Hydrometallurgy 155 (2015) 141–152

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Hydrometallurgy

journal homepage: www.elsevier.com/locate/hydromet

Study on the second stage of chalcocite leaching in column with redox

potential control and its implications
Xiaopeng Niu a,b, Renman Ruan a,⁎, Qiaoyi Tan a, Yan Jia a, Heyun Sun a
a
National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, CAS, Beijing 100190, China
b
School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

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

Article history: High-grade natural chalcocite (Cu2S) was leached in column under controlled redox potential (Eh). To satisfy the
Received 8 December 2014 requirements of the shrinking core model, the conditions in the column were kept as uniform as possible by
Received in revised form 19 April 2015 adopting a short height of the middle chalcocite layer, high acid Fe2(SO4)3 feed and high irrigation rate. The ef-
Accepted 26 April 2015
fects of temperature, Fe3+ concentration and Eh on the second stage of chalcocite leaching were investigated.
Available online 30 April 2015
The second stage is sensitive to temperature whereas insensitive to the variations in Eh and Fe3+ concentration
Keywords:
above a certain level. The second stage was divided into two “sub-stages” based on the inflection point at approx-
Chalcocite imately 70% copper dissolution. The excellent linear relationship plotted by the mixed-kinetics indicated that the
Column leaching second stage is controlled by the rates of both chemical reaction and diffusion, in which the limitation of the
Controlled redox potential chemical reaction rate is dominant. The second “sub-stage” (N 70% dissolution) is responsible for the slow kinetics
Shrinking core model of the second stage. Mineralogical study of the residues confirmed that a S0 product layer covered around a
Sulfur product layer shrinking CuS core during the second stage. In addition, high temperature resulted in a more porous S0 layer
which remarkably influences the ion diffusion rate. A dissolution model based on the shrinking core model
was proposed. Implications of the findings for heap bioleaching were discussed.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction CuS þ 2Fe3þ →Cu2þ þ 2Fe2þ þ S0 : ð2Þ

Chalcocite (Cu2S) is the most common secondary copper sulfide

Similar reactions can be written with O2 or Cu2 + as the oxidant.
mineral. Heap bioleaching of low-grade chalcocite ores is one of the
However, Fe3+ in a sulfate medium is the primary oxidant for commer-
most significant industrial applications of bioleaching (Domic, 2007;
cial heap bioleaching of chalcocite in terms of its high efficiency in
Petersen and Dixon, 2007; Watling, 2006). However, current
extracting electrons from a metal sulfide lattice, easy regeneration by
bioleaching operations exhibit low efficiency because of their unsatis-
iron-oxidizing bacteria, and low cost for separating and recovering
factory leaching rate (Bolorunduro, 1999; Brierley, 2008, 2010). Conse-
copper by solvent extraction–electrowinning.
quently, understanding the dissolution mechanism of chalcocite to
The first stage of chalcocite leaching is very fast relative to the sec-
promote copper leaching rate is necessary for commercial application.
ond stage even at ambient temperature. It is controlled by the diffusion
Oxidative dissolution of chalcocite by Fe3+, O2 or Cu2+, either in a
of oxidant to the mineral surface supported by low activation
sulfate or chloride system, occurs in two distinct stages with the produc-
energies(4–25 kJ/mol) and the first-order dependence on Fe3 + or
tion of secondary covellite (Cu1.0–1.2S) as an intermediate (Bolorunduro,
dissolved oxygen concentration (Cheng and Lawson, 1991a; Petersen
1999; Cheng and Lawson, 1991a; Dutrizac and MacDonald, 1974; Mao
and Dixon, 2003).
and Peters, 1983; Mcdonald and Langer, 1983; Miki et al., 2011; Mulak
The second stage is essentially the oxidation of the intermediate or
and Niemiec, 1969; Petersen and Dixon, 2003; Ruan et al., 2013; Ruiz
secondary covellite, which is also described as the “blue-remaining” co-
et al., 1998, 2007; Senanayake, 2007, 2009; Sullivan, 1930; Thomas et
vellite, to produce S0 and Cu2+. The secondary covellite is more reactive
al., 1967):
than the primary mineral (Cheng and Lawson, 1991a, 1991b; King,
1966; Walsh and Rimstidt, 1986). Miki et al. (2011) attributed this effect
Cu2 S þ 2Fe3þ →Cu2þ þ 2Fe2þ þ CuS ð1Þ
to the significantly increased surface area of the secondary covellite
formed by the dissolution of approximately 50% of copper from chalco-
⁎ Corresponding author at: Institute of Process Engineering, Chinese Academy of
cite. The leaching rate of the second stage is more dependent on tem-
Sciences, Beijing 100190, China. perature compared with the first stage, with reported activation
E-mail address: rmruan@ipe.ac.cn (R. Ruan). energies from 55 kJ/mol to 105 kJ/mol (Dutrizac and MacDonald,

http://dx.doi.org/10.1016/j.hydromet.2015.04.022
0304-386X/© 2015 Elsevier B.V. All rights reserved.
142 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152
1974; Petersen and Dixon, 2003). Such high activation energy values
may suggest that chemical and/or electrochemical reaction controls
the rate of the second stage (Bolorunduro, 1999; Ruan et al., 2013). Con-
sequently, the diffusion barrier, which is thought to be due to the forma-
tion of a sulfur product layer, is usually neglected. However, the
activation energy value may not be the only criterion that distinguishes
the rate-determining step. For instance, Ruiz et al. (1998) found that the
second stage of digenite leaching in oxygenated chloride media was
well described by the shrinking core model controlled by diffusion,
even though apparent activation energy of 84 kJ/mol was obtained.
Behavior of sulfur in the dissolution of a metal sulfide is an important
indicator of the mechanism. Acid-soluble metal sulfides such as ZnS,
PbS, CuFeS2, CuS and Cu2S are attacked by Fe3 + and H+, resulting in
the formation of S0 via the “polysulfide pathway”. More than 90% of
the sulfide moiety of these acid-soluble metal sulfides transforms into
S0 by chemical oxidation with FeCl3; this effect is due to the inert prop-
erty of S0 under moderate temperatures and pressures against any abi-
otic oxidation in acidic environments; however, data on CuS and Cu2S
are unavailable (Schippers and Sand, 1999). Similarly, the diffusion bar-
rier by the sulfur product layer during the process of leaching metal sul-
fides, such as ZnS, CuFeS2, CuS and PbS, has been studied extensively
(Aydogan et al., 2006; Bobeck and Su, 1985; Cheng and Lawson,
1991b; da Silva, 2004a, 2004b; Dutrizac, 1989; Fowler and Crundwell,
1999; Lu et al., 2000; Souza et al., 2007). With regard to chalcopyrite ox-
idation, metal-deficient sulfides, polysulfides, element sulfur and
jarosites have been proposed to be responsible for the passivation of
chalcopyrite dissolution (Dutrizac, 1989, 1990; Klauber, 2008; Yang
et al., 2015), which poses more to the different reaction pathways
(Senanayake, 2009). The complicated chalcopyrite oxidation may be
related to critical leaching conditions, particularly the solution Eh
(Nicol et al., 2010; Velásquez-Yévenes et al., 2010a, 2010b). Unlike
chalcopyrite, spontaneous oxidation in the second stage of chalcocite
leaching occurs if the potential for the oxidant couple is greater than
that for the oxidation of the secondary covellite (Miki et al., 2011).
Chalcocite oxidation always follows the “polysulfide pathway”.
Although the chalcocite leaching process appears to be very simple,
no clear evidence is available on sulfur behavior by both kinetics analy-
sis and mineralogy. Therefore, a detailed study including clear kinetics
analysis and mineralogy examination would help in elucidating the be-
havior of sulfur in chalcocite leaching.
In general, kinetics of chalcocite has been extensively studied. How-
ever, most of the studies that describe the kinetics have focused on
stirred leaching processes rather than column leaching which is more
similar to industrial heap bioleaching. In addition, very few studies
have been conducted to investigate chalcocite leaching under
controlled Eh condition (Bolorunduro, 1999; Ruan et al., 2013). Given
that an oxidant is consumed, the Eh decreases from the beginning of
the experiment. Moreover, the solution Eh in the heap is usually main-
tained at a steady level by iron-oxidizing bacteria. Hence, column
leaching experiments under controlled Eh can be employed to simulate
heap bioleaching.
In this work, the effects of temperature and Eh and Fe3+ concentra-
tion on chalcocite leaching in columns are investigated under controlled
Eh. Eh is controlled by H2O2 instead of KMnO4 to avoid jarosite produc-
tion (Bolorunduro, 1999; Ruan et al., 2013). Scanning electron microsco-
py (SEM)–energy dispersive spectroscopy (EDS), X-ray diffraction (XRD)
and Raman spectroscopy are utilized to characterize the mineralogical
changes and reveal the behavior of sulfur in chalcocite dissolution.
Table 1
Chemical analysis of chalcocite samples (wt.%).
Size fraction (μm) Cu S Fe Si
−74 + 54 71.64 20.95 1.85 0.97
−54 + 30 72.61 22.90 1.67 1.03
2. Experimental
2.1. Mineral samples
High-grade natural chalcocite specimen was manually sorted
from Zijinshan copper ores. The chalcocite sample was prepared by
wet grinding and wet sieving into two narrow size fractions
(− 54 + 30 μm and − 74 + 54 μm). Most of the experiments were
carried out using 1 g of chalcocite (− 54 + 30 μm size). Results of the
chemical analysis are given in Table 1. Powder XRD confirmed that chal-
cocite was the primary phase (Fig. 1). To minimize surface oxidation,
the particle fractions were stored under N2 atmosphere until required
for experiment.
2.2. Apparatus and leaching experiments
The column leaching apparatus is shown in Fig. 2. The leaching ex-
periments were conducted using a glass column (6 cm in diameter
and 30 cm in length). The column consists of three PVC shells with
5 cm diameter. A layer of glass beads (~5 cm thick) was placed on the
top PVC shell to facilitate the distribution of the acid Fe2(SO4)3 lixiviant
over the middle layer of chalcocite. In the middle of the PVC shell, a layer
of mixed chalcocite and quartz (~0.5 cm thick) was placed, followed by
a quartz layer (1 cm thick). In the bottom of the PVC shell, another layer
of glass beads (~5 cm thick) was placed to prevent the chalcocite from
washing off. The irrigation rate for the column was 5 mL/min. In this
study, the conditions within the column were kept as uniform as possi-
ble to satisfy the requirements of the shrinking core model. The condi-
tions were achieved through a combination of short height of middle
chalcocite layer, high acid Fe2(SO4)3 feed and high irrigation rate. The
design of the column was inspired by the methods reported by Lizama
(2004).
The solution Eh was monitored using a FermProbe Pt electrode with
Ag/AgCl reference electrode (3.8 M KCl). The pH was measured using a
METTLER TOLEDO SG8 pH electrode. The temperature of the solution in
the round-bottom flask was controlled using an oil bath equipped with
a digital thermostat and that of the column was controlled using a water
bath.
The chemical reagent Fe2(SO4)3 for the kinetic experiments was pre-
pared as follows: different amounts of Fe2(SO4)3 and 10 g of 98 wt.%
H2SO4 were dissolved in distilled water. Afterward, the solution was
adjusted to 1 L.
Approximately 600 mL of the prepared acid Fe2(SO4)3 solution was
placed into a round-bottom flask and heated to the required tempera-
ture. The solution Eh was controlled within ± 10 mV of the set value
♦
∇ SiO2
B ∇
♦ Cu2S
♦
♦
∇ ♦
♦
∇ ♦
Intensity
♦
A ♦
♦
♦ ♦
∇ ♦
10 20 30 40 50 60 70 80 90
2θ/°
Fig. 1. XRD patterns of initial chalcocite samples: (A) −54 + 30 μm and (B) −74 + 54 μm.
 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152 143

using 15 wt.% H2O2 solution, which was titrated into the round-bottom
flask using an ORP controller connected to a peristaltic pump. The
lixiviant was recycled with the use of a peristaltic pump.
Aliquots (2 mL) of the reaction solution were sampled periodically
using a calibrated pipette. The total Cu and Fe concentrations were mea-
sured using inductively coupled plasma optical emission spectrometry
(ICP-OES), and the Fe2+ concentration was titrated with potassium di-
chromate. The concentration of Fe3+ was calculated as the difference
between the total and ferrous ion concentrations. The leached residues
of chalcocite and quartz in the middle of the PVC shell were separated
by wet sieving. The separated chalcocite residue was washed five
times with H2SO4 at pH 1.05 to prevent possible contamination of the
surface by solution species, and then dried under nitrogen atmosphere
for further analysis.
2.3. XRD
The powder XRD patterns of the residues were collected using a
Rigaku Smartlab diffractometer fitted with a Cu tube and operated at
45 kV and 200 mA. XRD data were collected from 5° to 90° (2θ) in
0.02° steps at 9°/min speed.
2.4. Raman spectroscopy
For Raman spectroscopy (HORIBA JOBIN YVON ARAMIS), a 633 nm
line of He–Ne ion laser was used, which was standardized with silicon
before the test. Low intensity laser with 0.04 mW energy was used
throughout the experiment because the samples are easily damaged
by energy above 0.1 mW. The Raman data were recorded between
100 and 500 cm−1. Measurements were taken at four to five spots for
each sample.
2.5. SEM–EDS
Samples were coated with platinum by electro-deposition and ex-
amined by SEM (JSM-7001, Japan) coupled with EDS (INCAX-MAX) at
15 kV accelerating voltage.
A portion of the residues was placed into the bottom of the sample
cup, added with epoxy under vacuum, and allowed to harden. The hard-
ened epoxy mount was polished, coated with platinum, and then
measured by MLA 250 equipped with SEM (Quanta 250) and EDS
(GENESIS).

5
18

xx˚C

xx˚C 1 7
16
9 2
3
4
10

11
15
6
12
xxmL/min

17
14
13
xx mV xx˚C
xx˚C xx˚C

(a) (b)

(c)
Fig. 2. (a) Apparatus employed for column leaching under controlled Eh. (b) The configuration of the column. (c) Bottom of a PVC shell. 1—glass beads, 2—mixed chalcocite and quartz,
3—quartz, 4—glass beads, 5—dripper, 6—pedestal, 7—PVC shell, 8—pore, 9—jacket, 10—ORP probe, 11—round-bottom flask, 12—stirrer, 13—oil bath, 14—ORP digital controller, 15,
16—peristaltic pump, 17—H2O2, 18—water bath.
144 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152

0.9
3. Results and discussion
0.8
3.1. Effect of Fe3+ concentration
0.7
The main purpose of investigating the effect of Fe3+ concentration

Cu Dissolution
0.6
was to check if Fe3 + ion depletion during the reaction could be
neglected. Fig. 3 shows the effect of Fe3+ concentration on copper disso- 0.5 60˚C
lution, with an initial ferric concentration of 1, 3, and 10 g/L respectively. 45˚C
The results show that copper dissolution rate was almost independent 0.4
30˚C
of Fe3 + concentration above 1 g/L. In addition, Fe2 + concentration 25˚C
0.3
was approximately 0.4 g/L in 10 g/L Fe3+ whereas almost undetected
in 1 g/L and 3 g/L Fe3+. This finding confirmed that the criteria of the 0.2
shrinking core model, i.e., constant concentrations of liquid reactants
in solution, were satisfied. 0.1

3.2. Effect of temperature
Fig. 4 summarizes the dissolution curves obtained at different tem-
peratures. In general, 45 °C is the distinction of the favorable tempera-
ture between the mesophiles and moderate thermophiles, whereas
25 °C is the ambient temperature at which the heap works.
At all temperatures shown in Fig. 4, the leaching reaction had an ev-
ident stage of rapid dissolution, followed by a stage that proceeded at a
slow rate. This observation confirms again that the leaching process
proceeds by a two-stage mechanism. Copper was much more prone to
leaching at high temperatures than it is at low temperatures, especially
above approximately 45% copper dissolution. This finding shows that
temperature performs a dominant role in the rate of the second stage
leaching. The resident time between 70% and 80% copper dissolution
was almost equal to that between 45% and 70% copper dissolution
(Fig. 7). Furthermore, the average dissolution rate between 45% and
70% copper dissolution is approximately two fold than that between
70% and 80% copper dissolution. This phenomenon would not change
even though an increase in temperature can cause a significant
elevation in copper dissolution rate. A detailed discussion about the
slow dissolution in the second stage is presented in Section 3.4.
3.3. Effect of Eh
Leaching experiments were conducted at various potentials of 650,
700, 750, and 800 mV. The range of Eh was chosen based on heap
bioleaching practices (Ruan et al., 2013), and the values set were greater
0.0
0 25 50 75 100 125 150 175 200 225 250
Time(h)
Fig. 4. Effect of temperature on chalcocite dissolution. Conditions: size fraction,
−54 + 30 μm; Fe3+ concentration, 10 g/L; pH, 1.05 ± 0.05; Eh, 750 mV.
than the rest potential of chalcocite reported at approximately 600 mV
(Miki et al., 2011; Petersen and Dixon, 2003).
Figs. 5 and 6 present the effect of Eh on copper dissolution. The
slopes of the log rate between 50% and 80% dissolution vs. Eh plot
showed 0.002 and 0.001 at 30 and 45 °C respectively, which indicated
that the rate of the second stage leaching was insensitive to Eh. This re-
sult was contrary to that of the study by Bolorunduro (1999), who con-
cluded that Eh governed the rate of the second stage leaching. However,
the experiments were conducted at 75 °C only, thus disregarding the
variation of temperature on the effect of Eh. Miki et al. (2011) investi-
gated this process in a relatively low range of 500–600 mV in dilute
chloride solutions at 35 °C; they suggested that oxidation of primary
or secondary covellite requires at least 600 mV. The dependence of
the rate of chalcocite leaching on Eh, however, in the industrial range,
has not been determined in these studies.
The results of our work confirmed that the rate of the second stage of
chalcocite leaching was insensitive to Eh at moderate temperatures in
the industrial range of 650–800 mV.

0.9
1.0
0.8
0.9

0.8 0.7
Cu Dissolution

0.7 0.6 750mV

Cu Dissolution

0.6 10g/L 700mV

0.5
3g/L 650mV
0.5
1g/L 0.4
0.4
0.3
0.3
0.2
0.2
0.1
0.1
0.0
0.0 0 50 100 150 200 250
0 50 100 150 200 250
Time(h)
Fig. 3. Effect of Fe3+ concentration on chalcocite dissolution. Conditions: size fraction,
−54 + 30 μm; temperature, 30 °C; pH, 1.05 ± 0.05; Eh, 750 mV (throughout this paper Fig. 5. Effect of Eh on chalcocite dissolution. Conditions: size fraction: −54 + 30 μm;
potentials are quoted with reference to the standard hydrogen electrode, SHE). temperature, 30 °C; Fe3+ concentration, 10 g/L; pH, 1.05 ± 0.05.
 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152 145

0.9
(Cu1.0–1.2S). The second inflection point at approximately 70% copper
0.8 dissolution corresponds to the noticeable decline in dissolution rate,
which suggests that a change in reaction mechanism may have oc-
0.7 curred. Therefore, in this work, the second stage of chalcocite leaching
was divided into two “sub-stages”: the first “sub-stage” corresponds
Cu Dissolution

0.6 800mV
to 45% to 70% copper dissolution, and the second “sub-stage” corre-
750mV
sponds to N 70% copper dissolution. A part of this work focused on
0.5 700mV
analyzing the kinetics of these two “sub-stages”.
650mV
0.4 The fraction values of the reacted blue-remaining covellite
(Cu1.0–1.2S), X, were tested for the degree of fit to the shrinking core ki-
0.3 netic models given by Eqs. (3) and (4) (Bobeck and Su, 1985; Fowler
and Crundwell, 1999; Levenspiel, 1999; Liddell, 2005; Pritzker, 1996;
0.2
Safari et al., 2009; Su, 1976; Wen, 1968):
0.1
1−ð1−XÞ1=3 ¼ kC t ð3Þ
0.0
0 10 20 30 40 50
1−2=3X−ð1−XÞ2=3 ¼ kP t ð4Þ
Time(h)
MbKCC Cfc 2MbDe Cfs
Fig. 6. Effect of Eh on chalcocite dissolution. Conditions: size fraction, − 54 + 30 μm; Where Kc ¼ KP ¼
temperature, 45 °C; Fe3+ concentration, 10 g/L; pH, 1.05 ± 0.05. ρr0 ρr20

t ¼ t −tC :

3.4. Kinetics analysis As shown in Fig. 8(A–C), neither the chemical reaction control nor
the diffusion control model gave a good linear relationship throughout
Chalcocite or digenite leaching by ferric is widely known to occur in the second stage. In Fig. 8(A), for instance, the data deviated from the
two dramatically different stages. However, two inflection points were excellent linear relationship expected from Eq. (3) after 120 h, which
noticed in the dissolution curves as shown in Fig. 7. The first inflection was close to the time that corresponds to 70% dissolution; subsequently,
point at approximately 45% copper dissolution is consistent with the a distinct decreased rate was observed. However, the excellent linear re-
conversion of all the chalcocite (Cu2S) into blue-remaining covellite lationship obtained from Eq. (4) after 120 h indicated that diffusion

0.9 0.9

0.8
(A) 0.8
(B)
0.7 0.7
Cu Dissolution
Cu Dissolution

0.6 0.6

0.5 0.5

0.4 0.4

0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
0 25 50 75 100 125 150 175 200 225 250
0 10 20 30 40 50
Time(h) Time(h)

0.9
(C)
0.8

0.7
Cu Dissolution

0.6

0.5

0.4

0.3

0.2

0.1

0.0
0 2 4 6 8 10 12 14
Time(h)

Fig. 7. Dividing the dissolution curves into two “sub-stages” above 45% Cu dissolution. Conditions: size fraction, −54 + 30 μm; Fe3+ concentration, 10 g/L; pH, 1.05 ± 0.05; Eh, 750 mV.
(A) 30 °C; (B) 45 °C; (C) 60 °C.
146 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152

0.30 0.6

(A) (A')
0.25 1/3 0.5

1-(1-X) +B[1-2/3X-(1-X) ]
1-(1-X)

2/3
2/3
2/3
1-2/3X-(1-X)
or 1-2/3X-(1-X) 0.20 2
R =0.995 0.4
1/3
1-(1-X)

KC=0.00164 2
R =0.997
0.15 0.3 k=0.0027
2

1/3
0.10
R =0.996 0.2
KP=3.77193e-4

0.05 0.1

0.00 0.0
0 50 100 150 200 250 0 50 100 150 200 250
Time (h) Time (h)

0.30

(B) 0.5 (B')

0.25 1/3
1-(1-X)

1-(1-X) +B[1-2/3X-(1-X) ]
2/3
2/3
2/3

1-2/3X-(1-X) 0.4
or 1-2/3X-(1-X)

0.20
1/3
1-(1-X)

2
R =0.997 0.3 2
0.15
kC=0.00774 R =0.996
k=0.01259
2

1/3
0.10 R =0.988 0.2

kP=0.00201
0.05 0.1

0.00 0.0
0 10 20 30 40 0 10 20 30 40
Time (h) Time (h)

0.6
0.30
(C) (C')
1-(1-X) +B[1-2/3X-(1-X) ]

1/3 0.5
2/3

0.25 1-(1-X)
2/3
1-2/3X-(1-X)
2/3
or 1-2/3X-(1-X)

0.4
0.20
1/3

2 2
R =0.998
1-(1-X)

R =0.998
0.15 KC=0.0286 0.3 k=0.04809
1/3

2
0.10
R =0.994 0.2
KP=0.00778

0.05 0.1

0.00 0.0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Time (h) Time (h)

Fig. 8. Plot of data according to the shrinking core model. Conditions: size fraction, −54 + 30 μm; Fe3+ concentration, 10 g/L; pH, 1.05 ± 0.05; Eh, 750 mV. (A, A′) 30 °C; (B, B′) 45 °C; (C, C′)
60 °C.

control became prominent. Similar results observed in Fig. 8(B) and stage, indicating that both chemical reaction and diffusion control con-
(C) further verified the rate-determining step. In general, considering tributed to the dissolution rate throughout the second stage.
just a single control factor throughout the second stage may not be The mixed-model rate constants (Kr) obtained by the application of
reasonable because the relative importance of diffusion and reaction Eq. (5) were used in the Arrhenius plot in Fig. 9, from which, an activa-
control probably varied as the reaction progressed. tion energy of 80.77 kJ/mol can be calculated. This value was found to be
A mixed kinetic equation, i.e., Eq. (5) (Bobeck and Su, 1985; Cordell, within the range of 62.7–104.5 kJ/mol in the ferric sulfate medium
1968; da Silva, 2004b; Liu et al., 2010; Saxena and Mandre, 1992; Su, (Dutrizac and MacDonald, 1974).
1976) was then used to analyze the results: Fig. 10 illustrates the relative contribution of chemical reaction and

 diffusion control on the second stage. The following expressions are
2 plotted against the fractional conversion of blue-remaining covellite, X
Kr t ¼ 1−ð1−XÞ1=3 þ B 1− X−ð1−XÞ2=3 ð5Þ
3 (Bobeck and Su, 1985; Su, 1976):

MbKCC Cfs KCC r0 KC

Where Kr ¼ B¼ ¼ : ð6Þ
ρr0 2De KP
1−ð1−XÞ1=3
The data plotted according to Eq. (5) are shown in Fig. 8(A′–C′). This C¼ h i ð7Þ
1=3
1−ð1−XÞ þ B 1−2=3X−ð1−XÞ2=3
mixed kinetics equation was found to fit the data best for the second
 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152 147

-3.0
chemical reaction is dominant. Diffusion control becomes more promi-
nent especially in the second “sub-stage”.
2
-3.5
R =0.9996
k =9.7151
Ea=80.77KJ/mol 3.5. Mineralogy
-4.0
LnK

The changes in the solid phases after dissolution are illustrated by

-4.5
-5.0
-5.5
-6.0
3.00 3.05 3.10 3.15 3.20 3.25
Fig. 9. Arrhenius plot for the second stage of chalcocite leaching.
h i
B 1−2=3X−ð1−XÞ2=3
D¼ h i:
1−ð1−XÞ1=3 þ B 1−2=3X−ð1−XÞ2=3
“C” and “D” represent the percentage of chemical reaction and diffu-
sion control, respectively. At 30 °C, the percentage of chemical reaction
control is almost equal to that of diffusion control at approximately 80%
dissolution. At 45 and 60 °C, the percentages of diffusion control also
reached 45% at 80% dissolution. In summary, chemical reaction control
is dominant during the second stage, but diffusion control becomes
progressively prominent especially in the second “sub-stage”.
During the first “sub-stage”, the sulfur product layer may not be suffi-
ciently thick to impede the dissolution rate, whereas during the second
“sub-stage”, the diffusion control becomes prominent because of the in-
creasing thickness of the sulfur product layer. This presumption explains
the deviation from chemical reaction control after 70% dissolution.
The above kinetic analysis clearly shows that the second stage of
chalcocite leaching in ferric sulfate medium is controlled by the rates
of both chemical reaction and diffusion, in which the limitation of the
the XRD patterns in Fig. 11. At 60% copper dissolution, the residues
were composed mostly of CuS and S8; Cu2S was undetected. This result
suggests the transformation of all Cu2S into CuS after the first stage. In
the wake of the leaching front, as observed in Fig. 11(B–D), the residues
were still composed mostly of CuS and S8; however, the intensity of the
diagnostic peak of CuS became weak, whereas that of S8 became strong.
Upon further leaching to 90% copper dissolution (Fig. 11(E)), the reac-
tion product was nearly composed completely of S8. The XRD patterns
3.30 provide convincing evidence that the second stage of chalcocite
leaching is essentially the oxidation of the intermediate or secondary
covellite to produce S0.
As shown in Fig. 12, a characteristic of dissolution at different tem-
peratures was that the surfaces of the particles leached at high temper-
atures were much more porous than those leached at low temperatures.
The EDS analysis results given in Fig. 12(A′–D′) show that sulfur is
ð8Þ present on the surfaces as a reaction product. This finding indicates
that temperature significantly affects the sulfur morphology. The forma-
tion of porous sulfur results in less diffusion barrier than that of thick,
compact sulfur. This finding is consistent with Bolorunduro's (1999)
assumption that sulfur formed at high temperatures is porous and
does not significantly inhibit the second stage.
Raman spectroscopy was used to characterize the surfaces of
leaching residues. In general, Raman spectroscopy provides more sensi-
tive information on secondary solid phases than XRD (Sasaki et al.,
2009) and much more superficial composition information at depth of
ten or more nanometers compared with EDS. Elemental sulfur was
used as standard for Raman spectroscopy. In the Raman spectra
(Fig. 13), the peaks at 152 and 219 cm−1 are characteristic of elemental
sulfur caused by the S–S–S bending mode (Holmes and Crundwell,
2013; Mycroft et al., 1990; Zhu et al., 1993). The peak at 473 cm−1
could be assigned to either S0 or CuS for their overlapping peaks in the
471–476 cm−1 region (Mernagh and Trudu, 1993; Sasaki et al., 2009;
Yang et al., 2015). It is assigned to S0 because it is in proportion to the
other peaks for S0 and almost coincides with the standard spectra

∇
∇♠ ∇ SiO2 ♠ S8
E ♠♠
1.0 0.0 ♠ ♠ ♠ ♠ ♠♠ ♠ o ♠ ♦ Cu2S o CuS
60˚C ♠ ∇
45˚C D ♠♠
0.9 0.1 ♠ ∇ o♠ ♠ ♠ ♠
o♠
♠
30˚C
∇
Intensity

C ♠
0.8 0.2 ∇ ♠ ♠o ♠ ♠ ♠ ♠ ♠
C D ♠
o ♠
o
B oo
0.7 0.3 ∇ ♠ ∇♠
o o
♠ ♠ ♠♠ ♠ ♦ o
♦
∇
A ♦ ♦
0.6 0.4 ∇ ♦ ♦
∇ ♦

0.5 0.5
0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80
10 20 30 40 50 60 70 80 90
2θ/°
Cu Dissolution
Fig. 11. XRD patterns of the solid residues. Conditions: 3 g of chalcocite; size fraction,
Fig. 10. Relative contribution of chemical reaction and diffusion control of the second stage − 74 + 54 μm; temperature, 45 °C; Fe3+ concentration, 10 g/L; pH, 1.05 ± 0.05;
of chalcocite leaching. Conditions: size fraction, −54 + 30 μm; Fe3+ concentration, 10 g/L; Eh, 750 mV. (A) Unleached chalcocite, (B) after 60% Cu dissolution, (C) after 70% Cu
pH, 1.05 ± 0.05; Eh, 750 mV. dissolution, (D) after 80% Cu dissolution, and (E) after 90% Cu dissolution.
148 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152

Fig. 12. SEM images of chalcocite particles after leaching at different temperatures. Conditions: size fraction, −54 + 30 μm; Fe3+ concentration, 10 g/L; pH, 1.05 ± 0.05; Eh = 750 mV.
(A) 60 °C after 82% Cu dissolution, (B) 45 °C after 80% Cu dissolution, (C) 30 °C after 81% Cu dissolution, and (D) unleached chalcocite. (A′–D′) EDS spectra of the particles surfaces corre-
sponding to A–D, respectively.

of S0. Furthermore, the weak peak at around 438 cm− 1 is consistent
with the weak diagnostic peak of S0 at 438 cm− 1. No peaks for
polysulfides were observed, which are expected to be approximately
at the 452–460 cm−1 region (Mycroft et al., 1990). The Raman spectra
demonstrate that elemental sulfur is the predominant surface compo-
nent, which is in agreement with the polysulfide pathway for acid-
soluble metal sulfides (Schippers and Sand, 1999).
Fig. 14 shows the Backscattered electron (BSE) images of polished
sections of chalcocite particles found in the leached residues. A product
layer was found to cover around a shrinking unreacted core. Spot
analysis was performed by EDS at indicated numbers, as shown in
Fig. 14, and the results are provided in Tables 2–5.
Element O was not detected in the EDS analysis, which indicates
negligible oxidation of the product layer. A S0 product layer clearly
 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152 149

(A) increased thickness of the S0 product layer becomes progressively

60˚C @82% prominent.
2. The S0 product layer is almost inert with negligible abiotic oxidation.
45˚C @80% 3. Elevated temperatures significantly accelerate the rate. At Eh
Intensity

N650 mV and Fe3 + concentration N1 g/L, the rate is insensitive to

the variations in Eh and Fe3+ concentration.
30˚C @81% 4. Temperature significantly affects sulfur morphology, which influ-
ences the ion diffusion rate through the S0 product layer.
151 219 5. The diffusion barrier may cause approximately 10%–20% Cu (at.%) to
473
0 remain in the S0 product layer.
S 438

4. Implications for the heap bioleaching of secondary copper sulfide

100 150 200 250 300 350 400 450 500

Raman Shift(cm )
− 1 The results of this research provided some useful pointers to opti-
mize heap bioleaching in practice.
1. The slow rate of the second stage leaching is attributed to the second
(B) “sub-stage” (N70% dissolution) in which the diffusion barrier
45˚C @80%
becomes progressively prominent.
2. Appropriate conditions for the chemical kinetics of copper minerals
are crucial to increase efficiency of heap bioleaching. Elevated tem-
45˚C @70%
Intensity

45˚C @60%
151 219
473
0 438
S
100 150 200 250 300 350 400 450 500
− 1
Raman Shift(cm )
Fig. 13. Raman spectra of chalcocite leached (A) at different temperatures with approxi-
mately 80% Cu dissolution. Conditions: size fraction, −54 + 30 μm; Fe3+ concentration,
10 g/L; pH, 1.05 ± 0.05; Eh, 750 mV; (B) at 45 °C with different % Cu dissolutions. Condi-
tions: 3 g of chalcocite; size fraction, − 74 + 54 μm; Fe3+ concentration, 10 g/L; pH,
1.05 ± 0.05; Eh, 750 mV.
covered around a shrinking CuS core until it disappeared. This finding is
consistent with the XRD, SEM–EDS and Raman study, which strongly
supports the kinetics analysis.
Cheng and Lawson (1991a) also noticed the decline in leaching rate
after 70% dissolution in mixed chloride–sulfate solutions and attributed
this to the diffusion barrier. However, the authors did not provide suffi-
cient evidence to confirm the presence of S0 product layer.
Moreover, approximately 10%–20% Cu (at.%) remained in the S0
product layer even after repeated washing of the residues. The S0 prod-
uct layer not only retards the diffusion of Fe3+ toward the interior core
but also hinders the diffusion of produced Cu2 + toward the surface.
Unfortunately, only a few studies have realized the significance of this
phenomenon to heap bioleaching (Dutrizac, 1989). The remaining
Cu2 + in the S0 product layer coupled with argillic adsorption might
explain the unheard 90% copper recovery in commercial bioleaching
operations as reported by Domic (2007).
3.6. Proposed dissolution models
The dissolution model of the second stage of chalcocite leaching
based on the shrinking core model (Fig. 15) is summarized as
follows:
1. The second stage is comprised of two “sub-stages”: the first “sub-
stage” (45%–70% dissolution) is predominantly controlled by chemi-
cal reactions that occur at the sulfide–sulfur interface; in the second
“sub-stage” (N 70% dissolution), the diffusion barrier caused by the
perature accelerates the chemical reaction rate and causes the forma-
tion of porous S0 product layer, which decreases the prominent
diffusion barrier, especially in the second “sub-stage”.
3. The diffusion barrier becomes more prominent because of “particle
effect”. Consequently, elevated temperature is inadequate for an effi-
cient heap bioleaching because of its limited effect on the accelera-
tion of diffusion rate. In addition, above a certain level, the leaching
rate of the second stage is insensitive to the variations in Eh and
Fe3 + concentration. It indicates that above this level, increases in
Eh and Fe3+ concentration in the heap could no longer provide sig-
nificant benefits in terms of copper dissolution rates.
4. Oxidation of S0 product layer by sulfur-oxidizing bacteria results not
only in decreased diffusion barrier but also in the release of remain-
ing Cu in the layer. The increased thickness of the S0 product layer
because of “particle effect” may result in the decline in Fe3+ concen-
tration gradient as well as in diffusive fluxes. The attachment of iron-
oxidizing bacteria on mineral surface enables the direct oxidation of
Fe2+ to Fe3+, thereby avoiding aggregation of Fe2+ on the mineral
surface. The regenerated Fe3+ diffuses through the S0 layer to react
at the sulfide–sulfur interface. Furthermore, given the continuous
direct oxidation of Fe2 + to Fe3 +, the Fe2 + concentration gradient
between the sulfide–sulfur interface and the mineral surface may re-
main at a relatively steady level. The steady concentration gradient is
the driving force for the diffusion of Fe2+ through the S0 layer into
the mineral surface, thereby avoiding aggregation of Fe2 + at the
sulfide–sulfur interface.
5. Conclusions
The results of this study on column leaching of chalcocite in ferric
sulfate medium under controlled Eh led the following conclusions:
1. The slow rate of the second stage leaching is controlled by the rates of
both chemical reaction and diffusion, in which the limitation of the
chemical reaction rate is dominant.
2. The second stage is comprised of two “sub-stages”: the first “sub-
stage” (45%–70% dissolution) is predominantly controlled by chemi-
cal reactions that occur at the sulfide–sulfur interface; the second
“sub-stage” (N70% dissolution) is responsible for the slow rate of
the second stage leaching because of the prominent diffusion barrier
caused by the S0 product layer.
3. Elevated temperature significantly accelerates the rate of the second
stage leaching. At Eh N 650 mV and Fe3+ concentration N1 g/L, the
rate is insensitive to the variations in Eh and Fe3+ concentration.
4. A mineralogical study of the residue confirmed that a S0 product
layer covered around a shrinking CuS core. The S0 product layer is
150 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152

Fig. 14. BSE images of polished sections of leached chalcocite. Conditions: 3 g of chalcocite; size fraction, −74 + 54 μm; temperature, 45 °C; Fe3+ concentration, 10 g/L; pH, 1.05 ± 0.05; Eh,
750 mV. (A) unleached chalcocite, (B) after 70% Cu dissolution, (C) after 80% Cu dissolution, and (D) after 90% Cu dissolution.

almost inert with negligible abiotic oxidation. Temperature signifi- Acknowledgments

cantly affects the sulfur morphology, which remarkably influences
the ion diffusion rate.
5. To understand the role of bacteria, an investigation on the bio-
oxidation of sulfur that covered the mineral surface is being
conducted.
The authors acknowledge the funding from IPE, CAS “The introduc-
tion of outstanding technical talents” program. We thank the reviewers
for their enlightening comments and advice.

Table 4
EDS analysis of the residue after 80% Cu dissolution (at.%).

Table 2 Number Cu S Cu/S

EDS analysis of unleached chalcocite (at.%). 1 55.65 44.35 1.25
2 50.43 49.57 1.02
Number Cu S Fe Cu/S
3 46.59 53.41 0.87
1 66.21 31.81 1.98 2.08 4 8.73 91.27 0.10
2 65.39 32.06 2.55 2.04 5 12.13 87.87 0.14
3 68.17 31.05 0.78 2.20 6 11.76 88.24 0.13
4 68.52 30.96 0.52 2.21 7 8.50 91.50 0.09
5 68.37 31.02 0.61 2.20 8 19.07 80.93 0.24

Table 5
EDS analysis of the residue after 90% Cu dissolution (at.%).
Table 3
EDS analysis of the residue after 70% Cu dissolution (at.%). Number Cu S Cu/S

1 5.00 95.00 0.05

Number Cu S Cu/S
2 7.70 92.30 0.08
1 44.03 55.97 0.79 3 10.03 89.97 0.11
2 41.65 58.35 0.71 4 8.84 91.16 0.10
3 34.24 65.76 0.52 5 7.31 92.69 0.08
4 23.21 76.79 0.30 6 6.43 93.57 0.07
5 16.24 83.61 0.20 7 6.90 93.10 0.07
6 26.09 73.91 0.35 8 8.86 91.14 0.10
7 25.80 74.20 0.35 9 9.08 90.92 0.10
 X. Niu et al. / Hydrometallurgy 155 (2015) 141–152
Cu2+
Cu2+ CuS
Cu+ S-
+ e- e-
Cu+=Cu2 +e-
2+
Fe
2+
Fe
Fe3+
Fe3+
2+
Fe3++e-=Fe
Fig. 15. Schematic diagram of the second stage of chalcocite leaching in ferric sulfate medium. The covellite is referred to as Cu+S− (Goh et al., 2006).
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