Hydrometallurgy 129-130 (2012) 140–144

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Hydrometallurgy
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A study of recovery of copper and cobalt from copper–cobalt oxide ores by

ammonium salt roasting
Mingzhu Zhang, Guocai Zhu ⁎, Yuna Zhao, Xiujuan Feng
Institute of Nuclear and New Energy Technology, Beijing Key Lab of Fine Ceramics, Tsinghua University, Beijing 100084, PR China

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

Article history: Copper and cobalt recovery from a copper–cobalt ore of Democratic Republic of Congo (DRC) by ammonium
Received 30 January 2012 chloride roasting is studied. The effects of roasting temperature, roasting time, and the dosage of ammonium
Received in revised form 19 June 2012 chloride on the leaching rate of copper and cobalt are investigated. The results show 90% copper and 95% co-
Accepted 27 June 2012
balt recovery under the optimal experimental conditions of average particle diameter 0.10 mm and 1:2 am-
Available online 15 August 2012
monium chloride to ore mass ratio at a roasting temperature of 300 °C for 3 h. After adjusting the pH of the
Keywords:
leaching solution to 7 by ammonia addition, the copper and cobalt in the solution were precipitated by am-
Ammonium chloride monium bicarbonate at 60 °C for 40 min. Ammonium chloride crystals obtained after absorbing the exhaust
Roasting gas and filtration of the scrub liquor could be reused for the roasting process. With X-ray diffraction analysis
Copper–cobalt oxide ore on the calcined ore at different temperatures, the roasting mechanism of copper–cobalt oxide ores with am-
monium chloride was investigated. Co(NH3)6CuCl5 was found to be the main intermediate compound formed
at roasting temperatures below 320 °C, above which it was further decomposed to CoCl2 and CuCl2.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction Due to high capital and operating costs, no company in Congo (DRC)
is willing to recover cobalt and copper from ores with less than 5% of
Cobalt is an important strategic element, widely used in alloy Co (Wang et al., 2004; Zhou and Jiang, 2010).
manufacture and aerospace materials. It has strategic importance in Chloride roasting technology developed by the Tsinghua Universi-
both traditional and high-tech industries such as electronic and tele- ty for recovering rare earth has been successfully applied to produc-
com devices. Copper is also one of the most important raw materials tion of many mineral resources. Built on the success of chloride
for domestic economic development, widely used in the electronic, roasting technology (Chen et al., 2001; Lan and Mi, 2008; Li et al.,
electric power, mechanical, military and architecture industries. 2010; Peek et al., 2009; Xu et al., 2001), this study investigates a
With increasing domestic and international demand, both cobalt new ammonium salt roasting–leaching–precipitation process for
and copper resources are anticipated to be in shortage (Feng and recovery of copper and cobalt from local DRC copper–cobalt ores. It
Zhang, 2004; Kapusta, 2006; Moskalyk and Alfantazi, 2000). was found that using ammonium chloride to roast ore and leaching
Currently, acid pressure leaching, solvent extraction and biotechnol- of the calcined slag by hot water, the precipitation of copper and
ogy are the main technologies to extract cobalt from its most important cobalt from the leaching solution by adjusting pH with ammonia led
natural form of cobalt oxide. Although both sulfuric acid leaching and to a copper and cobalt recovery of 90% and 95%, respectively (Shi et
ammonium pressure leaching can be used in industry, there are signif- al., 1997; Xiao et al., 2010). By absorbing the exhaust gas, the recov-
icant challenges. Sulfuric acid leaching for example consumes a lot of ered ammonium chloride crystals can be reused in the roasting pro-
acid, while high-concentration sulfate wastes from the recovery process cess. Since this novel process does not generate waste water and
are harmful to environment. Ammonium pressure leaching requires emission of pollutant gasses, the proposed technique meets the stan-
specialty equipment to sustain high pressure operations, leading to dards of green chemistry and low environmental impact.
high capital and operating cost. Currently, sulfuric acid leaching has
been considered as the leachant to recover copper and cobalt from a Table 1
copper–cobalt ore of Democratic Republic of Congo (DRC) (Apua and The main chemical composition of copper and cobalt oxide ores.
Mulaba-Bafubiandi, 2011; Arslan and Arslan, 2002; Aymn and
Content/% Element
Ziyadanogullari, 2007; Gupta et al., 2003). However, many mine sites
Ca Co Cu Fe Mg Mn Ni Zn
in DRC are remote and the supply of chemicals becomes a challenge.
1# (%) 0.24 11.61 2.256 2.195 1.14 0.92 0.13 4.1
2# (%) 0.19 11.55 2.222 2.087 0.973 0.91 0.11 3.5
⁎ Corresponding author. Tel.: +86 10 89796081.
Avg (%) 0.215 11.58 2.24 2.142 1.06 0.915 0.12 3.58
E-mail address: zhugc@tsinahua.edu.cn (G. Zhu).

0304-386X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2012.06.014
 M. Zhang et al. / Hydrometallurgy 129-130 (2012) 140–144 141

5 spectrophotometer (SP-3520AAPC), which allowed the calculation of

4000 1 Co3O4
leachability of copper and cobalt.
2 CoO
Amountofmetalsleachedout
3000 3 CuO Leachability ¼  100%
Amountofmetalsintheore
Intensity

4 (Cu0.30Co0.70)Co2O4
2000 After adjusting the pH of the filtrate by ammonia, ammonium bi-
5 SiO2 carbonate was added to precipitate copper and cobalt as correspond-
ing carbonate at different temperatures and durations. After filtration,
1000 5 1 the residual content of copper and cobalt in the filtrate was analyzed,
4 11 4 from which the recovery of copper and cobalt was calculated.
32 4 4 32 The gas produced in the roasting process was absorbed by the
0
mother liquid recovered from the leaching, precipitation and filtra-
20 40 60 80
tion process, leading to crystallization of ammonium chloride which
2 / (°)
can be reused in roasting.
Fig. 1. The X-ray diffraction of copper–cobalt oxide ore.
3. Results and discussion

3.1. Roasting–leaching

3.1.1. Effect of ore particle size

2. Experimental
2.1. Mineral composition analysis
A copper and cobalt oxide ore from Congo (DRC) provided by
Liaoning BL Mining Company was used in this study. The main chem-
ical composition of the ore is given in Table 1. As shown in this table,
the average content of cobalt and copper is 11.58% and 2.24%, respec-
tively. The concentration of other elements, such as calcium, magne-
sium and iron, is very low.
According to the X-ray diffraction pattern of copper–cobalt oxide
ore shown in Fig. 1, the Co and Cu are mainly in the form of CoO,
Co3O4, CuO and the associated mineral (Cu0.3Co0.7)Co2O4.
2.2. Experimental
To test the feasibility of the novel process, the experiments were
conducted by following the process flowchart shown in Fig. 2. The
copper–cobalt ore was ground to 100 mesh. The ground ore and ammo-
nium chloride were mixed at a given proportion and roasted in a muffle
furnace at different temperatures for a given period of time. The roasted
slag was leached at a solid to hot water mass ratio of 1:5 and 60 °C
for 0.5 h. The mixture was then filtrated. The content of copper and co-
balt in the leaching solution was analyzed by atomic absorption
At roasting temperature of 250 °C, roasting time 2.5 h, the effect
of particle size on cobalt leaching is shown in Fig. 3. It is evident
that the amount of cobalt leached into the solution with 50% ammo-
nium chloride increases from about 20% to 60% with decreasing par-
ticle size from 300 μm to 100 μm. The observed increase in leaching
of cobalt with decreasing particle size is anticipated as decreasing
particle size increases specific surface area of particles, leading to
an increase in contact area of the ore particles with ammonium chlo-
ride. Such an increase promotes chemical reaction of ammonium
chloride with ore surfaces, improving the surface area-limited leach-
ability of cobalt. A further decrease in particle size did not lead to any
further increase in cobalt leaching, indicating that the system
reached reaction limit.
It is interesting to note a negligible leaching of copper under the
current leaching condition. This is attributed to the leaching temper-
ature below its critical value for effective leaching of copper.
3.1.2. Effect of the ammonium chloride concentration
The effect of ammonium chloride addition to ore roasting at differ-
ent roasting temperatures on cobalt and copper leaching is shown in
Figs. 4 and 5. For a roasting temperature of 250 °C, roasting time of
2.5 h and ammonium chloride addition of 10% during ore roasting,
about 40% of the cobalt in the ore was leached out from the roasted
ore of 100 μm. By contrast, copper showed a negligible leachability.

Ammonium chloride Mixing Copper-cobalt ores

NH4Cl
Crystallizing Roasting
Exhaust gas Calcine (chlorizate of Cu and Co)
(NH3 and NH 4Cl)
Leaching Hot water
Cooling

Absorption Filtration Residual

CuCl 2 and CoCl 2 solution
Mother liquids
Precipitation Ammonium bicarbonate

Copper and cobalt’s

Filtration Drying
mixed carbonate

Fig. 2. The process flow of recovering copper and cobalt from Congo ore.
142 M. Zhang et al. / Hydrometallurgy 129-130 (2012) 140–144

100
100
Leachability of Co and Cu / %

80

Leachability of Cu / %
Co 80 320
Cu 300
60 60
250
40 40

20
20

0
0
10 20 30 40 50
0.05 0.10 0.15 0.20 0.25 0.30
The dosage of NH4Cl used/%
Particle size / mm
Fig. 5. Effect of ammonium chloride addition on the leaching of copper.
Fig. 3. Influence of ore particle size on the leaching of copper and cobalt.

At this ammonium chloride dosage, increasing roasting temperature
showed a negligible effect on leachability of cobalt, but increased
leachability of copper slightly from 0% to 8%. For a given roasting tem-
perature, increasing the amount of ammonium chloride during the
roasting increased leachability of cobalt and copper steadily, more
so for the ores roasted at higher temperatures. For ores roasted at
250 °C, for example, the leachability of cobalt increased from 40% to
75% when ammonium chloride addition increased to 50%. A similar
increase in ammonium chloride addition led to an increase in leach-
ability cobalt from 35% to 90% and 95% when the ore was roasted at
300 °C and 320 °C, respectively. Similar trend was observed for leach-
ability of copper. Since a diminished improvement in leachability of
cobalt was observed when ammonium chloride addition increased
from 40% to 50%, we recommend to add 50% ammonium chloride to
Although increasing roasting time showed a negligible effect on
copper leaching when the ore was roasted at 200 °C, the roasting pe-
riod of 3.5 h, a significant increase in copper leachability with increas-
ing leaching time was observed when the roasting was conducted at
or above 280 °C. Higher roasting temperature led to a shorter roasting
time to achieve a leachability of copper greater than 80%. For exam-
ple, the leaching time reduced from 3.5 h to 2.8 h and 2 h when
roasting temperature increased from 280 °C to 300 °C and 320 °C,
100
Leachability of Co / %

the ore during roasting. 80

3.1.3. Effect of roasting time and temperature 60

The effect of roasting time on the leaching rate of cobalt and cop-
per at different roasting temperatures is shown in Figs. 6 and 7. At 40
200
50% ammonium chloride addition, the leachability of cobalt increases 250
significantly with increasing roasting time when the roasting temper- 300
20
ature is below 300 °C, more so for the roasting temperature between 320
250 °C and 300 °C. It is interesting to note that with lower roasting 350
0
temperature of 200 °C, increasing roasting time to 3.5 h could lead
to the same cobalt leachability above 90%, as is achieved when 1.5 2.0 2.5 3.0 3.5
using the ores roasted at higher temperature up to 350 °C . Also inter- Time / h
esting to note is rapid leaching of cobalt when the ores were roasted
at temperatures higher than 320 °C. Fig. 6. Effect of roasting time on the leaching of cobalt.

100
100

80
Leachability of Co %

Leachability of Cu / %

80

60 60 200
320 280
40
300 40 300
250 320
20
20

0
0
10 20 30 40 50 1.5 2.0 2.5 3.0 3.5
The dosage of NH4Cl used/% Time / h

Fig. 4. Effect of the amount of ammonium chloride on the leaching of cobalt. Fig. 7. Effect of roasting time on the leaching of copper.
 M. Zhang et al. / Hydrometallurgy 129-130 (2012) 140–144 143

Table 2 conditions of pH 7, precipitating temperature 60 °C, amount of

Precipitation of Co and Cu carbonates under different experimental conditions. NH4HCO3 50% and precipitating time 40 min.
No. pH T/°C NH4HCO3:ore t/min Co Cu
(mass ratio) precipitated/% precipitated/%

1 6 60 0.5 40 92.63 98.62 3.3. Roasting mechanism

2 7 60 0.5 40 93.29 98.68
3 8 60 0.5 40 93.17 98.22 To identify the roasting mechanism of the copper and cobalt from
4 7 50 0.5 40 92.29 97.21
the ores, the X-ray diffraction patterns of the calcined ore at different
5 7 60 0.5 40 93.19 97.67
6 7 70 0.5 40 92.70 97.22 temperatures are shown in Fig. 8.
7 7 60 0.4 40 90.95 95.09 As shown in Fig. 1, the Co and Cu in the original ore were mainly in
8 7 60 0.5 40 93.10 98.33 the form of CoO, Co3O4 and CuO. Being a strong oxidizer, Co3O4,
9 7 60 0.6 40 93.57 98.12 undergoes an oxidization–reduction reaction with Fe3O4 to form
10 7 60 0.5 30 92.55 98.39
CoO as shown by reaction (1). Under the roasting condition
11 7 60 0.5 40 93.98 98.43
12 7 60 0.5 50 93.06 98.46 (300 °C), CoO and CuO in the ore react with ammonium chloride to
form water soluble CoCl2 and CuCl2 as given in reactions (2) and
(3), respectively. The results in Fig. 8 suggest the formation of inter-
respectively. To achieve a leachability of cobalt and copper above 95% mediate compound Co(NH3)6CuCl5 in the process with roasting tem-
and 90%, respectively, roasting at 300 °C for 2 h is recommended. peratures below 320 °C. It was found that the Co and Cu in the ore
calcined at temperatures below 320 °C could be dissolved in water,
3.2. Precipitation and enrichment process proving that the intermediate compound Co(NH3)6CuCl5 was the co-
ordination compound formed by CoCl2,CuCl2 and NH3 as given by
In this set of tests, the copper–cobalt ore and ammonium chloride reaction (4). The intermediate compound Co(NH3)6CuCl5 would be
mixture of 2:1 mass ratio was roasted for 2 h at 300 °C. The calcined further decomposed to become soluble CoCl2, and CuCl2 at roasting
ore was leached for 0.5 h at 60 °C in hot water. The pH of the filtrate temperature higher than 320 °C as given by reaction (5). Based on
was adjusted to a desired value by ammonia, followed by NH4HCO3 these observations, the roasting mechanism of copper–cobalt oxide
addition for precipitation of copper–cobalt carbonates at different ore by ammonium chloride could be described as the formation of
conditions. The effect of the filtrate pH, temperature, the amount of the intermediate compound Co(NH3)6CuCl5 in the process at temper-
NH4HCO3 and precipitation time on copper and cobalt precipitation atures below 320 °C, followed by decomposition of the intermediate
is shown in Table 2. The content of copper and cobalt in the filtrate compounds to form soluble CoCl2,CuCl2 at 320 °C.
solution were analyzed by atomic absorption spectrophotometer
(SP-3520AAPC), which allowed the calculation of the amount of cop- Co3 O4 þ 2Fe3 O4 ¼ 3CoO þ 3Fe2 O3 ð1Þ
per and cobalt precipitated into the solid carbonates.
The results in Table 2 show that the precipitation of copper and
cobalt both reached more than 90% under the optimal experimental CoO þ 2NH4 Cl ¼ CoCl2 þ 2NH3 þ H2 O ð2Þ

a b

c d

Fig. 8. X-ray diffraction patterns of the calcined ore roasted with 50% ammonium chloride addition at roasting temperature: a) 280 °C; b) 300 °C, c) 320 °C and d) 340 °C.
144 M. Zhang et al. / Hydrometallurgy 129-130 (2012) 140–144
CuO þ 2NH4 Cl ¼ CuCl2 þ 2NH3 þ H2 O
CoCl2 þ CuCl2 þ 5NH3 þ NH4 Cl ¼ CoðNH3 Þ6 CuCl5
The reaction at higher temperature can be expressed as:
CoðNH3 Þ6 CuCl5 ¼ CoCl2 þ CuCl2 þ 5NH3 þ NH4 Cl:
4. Conclusions
Through this study, 95% copper and 90% cobalt were shown to be
leachable from a DRC copper–cobalt ore by ammonium roasting at
the following optimal conditions: the particle size of 0.10 mm, chlo-
rine ammonium to ore mass ratio of 1:2, roasting temperature of
300 °C, roasting time of 3 h, leaching time of 0.5 h and leaching tem-
perature of 60 °C. 90% copper and cobalt were precipitated for 40 min
at pH 7 and 60 °C, with 50% NH4HCO3 addition. After further separa-
tion of copper and cobalt of the copper and cobalt's mixed carbonate,
the products would be marketable.
The roasting mechanism of the copper–cobalt oxide ore by ammo-
nium chloride is proposed as follows: the formation of the intermedi-
ate compound Co(NH3)6CuCl5 in the process at temperatures below
320 °C , followed by decomposition of the intermediate compounds
to form soluble CoCl2,CuCl2 at 320 °C.
Ammonium chloride crystals obtained by crystallization of the fil-
trate with exhaust gas could be reused for the roasting process. Since
there is no waste water and gas release in the process, this technique
meets the standards of green chemistry and low environmental
impact.
ð3Þ Acknowledgment
This paper was revised by Prof. Zhenhe XU, Department of Chem-
ð4Þ ical Engineering, University of Alberta.
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