings are: pulp density of 30% (w/v), pH 1.5, temperature of 70 C, initial Fe 3 + concen-
tration of 15.7 g/L, no aeration, leaching for 1.5 h. This process resulted in solubilization of 81.6% copper and
37.7% zinc with the relatively low iron recovery of 26.2%. Metal content in the leach residue was 0.13% Cu and
3.69% Zn.
2012 Elsevier B.V. All rights reserved.

1. Introduction ecosystems reaches the critical level. Development of waste-free

technologies, including the technologies for ore mining and proces-
Slags are a left-over of the pyrometallurgical stages of recovery of sing which imply utilization of the by-products, is signicant for
non-ferrous metals from sulde materials. Production of 1 t of copper such a solution. Potentially, slags are a source of non-ferrous metals,
results on average in formation of 2.2 t of slag; the annual global out- which are often present in the concentrations exceeding those of
put of copper-smelting slags is ~ 25 Mt (Gorai et al., 2003). Due to the the processed ores. Slags may therefore be considered as a techno-
absence of an accepted efcient technology for extraction of iron and genic source. High metal prices make it economically desirable to pro-
non-ferrous metals from slags, they are accumulated in heaps. In Rus- cess the slags as sources of non-ferrous metals. After recovery of non-
sia, ~550 Mt of the slags of non-ferrous metallurgy have been accu- ferrous metals, the slags may be used in the production of construc-
mulated. Over 1.5 Mt of dumped slags, including converter slag tion mixtures and cements (Alp et al., 2008; Atzeni et al., 1996), lling
otation tailings, which contain up to 6000 t copper and 60,000 t railroad beds and highway shoulders (Shen and Forssberg, 2003), in
zinc, are produced yearly by the copper-smelting plants of the Ural production of glass ceramics (Coruh et al., 2006), etc.
Mining and Metallurgical Company (UMMC) alone. Signicant areas Techniques for processing the slag heaps have been investigated
required for stockpiling of the slags and the products of their proces- for decades. Several methods of processing of the slags of copper
sing are unavailable for land utilization. Leakage uxes of toxic metals smelting and converting have been suggested, including reductive-
developing around the sites of slag stockpiling have a long-term neg- suldizing depletion in electric furnaces (Kim, 1981), sulfating roast-
ative effect on the biosphere (Manz and Castro, 1997). The Ural terri- ing with H2S, H2SO4, Fe2(SO4)3xH2O, (NH4)2SO4 and other reagents
tory is an industrial region where the anthropogenic load on the (Altundogan and Tumen, 1997; Arslan and Arslan, 2002; Hamamci
and Ziyadanogullari, 1991; Sukla et al., 1986; Ziyadanogullari,
1992), and otational depletion (Barnes et al., 1993; Rao and Nayak,
Corresponding author. Tel.: + 7 499 135 0421; fax: + 7 499 135 6530. 1992). The resulting products are processed further (Rudnik et al.,
E-mail address: [email protected] (M.I. Muravyov). 2009) or returned for smelting, while the waste is collected in heaps.

0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2012.03.001
 M.I. Muravyov et al. / Hydrometallurgy 119-120 (2012) 4046 41

Hydrometallurgical techniques for processing (leaching) the slags Thus, the treatment of converter slag otation tailings may be car-
and the products of their depletion recently attracted attention. These ried out as follows: (a) the chemical leaching by a biogenic ferric sul-
techniques include: leaching with chlorate (Yang et al., 2010), hydro- fate solution in sulfuric acid medium; (b) removal of Fe 3 + ions after
gen peroxide (Banza et al., 2002), solutions of sulfuric acid (Anand et the chemical leaching of slag by addition of CaO or CaCO3 into the
al., 1983), ferric sulfate or chloride (Anand et al., 1980; Carranza et al., pulp with following solidliquid separation; (c) copper cementation
2009a, 2009b), potassium dichromate (Altundogan et al., 2004), and from liquid phase; (d) removal of zinc (as ZnS) by addition of NaHS
aquatic solutions of SO2 (Ahmed et al., 2000; Gbor et al., 2000). Indus- (Khalezov et al., 2005) with following solidliquid separation; and
trial application of these techniques is, however, impeded by their (e) separation obtained liquor (after non-ferrous metal removal)
high cost and the heavy environmental problems caused by discharge into two parts, the rst part of the ow may be used as a coagulator,
of toxic liquid waste. the second part (after dilution with an aqua) is sent to biooregenera-
Since most minerals exist in mineral associations, recovery of non- tion and further to step (a).
ferrous and noble metals from technogenic waste is a difcult task. The goal of the present work was to investigate the processes of
Bioleaching (biooxidation) of sulde materials and non-ferrous met- leaching of non-ferrous metals from otation tailings of the copper
allurgical waste may be an efcient and environmentally friendly al- converter slag with ferric sulfate solutions in sulfuric acid medium
ternative to traditional pyro- and hydrometallurgical processes. obtained using a consortium of acidophilic chemolithotrophic
Bioleaching of refractory sulde ores for gold recovery (van Niekerk, microorganisms.
2009) and heap bioleaching of non-ferrous metals from off-grade
and low-grade ores (Watling, 2006) have long been used as efcient 2. Materials and methods
and economically protable techniques for processing such materials.
The processes of two-stage bacterialchemical leaching were pro- 2.1. Slag otation tailings characterization
posed by various authors for treatment of sulde raw materials and
concentrates. Its modications have been tested using sulde copper Flotation tailings were obtained under industrial conditions as a
concentrates (Kinnunen et al., 2006; Muravyov et al., 2011; Romero waste of dressing of converter slag of the Svyatogor copper smeltery
et al., 2003), copperzinc waste of sulde ore dressing (Fomchenko (Sverdlovsk region, Russia), at the same time the otation concen-
and Biryukov, 2009), and gold-bearing sulde concentrates trate is recycled to the smelter. The product contains mainly magne-
(Fomchenko et al., 2010), etc. During the rst stage, the metals are tite Fe3O4, fayalite Fe2SiO4, and glass in fusion with franklinite
leached by microbially produced ferric sulfate. The pulp density may ZnFe2O4 and zinc silicates. Copper minerals were represented by in-
be signicantly higher than in traditional biohydrometallurgical tech- clusions and fusions with glass of digenite, bornite, chalcopyrite, and
nology and the process temperature may be up to 80 C, which in- metallic copper. The P95 was 0.071 mm. The chemical composition
creases its rate signicantly. During the second stage, ferric iron is of the converter slag otation tailings is presented in Table 1.
regenerated, elemental sulfur is oxidized, and suldes are terminally
oxidized. Depending on the temperature conditions at the rst 2.2. Generation of ferric iron for the chemical leaching experiments
stage, regeneration is carried out by different communities of acido-
philic chemolithotrophic microorganisms. Biological oxidation is the A moderately thermophilic microbial community containing Sulfo-
most simple way to regenerate of ferric iron at a low cost. The separa- bacillus thermosuldooxidans VKM B-1269 T, Sulfobacillus strains Sh1
tion of the chemical and biological stages of the process makes it pos- and Sh8, as well as the pulp from the bioreactors of the Olimpiada
sible to create conditions favorable for the chemical processes of gold processing plant (Krasnoyarsk region, Russia), and the enrichment
mineral oxidation and for microbial activity. This technique for leach- culture obtained on the copperzinc otation waste of the Uchalinskoe
ing of non-ferrous metals is sufciently exible to be applied to al- deposit were used as inocula to obtain the ferric iron-containing culture
most any material containing non-ferrous metals as sulde liquid for the subsequent chemical leaching experiments. Biooxidation
minerals, including converter slags of copper-smelting plants. Analy- of ferrous iron (FeSO47H2O) was carried out in a 5.0-L vessel with
sis of the slags revealed that copper was mostly present as suldes 4.0 L of the liquid at 40 C and aeration rate 4 min- 1. The liquid phase
fused with glass, oxidized minerals, and metal copper (Carranza et was 9 K medium (Silverman and Lundgren, 1959) supplemented with
al., 2009b), which is also oxidized and solubilized by solutions of fer- 0.02% (w/v) of yeast extract and 10% (v/v) inoculum. The nal Fe3 +
ric sulfate. Converter slags of copper-smelting plants are specic concentration was 33.6 g/L at pH 1.6. This liquid (microbial cells were
products containing up to 50% iron, mainly as magnetite and silicate not separated) or its dilutions with distilled water were used as lixiviant
(fayalite), as well as silicates of other metals, including zinc. Dissolu- during the chemical leaching experiments.
tion of silicates in sulfuric acid medium used in the processes of bac-
terialchemical leaching may result in formation of silica gel 2.3. Chemical leaching experiments
according to the following equations:
Chemical leaching was carried out in a 2.0-L reactor containing
M2 SiO4 2H2 SO4 2MSO4 H4 SiO4 1 1.0 L of the pulp. The stirring rate was 760 rpm. The temperature
was maintained by means of heat exchangers connected to a thermo-
stat. The leaching was carried out at batch conditions. The solid phase
H4 SiO4 H2 SiO3 H2 O 2
was loaded and mixed with the Fe 3 +-containing solution. The liquor
was preheated to the desired temperature. Sulfuric acid (98.5%) was
H2 SiO3 SiO2 H2 O 3 added when necessary to maintain the pH value. The data obtained
were used to calculate the metals recovery into solution and the aver-
where M is a metal (Fe, Zn, Cu, Co, etc.). age rate of changes of the copper and zinc ions concentrations in the
The presence of a silica gel makes it difcult or impossible to carry liquid phase.
out the subsequent operations of phase separation (ltration or sedi-
mentation) and extraction of metals from the solutions (liquid ex- Table 1
traction, chemical precipitation, etc.). The process of recovery of Analytical data for the converter slag otation tailings.
non-ferrous metals from industrial slags should therefore create the Element Fe Cu Zn S SiO2
conditions making it possible to solubilize non-ferrous metals with
Content (wt.%) 43.3 0.56 4.74 1.4 21.02
the minimal dissolution of the silicate phase.
42 M.I. Muravyov et al. / Hydrometallurgy 119-120 (2012) 4046

2.4. Analytical methods Moreover, decreased pH during chemical leaching means excessive
consumption of sulfuric acid.
The values of pH and Eh were measured with a pH-150MA pH The experiments were carried out at 40 C, initial Fe 3 + concentra-
metermillivoltmeter (Belarus). Redox potential was measured with tion in the liquid phase of 5.3 g/L, and 10% pulp density (w/v). The pH
a platinum electrode relative to the silver chloride electrode; the value was adjusted at 1.5 or 1.8.
values were recalculated relative to the normal hydrogen electrode. The results are presented in Fig. 1. They show that while ~40% of
The concentrations of Fe 3 + and Fe 2 + ions in the liquid phase were copper was solubilized during the rst 5 min of the process, zinc ex-
determined by reaction with potassium thiocyanate (Reznikov et al., traction did not exceed 10%. This may be due to the fact that oxidized
1970) on a KFK-3 photometer (Russia) at = 475 nm. The concentra- copper compounds and metallic copper reacted during the rst mi-
tions of copper and zinc ions were determined on a Perkin Elmer nutes of the process. Suldes were probably oxidized later. During
3100 ame atomic absorption spectrometer (USA). 5 h of chemical leaching of converter slag otation tailings at pH
The content of copper, zinc and iron in the solid phase was deter- 1.5, 73.0% copper and 23.8% zinc was solubilized, while at pH 1.8
mined by its dissolution in the mixture of concentrated hydrochloric the values were 65.2 and 17.0%, respectively.
and nitric acids (3:1 v/v) supplemented with ammonium uoride Consumption of sulfuric acid for pH maintenance at 1.5 and 1.8
under boiling conditions and subsequent determination of the con- during ve hours was 258 and 201 g/kg, respectively. Over 50% of
centrations of dissolved copper, zinc and iron by the atomic absorp- the acid was consumed during the rst 5 min of the process.
tion method. Dissolution of fayalite, as expressed by solubilization of ferrous
iron, was higher at pH 1.5. In this case, iron extraction was 17.1%,
3. Results and discussion while it was only 11.0 at pH 1.8. Moreover, a decrease of Fe 3 + con-
centration was more pronounced than at pH 1.5 because of jarosite
Considering the mineralogical composition of converter slag ota- formation.
tion tailings from the Svyatogor copper smeltery (Sverdlovsk region, Thus, pH 1.5 is preferable for chemical leaching of otation tailings
Russia), chemical leaching of non-ferrous metals with ferric iron- of converter slag due to better solubilization of copper and zinc, a
containing sulfuric acid solutions should be based mainly on the fol- small increase in fayalite solubility, and less intense formation of jar-
lowing reactions of oxidation or dissolution of metallic copper, digen- osite sediments.
ite, bornite, magnetite, and copper and franklinite:
3.2. Effect of pulp density
0 3 2 2
Cu 2Fe Cu 2Fe 4
The hydrodynamic conditions of a reactor is an important param-
3 2 2 eter of chemical processes. It is crucially important in reactions con-
u9 S5 8Fe 5CuS 4Cu 8Fe 5
trolled by the rate of diffusion processes. The content of the solid
u5 FeS4 4Fe
3
2CuS uFeS2 2Cu
2
4Fe
2
6 phase in a suspension (pulp density) is one of the major parameters
affecting hydrodynamic conditions in the reactor. In order to deter-
3 2 2 0 mine the effect of the hydrodynamic situation in the reactor on the ef-
CuS 2Fe Cu 2Fe S 7
ciency and rate of chemical leaching of non-ferrous metals from
2 3
converter slag otation tailings, experiments at different pulp densi-
CuO  Fe2 O3 8H Cu 2Fe 4H2 O 8 ties were carried out.
The experiments were carried out at the previously accepted pH
2 3
Fe3 O4 8H Fe 2Fe 4H2 O 9 1.5, 40 C, and initial Fe 3 + concentration in the leaching solution of
5.3 g/L. The solid phase was introduced into the reactor in order to
2 3
ZnFe2 O4 8H Zn 2Fe 4H2 O: 10 obtain pulp densities of 10, 20, and 30% (w/v).
The results are presented in Fig. 2. Variations in pulp density from
Reactions of dissolution of iron (fayalite) and zinc silicates may 10 to 30% had no effect on zinc recovery, while copper recovery de-
occur in the system according to Eq. (1), with formation of silica gel creased with increasing pulp density. It is noted that within the rst
according to Eqs. (2)(3). The higher the temperature and pH of the 30 min of the leaching a signicant decrease of the rate of copper re-
pulp, the higher is the rate of the reaction with jarosite formation covery with increasing of the pulp density from 10% to 2030% was
(Dutrizac, 1980): observed. Later it was more or less the same at all variants of the
 
3Fe2 SO4 3 12H2 O M2 SO4 2 M Fe3 SO4 2 OH6 100
6H2 SO4 11 90
80
where M = K +, Na +, NH4+, H3O + 1
70
Taking into consideration the chemistry of leaching of converter
Recovery (%)

2
slag otation tailings, the experiments were planned in order to max- 60
imize the solubilization of non-ferrous metals (primarily copper) and 50
minimize the solubilization of silicates (mostly fayalite) and jarosite
40
formation.
30
3
3.1. Effect of pH 20
4
10
The pH value is the key parameter of leaching with sulfuric acid
0
solutions of ferric iron. Its increase to a certain value results in inten- 0 1 2 3 4 5 6 7
sication of the reaction according to Eq. (11), up to complete binding
Time (h)
of ferric ions in complexes which form precipitates. On the other
hand, reactions according to Eqs. (1) and (2), which are intensied Fig. 1. Copper (1, 2) and zinc (3, 4) recovery during chemical leaching of converter slag
at extremely low pH, result in formation of unlterable gels. otation tailings at pH 1.5 (1, 3) and 1.8 (2, 4).
 M.I. Muravyov et al. / Hydrometallurgy 119-120 (2012) 4046 43

100 100

90 90

80 80
1
70 70

Zn recovery (%)
Recovery (%)

2
60 60
3

50 50

40 40

30 6 30 1
2
5
20 4 20 3

10 10

0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
Time (h) Time (h)

Fig. 2. Copper (1, 2, 3) and zinc (4, 5, 6) recovery during chemical leaching of converter Fig. 4. Zinc recovery during chemical leaching of converter slag otation tailings at
slag otation tailings at different pulp densities: 1, 410%, 2, 520%, 3, 630%. different initial Fe3 + concentrations: 10 g/L, 25.3 g/L, 315.7 g/L.

experiment. This can be explained by a multi-component composi- As was already mentioned, over 50% of sulfuric acid required for
tion of the converter slag otation tailings (metallic copper, suldes, pH maintenance was consumed during the rst few minutes of the
copper ferrite) and by different inuence of hydrodynamic conditions process (up to 258 g/kg at 10% pulp density and pH 1.5). Converter
in the reactor on mass transfer processes of different copper phases in slag otation tailings are thus a highly acid-consuming material.
leaching solution. While copper recovery was 73.0% after 6 h of treat- This may result in abrupt pH increases during continuous chemical
ment at 10% pulp density, it was only 58.3% at 30% pulp density. A leaching in reactors, which will have a negative effect on the result.
similar pattern of copper solubilization depending on pulp density Preparation of the slag otation tailings by treatment with sulfuric
was reported by Carranza et al. (2009b) and may result from the acid solutions prior to chemical leaching seems logical, similar to
fact that during leaching at higher pulp density (i.e., higher amount the analogous techniques for processing of sulde materials
of the solid phase per unit volume) Fe 3 + concentration in the solu- (Fomchenko et al., 2010). For this purpose, the control variant was
tion is lower at a given moment. This is the consequence of batch designed, where the mineral salt base of 9 K medium acidied with
mode of the experiments, when only the initial iron concentration sulfuric acid and containing no ferric or ferrous iron was used as a
in the leaching solution is specied. leaching solution.
The effect of ferric iron concentration on copper and zinc leaching The results are presented in Figs. 35. They show that in the pres-
will be considered below. ence of Fe 3 + ions copper recovery increased, while recovery of zinc
Since a threefold increase in pulp density resulted in only a 1.25- and iron decreased, especially during the rst 30 min of the process.
fold decrease in copper recovery (after 6 h) and had no effect on Thus, copper recovery after 30 min without iron in the leaching solu-
zinc recovery, while the economical efciency of the process in- tion and at 5.3 g/L Fe 3 + was 21 and 42.6%, respectively, while zinc re-
creased at higher pulp density, the 30% value is optimal within the covery was 25.4 and 13.6%, respectively. Iron recovery was similar to
studied range. that of zinc: 25.1 and 9.3% after 30 min in the absence of iron and at
5.3 g/L Fe 3 + in the leaching solution, respectively. These results may
be explained by the fact that while Fe 3 + ions are reagents in the reac-
3.3. Effect of the concentration of ferric iron ions tions of copper leaching (4)(7), so that their increased concentration
increases the reaction rate, they are products in the reactions of zinc
The experiments were carried out at 40 C, pH 1.5, and pulp den- (9) and iron leaching (10), so that their elevated concentration in-
sity 30% (w/v). The reactor was lled with the leaching solution with- hibits the reactions.
out Fe 3 + ions or with initial Fe 3 + concentrations of 5.3 and 15.7 g/L. The concentration changing of ferrous and ferric iron during the
chemical leaching with sulfuric acid solution and in the presence of
100
90 100

80 90
3 80
70
Cu recovery (%)

Fe recovery (%)

70
60
2 60
50
50
40
1 40
30 1
30
20 2
20
10 10 3

0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
Time (h) Time (h)

Fig. 3. Copper recovery during chemical leaching of converter slag otation tailings at Fig. 5. Iron recovery during chemical leaching of converter slag otation tailings at
different initial Fe3 + concentrations: 10 g/L, 25.3 g/L, 315.7 g/L. different initial Fe3 + concentrations: 10 g/L, 25.3 g/L, 315.7 g/L.
44 M.I. Muravyov et al. / Hydrometallurgy 119-120 (2012) 4046

45 100

40 90
1'
80
35
2'
Concentration (g/L)

70

Zn recovery (%)
30
60
25
4
3' 50 5
20 3
40
15 30
2
10 3 20
1
5 10
2
1 0
0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
Time (h) Time (h)

Fig. 6. Fe3 + (1, 2, 3) and Fe2 + (1, 2, 3) concentrations during chemical leaching Fig. 8. Zinc recovery during chemical leaching of converter slag otation tailings at
of converter slag otation tailings at different initial Fe3 + concentrations: 10 g/L, different temperatures: 128 C, 240 C, 355 C, 470 C, 585 C.
25.3 g/L, 315.7 g/L.

3.4. Effect of temperature

5.3 or 15.7 g/L ferric iron in the leaching solution are demonstrated in
Fig. 6. Under conditions of the sulfuric acid leaching converter slag Temperature is known to be the most important factor affecting
otation tailings ferrous iron concentration dramatically increased the rates of chemical reactions. Effect of temperature on the dynamics
due to fayalite dissolution, resulting in silica gel forming after 2 h. In of leaching of iron and non-ferrous metals from converter slag ota-
addition, ferric iron emergence in the solutions due to dissolution of tion tailings was therefore investigated. The experiments were car-
non-ferrous metals ferrites was observed, its concentration reached ried out at the parameter values determined previously: pH 1.5,
above 1 g/L within 2 h of leaching. In the processes of ferric leaching initial Fe 3 + concentration in the leaching solution 15.7 g/L, and pulp
an increase of ferrous iron concentration was much less and with in- density 30% (w/v).
creasing initial ferric iron concentration in the leaching solution the The experimental results of non-ferrous metals recovery during
growth rate of ferrous iron concentration reduced. The ferric iron leaching of converter slag otation tailings are presented in Figs. 7
concentration didn't reduced signicantly, especially in the variant and 8. They show that the rate and efciency of zinc and copper re-
of the experiment with initial concentration of ferric iron 5.3 g/L. covery increased with temperature. Increase in temperature from
It may therefore be concluded that due to pronounced dissolution 40 to 70 C resulted in 1.5-fold increase in copper recovery and 2.3-
of silicates acidic treatment of converter slag otation tailings should fold zinc recovery after 1 h. The data on metal solubilization and
not be used prior to chemical leaching. their content in the leach residue after 1.5 h of treatment at 70 C
Comparison of the processes carried out at initial Fe 3 + concentra- are presented in Table 2.
tions of 5.3 and 15.7 g/L showed more efcient copper recovery in the The average rates of solubilization for copper and zinc within 1.5 h
latter case. Thus, after 6 h of treatment, 70.2% copper recovery was were 0.91 and 3.35 g L 1 h 1, respectively. Since intense dissolution
achieved at 15.7 g/L Fe 3 +, while at 5.3 g/L recovery was only 58.3%. of silicates occurs at the temperatures exceeding 70 C and the gel
Recovery of zinc and iron was 20.0 and 12.5%, respectively, in the produced probably sorbs copper, resulting in underestimates of cop-
rst case and 27.2 and 23.1%, respectively, in the second case. per concentration and therefore recovery, further increase in temper-
Thus, chemical leaching with ferric sulfate at initial concentration ature is undesirable (Fig. 7).
of 15.7 g/L was chosen as the preferable variant due to higher recov- The dissolution or oxidation of copper and zinc minerals in acidic
ery of copper, the most expensive component of otation tailings, ferric sulfate solutions are heterogeneous reactions. The kinetics of
lower recovery of the less valuable zinc, and iron recovery decreased these processes may be determined by the rate of diffusion of a re-
almost twofold after 6 h of the process. agent through the lm surrounding a particle, the rate of diffusion
through the layer of reaction products to the reacted nucleus, the
rate of chemical reactions on the particle surface, or their combina-
100
tion (Levenspiel, 1962). The activation energy characterizing the con-
trol step, may be calculated from the Arrhenius equation:
90 4 3
80 5 k k0 expE=RT 12
Cu recovery (%)

70
2
60 where k is the reaction rate constant, k0 is a pre-exponential factor, E is
50 1
the activation energy (J/mol), R is the gas constant (8.31 J mol 1 1),
40
and T is absolute temperature ().
30
20 Table 2
10 Main results of the leaching of converter slag otation tailings.

0 Metals Content in the leach residue, wt.% Recovery,

0 1 2 3 4 5 6 7 wt.%
Time (h)
Cu 0.13 81.6
Zn 3.69 37.7
Fig. 7. Copper recovery during chemical leaching of converter slag otation tailings at
Fe 39.9 26.2
different temperatures: 128 C, 240 C, 355 C, 470 C, 585 C.
 M.I. Muravyov et al. / Hydrometallurgy 119-120 (2012) 4046 45

4.5 100
Zn 90
4
R = 0.987 1
80
3.5 2

Recovery (%)
Cu 70
3
60
2.5
-ln k

R = 0.973 50
4
2 40
3
1.5 30
1 20

0.5 10
0
0 0 0.5 1 1.5 2 2.5
2.7 2.8 2.9 3 3.1 3.2 3.3 3.4
Time (h)
1000/T (K-1)
Fig. 11. Copper (1, 2) and zinc (3, 4) recovery during chemical leaching of converter
Fig. 9. The Arrhenius plot for the Cu and Zn using linear slopes of the curves in Figs. 7 slag otation tailings under bubbling with air (1, 3) and argon (2, 4).
and 8.

3.5. Effect of dissolved oxygen

The Arrhenius equation becomes linear in the coordinates ln k
versus 1/T, and the slope corresponds to the activation energy. The re- Considering the data on the mineralogical composition, the fol-
sults of our calculations presented in Fig. 9 show that the regression lowing reactions may be expected during leaching with acidic solu-
coefcients for approximation straight lines are relatively high for tions of ferric sulfate:
both zinc and copper (0.987 and 0.973, respectively). The apparent
activation energy was 53.8 and 51.3 kJ/mol for zinc and copper, re- 2
u9 S5 2O2 8H 5CuS 4Cu 4H2 O 13
spectively. These results show that the processes of zinc and copper
leaching from converter slag otation tailings are controlled by the 0 2
2CuS O2 4H 2S 2Cu 2H2 O 14
rates of the chemical reactions on the particle surface (Habashi,
1969).
0 2
The data on sulfuric acid consumption (g per 1 kg of the solid 2Cu O2 4H 2Cu 2H2 O: 15
phase) during chemical leaching of converter slag otation tailings
at 70 C and on specic consumption of sulfuric acid (g per 1 g of lea- In order to determine the effect of dissolved oxygen on chemical
ched copper) are presented in Fig. 10. leaching of converter slag otation tailings, experiments were carried
These data show that the highest rate of sulfuric acid consumption out with bubbling the suspension with air or with argon as the con-
occurred during the rst 10 min of the process; it afterwards de- trol (an inert gas, which displaces oxygen from the reaction zone)
creased and remained almost constant till the end of the process. Spe- at the ow of 4 min 1. The experiments were carried out under the
cic consumption of sulfuric acid relative to copper (the most previously chosen parameters: pH 1.5, initial Fe 3 + concentration in
valuable component) exhibited, however, a pronounced minimum the leaching solution 15.7 g/L, and 30% pulp density (w/v) at 66 C.
from 0.5 to 1.0 h. Leaching for over 1.5 h is therefore undesirable. The results are presented in Fig. 11. It can be seen that, in agree-
Consumption of sulfuric acid during 1.5 h at 70 C was 380 g/kg. ment with the theoretical concepts, the presence of dissolved oxygen
Thus, the process carried out at 70 C for 1.5 h should be recom- had no effect on zinc solubilization. Dissolved oxygen had a similar ef-
mended, since it resulted in high recovery of copper (81.6%), as well fect on iron recovery (data not shown). Copper recovery was higher
as recovery of 37.7% zinc and relatively low (26.2%) recovery of under aeration. Thus, 81.0 and 75.6% copper was recovered after
iron. Although longer chemical leaching resulted in a slight increase 1.5 h under aeration and under argon bubbling, respectively.
in copper recovery, it also caused pronounced dissolution of iron sil- Thus, aeration results in an insignicant increase in copper solubi-
icate (fayalite). lization compared to bubbling with argon. Considering the expenses
for the operation of compressor systems and air preparation, as well
as the carry-over of sulfuric acid vapors, chemical leaching under aer-
ation is unpractical.
700 120
Specific consumption H2SO4 (g/g)

2
4. Conclusions
600 100
Consumption H2SO4 (g/kg)

1
500 The process of leaching of converter slag otation tailings from the
80 Svyatogor copper smeltery (Sverdlovsk region, Russia) by sulfuric
400 acid solutions containing Fe 3 + ions was investigated. The effect of
60 pH, pulp density, temperature, initial Fe 3 + concentration, and the
300 presence of dissolved oxygen on the dynamics of copper, zinc, and
40 iron leaching was studied. Chemical leaching at pH 1.5 yielded the
200
best results with higher solubilization of copper and zinc, low in-
20 crease in fayalite dissolution, and less intense formation of the jaro-
100
site precipitate. Increasing pulp density from 10% to 30% resulted in
0 0 only an 1.25-fold decrease in copper recovery (after 6 h) and had no
0 1 2 3 4 5 effect on zinc recovery. Since the decrease in copper recovery may
Time (h) be compensated by increased Fe 3 + concentration in the leaching so-
lution, while the economical efciency of the process increases at
Fig. 10. Consumption of sulfuric acid during chemical leaching of converter slag
otation tailings at 70 C: 1 g H2SO4 per 1 kg of the solid phase; 2 g H2SO4 higher pulp densities, 30% density is the optimum within the investi-
per 1 g of leached copper. gated range. The presence of high concentration of Fe 3 + ions was
46 M.I. Muravyov et al. / Hydrometallurgy 119-120 (2012) 4046

found to inhibit the leaching of zinc and iron. After 30 min, copper re- Arslan, C., Arslan, F., 2002. Recovery of copper, cobalt, and zinc from copper smelter
and converter slags. Hydrometallurgy 67, 17.
covery in the absence of ferric iron in the leaching solution was 21%, Atzeni, C., Massidda, L., Sanna, U., 1996. Use of granulated slag from lead and zinc pro-
while in the presence of 5.3 g/L Fe 3 + it was as high as 42.6%, while cessing in concrete technology. Cem. Concr. Res. 26, 13811388.
zinc recovery was 25.4% and 13.6%, respectively. Iron recovery in Banza, A.N., Gock, E., Kongolo, K., 2002. Base metals recovery from copper smelter slag
by oxidizing leaching and solvent extraction. Hydrometallurgy 67, 6369.
the absence of ferric iron and at 5.3 g/L Fe 3 + in the solution was Barnes, C.D., Lumsdaine, J., O'Hare, S.M., 1993. Copper converter slag treatment at
25.1% and 9.3%, respectively after 30 min. Chemical leaching at the Mount Isa Mines Limited, Mount Isa. Qld. AusIMM Proc. 298, 3135.
initial concentration of ferric of 15.7 g/L was shown to be the best Carranza, F., Iglesias, N., Mazuelos, A., Romero, R., Forcat, O., 2009a. Ferric leaching of
copper slag otation tailings. Miner. Eng. 22, 107110.
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The work was supported by Svyatogor Company, the Programs Romero, R., Mazuelos, A., Palencia, I., Carranza, F., 2003. Copper recovery from chalco-
23 and 24 of the Presidium of the Russian Academy of Sciences and pyrite concentrates by BRISA process. Hydrometallurgy 70, 205215.
grant of the Russian Foundation for Basic Research no. 10-04-00589. Rudnik, E., Burzynska, L., Gumowska, W., 2009. Hydrometallurgical recovery of copper
and cobalt from reduction-roasted copper converter slag. Miner. Eng. 22, 8895.
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