Hydrometallurgy 183 (2019) 71–78

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

Kinetic study of copper leaching from chalcopyrite concentrate in alkaline T

glycine solution
⁎
Doyun Shina,b, Junmo Ahna, Jaeheon Leea,
a
Department of Mining and Geological Engineering, University of Arizona, Tucson, USA
b
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: Recently, glycine, one of the simplest amino acids, has been emerging as an efficient and environmental-friendly
Chalcopyrite lixiviant for copper leaching. In the present study, an alkaline glycine–peroxide lixiviant system was used to
Glycine leach copper from chalcopyrite concentrate by a suite of kinetic studies under different conditions. The particle
Alternative lixiviant size of the concentrate was P80 40 μm. Glycine concentration was varied from 0.5 to 3.0 M (glycine to copper
Passivation
molar ratio of 1.1 to 6.6:1) and the pH was maintained at 11 during the experiment. The copper extraction
within 96 h was observed from 13 to 14% with glycine concentrations from 0.5 to 2 M, while the copper ex-
traction decreased at 3 M of glycine. By reconstituting the glycine concentration during the leach test and adding
hydrogen peroxide periodically, the copper extraction with 1 M glycine at 96 h increased from 14 to 21%,
respectively. By changing the glycine and hydrogen peroxide solution every 24 h, 42% of copper extraction was
achieved within 168 h. With increasing temperature, copper extraction decreased, while iron dissolution in-
creased. Copper sulfide and copper sulfate precipitates were found in the leaching liquor at 22 °C test. Poorly
crystalline copper-iron sulfate phase was observed in the leaching liquor at 35 and 45 °C. This precipitation is
believed to be one of the factors to decrease the copper recovery from chalcopyrite.

1. Introduction this passivation to increase the leaching efficiency. To overcome this

The greatest global resource of copper is low-grade chalcopyrite and
heap bioleaching may be the only economic option for its processing.
However, formation of a passivating layer on the surface of chalcopyrite
slows down the oxidation reaction and reduces the efficiency of the
process.
CuFeS2 + 4 Fe3 + → Cu2 + + 5 Fe2 + + 2S°
Passivation phenomenon is traditionally described in ferric medium
following Eq. (1). There is a diffusion barrier of polysulfide or elemental
sulfur between the leaching solution and the chalcopyrite that slows
down the dissolution rate. Iron deposition on the surface of the ore is
also a very important issue in passivation. It is clear that chalcopyrite
passivation is related to high redox potentials or high Fe3+/Fe2+ ratios
(Córdoba et al., 2008). If the initial potential is very high, equilibrium
of ferric/ferrous sulfate moves and rapid precipitation of ferric ion as
jarosite occurs resulting in the formation of passivation layer. At high
solution potential (i.e., > 600 mV vs. Ag/AgCl), a passivation layer
could be formed.
Many alternative leaching systems have been investigated to avoid
passivation, it is required to artificially control redox potential during
the bioleaching process (Yu et al., 2011) or use thermo-acidophilic
system (Gericke et al., 2009) to keep the redox potential low and the
ferrous ion concentration high. Addition of silver and chloride ions as
catalyst to increase the solubility of metal was reported (Feng et al.,
2013) resulting in less production of S0 membrane and jarosite pre-
cipitation. Panda et al. proposed to wash the system with sodium and
(1)
ammonium carbonate to remove the passivation layer (Panda et al.,
2013).
Recently, glycine, one of the simplest amino acids, has been emer-
ging as an efficient and environmentally friendly lixiviant to leach
copper (Oraby and Eksteen, 2014; Tanda et al., 2017). Comparing with
other amino acids, glycine is relatively inexpensive and the perfor-
mance was proved (Eksteen and Oraby, 2015). In alkaline condition
(above pH 10), most of glycine exists as an anion (H2NCH2COO−), and
forms a strong complex with copper (I) and (II) (Eqs. (2)–(4)) (Aksu and
Doyle, 2001).
Cu2 + + H2 NCH2 COO− → Cu(NH2 CH2 COO)+ (2)
Cu2 + + 2H2 NCH2 COO− → Cu(NH2 CH2 COO)2 (3)

⁎
Corresponding author.
E-mail address: jaeheon@email.arizona.edu (J. Lee).

https://doi.org/10.1016/j.hydromet.2018.10.021
Received 26 January 2018; Received in revised form 18 October 2018; Accepted 26 October 2018
Available online 29 October 2018
0304-386X/ © 2018 Elsevier B.V. All rights reserved.
D. Shin et al. Hydrometallurgy 183 (2019) 71–78

Table 1
Elemental analysis of chalcopyrite concentrate used in this study.
Element (%)

Cu S Fe Al Ca K Mg Na Ag (ppm) As (ppm) Pb (ppm) Zn (ppm) Mo (ppm)

Content 28.8 31.1 26.4 0.62 0.28 0.38 0.09 0.14 90.5 194 582 1780 1890

25 25
(a) 0.5 M glycine (Figure 2)
10 g/L H2SO4 and 10 g/L ferric
Constant 0.5 M glycine
1 M glycine and 3% H2O2
1 M glycine (Figure 2)
20 20
Constant 1 M glycine

Cu extracted (%)
Cu extracted (%)

15 15

10 10

5 5

0 0
0 20 40 60 80 100 0 20 40 60 80 100

Leaching time (hr) Leaching time (hr)

Fig. 1. Copper extraction by H2SO4-ferric and glycine-peroxide from the chal- 25

copyrite concentrate: 6% pulp density, 10 g/L H2SO4 + 10 g/L ferric or 1 M (b)
glycine +3% hydrogen peroxide, room temperature, bottle roll.
20
25
Cu extracted (%)

0.5 M glycine and 3% H2O2

0.5 M glycine and 5% H2O2 15
20 1 M glycine and 3% H2O2
Cu leaching efficiency (%)

1 M glycine and 5% H2O2

2 M glycine and 3% H2O2 10
15 3 M glycine and 3% H2O2
w/o glycine, 3% H2O2
5 0.5 M glycine, periodic addition of 3% H2O2
10 1 M glycine, periodic addition of 3% H2O2
Constant 1 M Glycine, periodic addition of 3% H2O2
0
5 0 20 40 60 80 100

Leaching time (hr)

0 Fig. 3. Effect of (a) glycine or (b) hydrogen peroxide addition during the
0 20 40
Leaching time (hr)
Fig. 2. Effect of glycine and hydrogen peroxide concentration on copper ex-
traction: 0.5 and 1 M glycine, 3 and 5% H2O2, pH 11, room temperature, bottle
roll.
Cu+ + 2H2 NCH2 COO− → Cu(NH2 CH2 COO)2−
This complexation reaction can be enhanced by addition of hy-
drogen peroxide as an oxidant. The oxidation rate of copper is increased
because the anodic reaction is inhibited and the cathodic reaction (Eqs.
(5)–(6)) is enhanced in the presence of hydrogen peroxide (Du et al.,
2004).
H2 O2 + 2e− → 2OH−
H2 O2 ± e− → OH·± OH–
Also, under alkaline conditions, hydroxyl radicals (OH·) which are
more powerful oxidizing agents than hydrogen peroxide can be pro-
duced from hydrogen peroxide by catalysis of copper-amino acid
60 80 100 leaching test on copper extraction: 0.5, 1, 2, and 3 M glycine, 3% H2O2 (a) or
1% H2O2 was added at 0, 6, and 24 h (total 3%, b), pH 11, room temperature,
bottle roll.
complex (Hariharaputhiran et al., 2000). Thus, the generation of these
hydroxyl radicals increases copper dissolution in glycine-hydrogen
peroxide system. Hydrogen peroxide is also environmentally benign
(4) because it decomposes to water.
Very few studies have been reported on copper leaching from
chalcopyrite in the alkaline glycine-peroxide system. Eksteen et al.
(2017) have attempted to recover copper from chalcopyrite and found
that alkaline atmospheric pre-oxidation and ultra-fine grinding was
needed to obtain higher leaching efficiency by 40 g/L glycine with
oxygenation (0.75 mL/min O2) at 60 °C.
(5) In the present study, the authors investigated an alkaline glycine–-
peroxide system to leach copper from chalcopyrite by a suite of kinetic
(6)
studies under different conditions. The leaching solution, leached re-
sidue and byproducts were analyzed by various instrumental techni-
ques.

72
D. Shin et al. Hydrometallurgy 183 (2019) 71–78

40 400 50
Cu extracted - Constant 1 M glycine, 3% H2O2
Cu extracted - Constant 1 M glycine, periodic 3% H2O2
Glycine consumed - Constant 1 M glycine, 3% H2O2

Glycine consumption (mmol)

40

Cu extraction efficiency (%)

30 Glycine consumed - Constant 1 M glycine, periodic 3% H2O2 300
Cu extracted (mmol)

30
20 200

20

10 100

10
96 hr leach w/o changing lixiviants
0 0 Changing lixiviants every 24 hrs
0 20 40 60 80 100
0
Leaching time (hr) 0 20 40 60 80 100 120 140 160 180

Fig. 4. Comparision between the amount of copper extracted and glycine Leaching time (hr)
consumed during the leaching of Fig. 3 (a) and (b). Full and open symbols
Fig. 6. Effect of changing a lixiviant and an oxidant on copper extraction: 6%
represent the amount of copper extracted and glycine consumed, respectively.
pulp density, 1 M glycine, 3% H2O2, pH 11, room temperature bottle roll.

25
(a) Cu copper mine in Southern Arizona. The elemental composition of the
RT bottle roll concentrate was analyzed using acid digestion followed by solution
35 C analysis for different metals using inductively coupled plasma optical
20
45 C
emission spectrometry (ICP-OES) (Table 1). X-ray diffraction showed
that the concentrate consisted of 89.5% chalcopyrite, 5.0% pyrite, 0.2%
Cu extracted (%)

15 molybdenite, 0.7% quartz, 3.1% K-Feldspar, and 1.5% plagioclase. The

particle size of the sample used in the leaching experiments was P80
40 μm.
10

2.2. Leaching study

5
A bottle roll leaching system was used to investigate the effect of
glycine and hydrogen peroxide concentration at room temperature. The
slurry was agitated by rolling the bottle on a rack at 60 rpm. For tem-
0
perature-controlled experiments, a 1-liter volume glass reactor
0 20 40 60 80 100
equipped with an aerator was used. The slurry was mixed with a
Leaching time (hr)
magnetic stirrer at 400 rpm and the temperature was maintained at 35
and 45 °C. The pulp density was 6.25% (20 g solid and 300 mL solu-
7.0
tion). Glycine concentration was varied from 0.5 to 3.0 M (glycine to
(b) Fe
RT bottle roll copper molar ratio = 1.1 to 6.6:1) and the hydrogen peroxide con-
6.5
35 C centration was changed between 3 and 5%. Kinetic samples were col-
0.8
45 C lected at 1, 6, 24, 48, 72, and 96 h of leaching using a syringe-mem-
brane filter of 0.45 μm pore size. The solution pH was maintained at
Fe extracted (%)

11.0 by adding 50% NaOH solution at every sampling point. The

0.6
average pH drop was observed to be about 0.5 in 24 h. Glycine con-
centrations in the kinetic samples were measured based on formol ti-
0.4
tration method (Zoecklein et al., 1995) and reconstituted to the initial
concentration if needed. The filtrates were analyzed for copper and iron
by atomic absorption spectrometry (AAS; Perkin-Elmer 2380, Perkin
0.2 Elmer, MA, USA) with air and acetylene gas. Dissolved oxygen, Eh, and
pH were monitored during the leaching experiments. Sulfuric acid was
also used as a lixiviant for copper leaching at 10 and 20 g/L with 10 g/L
0.0 ferric ion to compare the extraction efficiency.
0 20 40 60 80 100 The mineralogical compositions of the sample before and after
Leaching time (hr) leaching were analyzed by X-ray diffraction (XRD), scanning electron
microscope (SEM) and energy-dispersive X-ray spectroscopy (EDS). The
Fig. 5. Effect of temperature on copper extraction: 1 M glycine, 3% H2O2, chemical composition of the leaching residue and the precipitates were
pH 11, room temperature bottle roll, 35, and 45 °C (stirred reactor). analyzed by inductively coupled plasma mass spectrometer (ICP-MS;
Perkin-Elmer Elan DRC-II ICP-MS, Perkin Elmer, MA, USA) followed by
2. Materials and methods 3-acid digestion (fluoboric-nitric-hydrochloric).

2.1. Sample preparation 3. Results and discussion

Chalcopyrite flotation concentrate was received from an operating Fig. 1 shows < 2% of copper extraction by sulfuric acid with ferric

73
D. Shin et al. Hydrometallurgy 183 (2019) 71–78

Fig. 7. SEM images of the leaching residue after 168 h with changing the lixiviant, Magnification 1000×. (a) BSE, (b) EDS images. The detailed investigations are
given in the text.

ion as an oxidant while glycine with hydrogen peroxide dissolved up to
15% of copper within 96 h. The formation of an elemental sulfur layer
or iron deposition on chalcopyrite surface inhibited the reaction
(Munoz et al., 1979) thus copper extraction did not increase after 6 h in
sulfuric acid and ferric solution. The effect of glycine and hydrogen
peroxide concentrations is shown in Fig. 2. The molar ratio of glycine to
copper was 1.1 to 6.6:1 (0.5–3 M). Without glycine, in the presence of
hydrogen peroxide only, no copper extraction was observed as ex-
pected. The copper extraction within 96 h was observed from 13 to 14%
with glycine concentrations from 0.5 to 2 M, while the copper

74
D. Shin et al.
Fig. 8. The images of (a) the leaching liquor freshly taken and after 24 h, (b) the
precipitate collected at room temperature, and (c) the precipitate at 45 °C.
extraction decreased at 3 M of glycine. The effect of hydrogen peroxide
on leaching efficiency was not significant. It is worth to note that the
results shown in Fig. 2 were obtained without reconstituting the glycine
concentration during the tests.
Copper extractions were calculated while maintaining the glycine
concentration by reconstituting it when kinetic samples were collected.
(Fig. 3 (a)). Comparing with the results shown in Fig. 2, the copper
extraction with 1 M glycine at 96 h increased from 14 to 21%. As shown
in Fig. 3 (b), periodic addition of hydrogen peroxide in 24 h enhanced
copper extraction, from 14 to 20% in the presence of 1 M glycine. When
the glycine concentration was 0.5 M, the copper extraction did not in-
crease much by reconstituting glycine concentration or periodic addi-
tion of hydrogen peroxide. In the constant 1 M glycine sample with
periodic addition of hydrogen peroxide, the rate of copper extraction
increased, but the copper extraction at 96 h (21%) was about the same
with the 1 M glycine sample with periodic addition of hydrogen
75
Hydrometallurgy 183 (2019) 71–78
peroxide (20%). Thus, both of glycine and hydrogen peroxide addition
enhanced the copper extraction and its kinetics.
Glycine consumption was also compared as shown in Fig. 4. At
every 24 h, the glycine consumption of the sample with constant 1 M
glycine and 3% hydrogen peroxide (Fig. 3(b) inverse open triangle) was
about 0.08–0.09 M, and the sample with constant 1 M glycine and
periodic 3% hydrogen peroxide (Fig. 3(b) solid square) was about
0.2–0.3 M, showing about 10 and 30% glycine was consumed by adding
hydrogen peroxide once or periodically within 24 h, respectively. At
every sampling point, the glycine concentration was reconstituted to
1 M. Even though the copper extraction efficiencies at each time point
were almost similar with 1 M glycine and periodic addition of 3% hy-
drogen peroxide (Fig. 3(b) inverse open triangle) and constant 1 M
glycine and 3% hydrogen peroxide (Fig. 3(a) open triangle), the glycine
consumption in the test with periodic addition of 3% hydrogen per-
oxide was higher than the test with constant glycine concentration.
Since the hydroxyl radicals oxidize glycine (Berger et al., 1999) and the
production of hydroxyl radicals from hydrogen peroxide is promoted by
copper-glycine complex (Du et al., 2004), glycine may be excessively
consumed when hydrogen peroxide is freshly added. Also, as shown in
Eqs. (2)–(4), one mole of copper should consume one or two moles of
glycine, however, the glycine consumption was about 10 times than the
copper extracted, possibly due to glycine oxidation by hydroxyl radical
and formation of ligand complex with other metals.
With increasing temperature (from room temperature to 45 °C), the
copper extraction decreased (Fig. 5 (a)), while the iron extraction in-
creased (Fig. 5 (b)). To control temperature, a 1-l volume stirred reactor
equipped with an aerator was used. These data indicate that copper
extraction is possibly inhibited, and the inhibition might be promoted
by increasing temperature or glycine concentration > 1 M. For com-
parison, pure copper powder was leached by 1 M glycine and 3% hy-
drogen peroxide at room temperature and 45 °C. After 1 h, the copper
extraction was 7% and 11% at room temperature and 45 °C, respec-
tively. Previous studies on chalcopyrite leaching in acid ferric sulfate
medium also reported that the activation energy during chalcopyrite
leaching with ferric ion is quite high, and the copper recovery rate
increased with temperature (Munoz et al., 1979; Córdoba et al., 2008).
Thus, it is believed that the lower copper extraction at high temperature
in glycine peroxide system is not common, but only observed in the
chalcopyrite leaching. Eksteen et al. reported that copper extraction
was enhanced by increasing temperature from room temperature to
60 °C and it is believed due to the different experimental condition of
the tests (Eksteen et al., 2017). In this study, air was only used to supply
oxygen, but pure oxygen was used in their study. In the case of other
copper minerals, since the glycine-peroxide system dissolved up to 80%
of total copper from the gold-copper concentrate including chalcocite,
Cu-metal, cuprite, chalcopyrite, and bornite (Oraby and Eksteen, 2014),
the effect of temperature on copper leaching was not investigated.
A series of tests were carried out using fresh lixiviant and the oxi-
dant (i.e., the 1 M glycine and 3% hydrogen peroxide solution) by
changing them every 24 h at room temperature. Copper extraction was
42% within 168 h (Fig. 6). At 96 h, the copper extraction was 29%,
indicating increase of copper extraction efficiency comparing with the
96 h leach test without changing the solution (21% on Fig. 3(a)). This
result indicates that the leaching residue still contains glycine soluble
copper. After 168 h of leaching, the residue was analyzed by ICP
showing 18.6% Cu, 36.8% Fe, and 23.01% S. XRD analysis was also
performed to see the mineralogy of the residue showing 2% quartz
(SiO2), 8% K-feldspar (KAlSi3O8), 6% plagioclase (NaAlSi3O8 –
CaAl2Si2O8), 6% pyrite (FeS2), 4% bornite (Cu5FeS4), 54% chalcopyrite
(CuFeS2), and 20% amorphous fraction. Comparing with the chalco-
pyrite content and Cu grade of the original concentrate (95 and 28.8%,
respectively), 54% of chalcopyrite and 18.6% of copper in the residue
are acceptable numbers based on 42% of copper extraction. Fig. 7
shows the BSE (Back Scattered Electron) SEM images and EDS mapping
images of the residue. The unreacted chalcopyrite grains were observed
D. Shin et al. Hydrometallurgy 183 (2019) 71–78

Table 2
The (a) elemental and (b) mineralogical composition of the precipitates collected at room temperature (RT), 35 °C, and 45 °C.
(a) Elemental composition (%)

Cu S Fe Al Ca K Mg Na Ag (ppm) As Pb (ppm) Zn (ppm) Mo (ppm)

(ppm)

RT 61.8 15.2 0.45 – – 0.08 – 3.4 89.1 14.7 – – –

35 °C 31.7 10.7 15.4 0.56 0.36 0.22 0.22 3.9 151.3 93.7 0.11 0.03 0.16
45 °C 33.7 10.1 16.9 0.69 0.57 0.20 0.46 2.8 96.7 100.4 0.47 0.02 0.06

(b) Mineralogy composition (%)

RT 35 °C 45 °C

Plagioclase (NaAlSi3O8 – CaAl2Si2O8) – – 5

Siderite (FeCO3) – – 3
Chalconatronite (Na2Cu(CO3)2•3(H2O)) 5 – –
Pyrite (FeS2) – – 3
Chalcopyrite (CuFeS2) – 3 7
Chalcocite Group (Cu2S) 58 36 35
Perkovaite (CaMg2(SO4)3) – 2 –
Butlerite (Fe3+(SO4)(OH)•2(H2O)) 3 1 –
Poitevinite ((Cu,Fe2+,Zn)SO4•(H2O)) 3 – –
Bonattite (CuSO4•3(H2O)) 2 4 –
Alpersite ((Mg,Cu)SO4•7H2O) – 2 –
Antlerite (Cu3(SO4)(OH)4) 1 – –
(NH4)3Cu2(SO4)3(OH) 3 2 –
Kobyashevite (Cu5(SO4)2(OH)6·4H2O) 5 – –
Natrite (Na2CO3) 5 5 –
Amorphous fraction 16 46 47
Total 100 100 100

as shown at spot 1, and the poorly-crystalline materials associated with
iron and oxygen as shown at spot 2 might be iron (hydr)oxide, possibly
this is the principal component of the 20% amorphous fraction de-
termined by XRD. Eksteen et al. (2017) has also reported that amor-
phous iron oxy-hydroxide was detected.
Interestingly, a dark-brown precipitate was observed in the leaching
liquor after only a few minutes of sampling even though it was filtrated
with 0.45 μm pore filter (Fig. 8 (a)). The precipitates were harvested
from the leaching liquor after 96 h at room temperature, 35, and 45 °C
tests shown on Fig. 5, filtered with P4 grade filter paper (particle re-
tention 4–8 μm), settled down the precipitates followed by decanting
the supernatant, and centrifuged at 3000 rpm for 30 mins. The mor-
phological characteristics of the precipitates in the leaching liquor at
different temperature were different. The precipitate collected from
room temperature test was flakier and easily broken-up (Fig. 8 (b)), but
the precipitates at 35 and 45 °C were harder solid (Fig. 8 (c)). The
chemical and mineralogical compositions of precipitates were analyzed
by chemical analysis and XRD. As shown in Table 2 (a), the precipitate
at room temperature consists of mostly copper and sulfur, while the
precipitates at 35 and 45 °C contain significant amount of iron with
copper and sulfur. In the mineralogical data, most of crystalline copper
and sulfur were found to be chalcocite (Cu2S) in all the precipitates. The
content of chalcocite decreased with increasing temperature, while the
content of amorphous fraction significantly increased with increasing
temperature. Some copper sulfate minerals such as bonattite, antlerite,
and kobyashevite were detected in the precipitate at room temperature
and 35 °C. To characterize the poorly crystalline fractions, SEM-EDS/
BSE imaging analysis was performed (Fig. 9 and Table 3). The poorly
crystalline material in the precipitate at room temperature mostly
consisted of copper sulfide and copper sulfate, based on the elemental
composition from the SEM-EDS analysis. Several grains of chalcona-
tronite (Na2Cu(CO3)2•3(H2O)) were also detected. In the precipitate at
35 and 45 °C, the majority of the poorly crystalline material was copper
iron sulfate. A high sodium phase that is likely natrite (Na2CO3) was
visible in several of the spectra, mixed in with the copper iron sulfate.
Sodium carbonate minerals might be originated from glycine oxidation
by hydrogen peroxide and addition of sodium hydroxide to adjust pH.
Since the hydroxyl radicals oxidize glycine (Berger et al., 1999) and the
production of hydroxyl radicals from hydrogen peroxide is promoted by
copper-glycine complex (Du et al., 2004), carbonate can be produced
from the oxidation reaction and reacted with high sodium from adding
sodium hydroxide. Sodium carbonate can crystallize within the porous
building materials when soluble sodium compounds in an alkaline en-
vironment. Several small grains (~1 μm) of plagioclase (NaAlSi3O8 –
CaAl2Si2O8) were observed in the precipitate at 35 °C, and several
grains of hornblende (Ca2(Mg,Fe,Al)5(Al,Si)8O22(OH)2) and other sili-
cate material were observed below the detection limits of XRD in the
precipitate at 45 °C.
Based on the data of the chemical analysis, XRD, and SEM-EDS/BSE
imaging analysis it was found that some of leached copper, iron, and
oxidized sulfur may be precipitated after leaching occurred and the
precipitation pattern changed in different leaching temperatures. At
room temperature, copper can be precipitated with sulfate and sulfide,
which complexed with the byproduct of leaching, sulfur. This copper
sulfide precipitation in alkaline condition has been previously reported
in enargite leaching (Baláž et al., 2000; Curreli et al., 2009). In enargite
alkaline leaching by Na2S and NaOH, arsenic was totally decomposed
and new sulfide product, covellite (CuS) or Cu1.5S, was produced. The
formation of covellite was also found in the copper‑gold concentrate
leaching including chalcocite, Cu-metal, cuprite, chalcopyrite, bornite,
and covellite (Oraby and Eksteen, 2014). Copper as this secondary
covellite is concentrated in the leaching residue, and not further lea-
ched. The low leachability of secondary covellite as an intermediate
product of chalcocite leaching has been studied (Duda and Bartecki,
1982; Cheng and Lawson, 1991), however, the secondary covellite in
this study is newly crystalized from the dissolved copper of chalco-
pyrite, not from the residue of chalcocite leaching. Further research and
investigation will be needed to clearly understand the formation me-
chanism of this secondary covellite. In the glycine-peroxide system, this
secondary covellite was not dissolved but precipitated out, while some
of the precipitates were dissolved in DI water after harvesting.
The precipitation patterns at 35 and 45 °C leaching were totally

76
D. Shin et al.
Fig. 9. SEM images of the precipitates collected from the leaching liquor at (a)
room temperature, (b) 35 °C, and (c) 45 °C. The detailed investigations on the
red spots are given in Table 3. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
77
Hydrometallurgy 183 (2019) 71–78
different with the room temperature leaching. It is believed that oxygen
would not be limited because the system was aerated during the test in
higher temperatures, and the oxygen solubility at atmospheric pressure
is 8.7, 6.9, and 6.4 mg/L at 22, 35, and 45 °C, respectively
(U.S._Geological_Survey, 1998). Interestingly, with increasing tem-
perature, iron leachability was increased as shown in Fig. 5 (b). A hy-
pothesis is proposed as follows. By increasing temperature or con-
centration, the solubility of iron would be increased and the dissolved
iron may form copper iron sulfate with copper and sulfate in the so-
lution followed by the precipitation of iron. Iron leaching by the gly-
cine-peroxide system was also tested in this study by using pyrite, and
almost no iron was leached from pyrite. Unfortunately, increase of iron-
glycine complex solubility with temperature has not been reported. The
standard state equilibrium constants (log β) of ferrous-glycinate and
cupric-glycinate were not changed much in the range of 0–50 °C (Shock
and Koretsky, 1995). For copper‑iron-sulfate reaction, very few studies
have been reported only in acidic condition (Gylienė et al., 2010). Cu
(II) complex with tartrate, glycine, and quadrol in the electroless copper
plating solution was reduced by adding reducing agents such as me-
tallic iron. The composition of the precipitate is organic matter, co-
precipitated copper and iron, and the rest of them are some iron hy-
droxyl-compounds and basic iron sulfate. The three different ligands
show different interactions with iron surface, dissolved ferrous and
ferric ions and possible different behavior in co-precipitation. Cu (II)
and Fe (III) form insoluble complex and co-precipitate with organic
ligands such as citric and tartaric acid at alkaline pH while the pre-
cipitation of Fe (II) was very slow at acid pH (Gylienė et al., 1997). The
completeness of precipitation depends on pH and much less on the
metal ion concentration. Another study has been also reported that
ferric ion forms an unstable violet complex by involving linkages
through the sulfur atoms of cysteine (Perrin, 1958).
As stated above, since the precipitates at 35 and 45 °C was more
solid-like and hard to break-up, the precipitation of copper iron sulfate
may inhibit the access of glycine and hydrogen peroxide toward chal-
copyrite surface. In the conventional acidic ferric sulfate chalcopyrite
leaching, as shown in Eq. (1), elemental sulfur is precipitated to form a
passivation layer, however, the results in this study show that some
other mechanisms may be involved in glycine leaching of copper from
chalcopyrite. It is different with the proposed mechanism in the study of
Eksteen et al. (2017), thus more study is needed to identify the detailed
leaching mechanism in various temperature. Although this remains to
be verified through more rigorous study, it is quite clear that under the
conditions used with the specific chalcopyrite concentrates from the
region, increasing temperature has a negative impact on copper ex-
traction by glycine from chalcopyrite, due to copper precipitation and
its passivation effect. Therefore it would be important to develop the
leaching process for minimizing this copper and iron precipitation and
increasing copper leaching efficiency based on these data. More rig-
orous studies are needed to verify which factors affect the precipitation
such as type of oxidants (peroxide or oxygen), oxygen or radical con-
centration, or temperatures and investigate the detailed leaching me-
chanisms of copper from chalcopyrite by glycine-peroxide.
4. Conclusions
The alkaline glycine-peroxide system was used to leach copper from
chalcopyrite concentrate. The addition of glycine and hydrogen per-
oxide during leaching considerably increased copper extraction. In
addition, copper sulfide and copper sulfate precipitation was detected
in the room temperature leaching liquor, while copper iron sulfate
precipitation was observed in the 35 and 45 °C leaching liquor. This
precipitation may hinder copper extraction rate acting as a possible
passivation layer. The finding in this study is important to understand
the glycine leaching mechanism of copper from chalcopyrite con-
centrate.
D. Shin et al. Hydrometallurgy 183 (2019) 71–78

Table 3
The elemental composition of the spots in the SEM images in Fig. 9. Data is presented directly from analysis and not normalized. The total values do not equal 100%
due to surface area roughness. A polished flat sample is ideal to obtain values closer to 100%.
Fig. 9 (a) RT Elemental (%)

Spot # Na S Fe Cu O Total

1 – 15.2 0.15 52.8 – 68.2

2 – 14.4 0.16 44.2 9.3 68.0
3 – 15.9 0.10 52.2 8.6 76.8
4 – 11.4 0.22 62.2 – 73.8
5 4.9 19.2 0.40 57.5 9.6 91.8
6 3.3 14.1 0.46 47.9 8.8 74.5

Fig. 9 (b) 35 °C Elemental (%)

Spot # Na Al Ca K Si S Fe Cu O Total

1 – – 0.20 0.09 1.2 20.7 15.5 39.3 12.5 89.5

2 – – 0.40 0.24 2.8 14.4 13.0 43.9 16.4 91.0
3 4.0 – 0.20 0.18 11.2 8.2 13.1 27.1 23.7 87.7
4 – – 0.30 0.17 3.2 12.9 15.9 36.1 21.9 90.4
5 6.4 1.9 0.80 0.25 9.1 8.0 18.3 23.2 34.5 102.5
6 – – 0.60 0.39 6.1 13.2 18.2 38.4 28.4 105.2

Fig. 9 (c) 45 °C Elemental (%)

Spot # Na Al Ca K Mg Pb Si S Fe Cu O Total

1 8.5 0.69 4.3 0.80 2.6 – 32.6 – 0.29 0.52 40.8 91.1
2 5.4 – 0.92 0.10 – 0.84 3.6 4.3 27.4 16.1 31.4 90.0
3 – – 0.65 0.10 – – 3.6 7.8 20.0 26.7 26.6 85.4
4 – – 0.28 0.10 – – 1.6 10.3 12.2 43.2 6.8 74.5
5 5.2 – 1.29 0.10 – 0.49 2.4 6.6 20.6 22.8 15.6 75.0
6 – – 7.84 – – – 4.5 11.5 12.7 30.4 30.5 97.5

Acknowledgments
D. Shin was supported for her sabbatical at the University of Arizona
by the Basic Research Project (GP2017-025) of the Korea Institute of
Geoscience and Mineral Resources (KIGAM), funded by the Ministry of
Science and ICT of Korea.
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