processes

Article
A Novel Technology for Separating Copper, Lead and
Zinc in Flotation Concentrate by Oxidizing Roasting
and Leaching
Qian Zhang 1,2 , Qicheng Feng 1,2, *, Shuming Wen 1,2 , Chuanfa Cui 3 and Junbo Liu 1,2
1 Faculty of Land Resource Engineering, Kunming University of Science and Technology,
Kunming 650093, China; zqian9865@163.com (Q.Z.); shmwen@126.com (S.W.);
18314563709@163.com (J.L.)
2 State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization,
Kunming University of Science and Technology, Kunming 650093, China
3 Civil engineering institute, Zhengzhou Vocational University of Information and Technology,
Zhengzhou 450000, China; ccf99999@126.com
* Correspondence: fqc@kmust.edu.cn or fqckmust@126.com; Tel.: +86-159-8719-0563




Received: 24 May 2019; Accepted: 14 June 2019; Published: 18 June 2019


Abstract: In this work, oxidizing roasting was combined with leaching to separate copper, lead, and
zinc from a concentrate obtained by bulk flotation of a low-grade ore sourced from the Jiama mining
area of Tibet. The flotation concentrate contained 7.79% Cu, 22.00% Pb, 4.81% Zn, 8.24% S, and 12.15%
CaO; copper sulfide accounted for 76.97% of the copper, lead sulfide for 25.55% of the lead, and zinc
sulfide for 67.66% of the zinc. After oxidizing roasting of the flotation concentrate, the S content in
the roasting slag decreased to 0.22%, indicating that most sulfide in the concentrate was transformed
to oxide, which was beneficial to leaching. The calcine was subjected to sulfuric acid leaching for
separation of copper, lead, and zinc; i.e., copper and zinc were leached, and lead was retained in the
residue. The optimum parameters of the leaching process were: a leaching temperature of 55 ◦ C;
sulfuric acid added at 828 kg/t calcine; a liquid:solid ratio of 3:1; and a leaching time of 1.5 h. Under
these conditions, the extents of leaching of copper and zinc were 87.43% and 64.38%, respectively.
Copper and zinc in the leaching solution could be further separated by electrowinning. The effects of
leaching parameters on the extents of leaching of copper and zinc were further revealed by X-ray
diffraction and scanning electron microscopy analysis.

Keywords: copper–lead–zinc of flotation concentrate; oxidizing roasting; leaching

1. Introduction
As the three most common nonferrous metals, copper, lead, and zinc are extensively applied
in various industrial fields and all aspects of modern life, including use in the medical industry,
alloys, electroplating, rubbers, galvanizing, and chemical engineering [1–4]. With rapid industrial and
economic development, resource consumption is increasing and single-metal deposits are gradually
decreasing. As high-grade ores decline and ores increase in complexity, development and utilization of
complex low-grade refractory ores has become an inevitable trend [5]. In nature, there are few deposits
of single sulfide ores. Oxidized ores, which are generally related to sulfide ores, comprise mainly
silicate and carbonate minerals of copper, lead, and zinc [6].
Froth flotation is widely applied in mineral processing for the production of copper–lead–zinc
concentrates [7,8]. Mixed ores are difficult to recover through beneficiation operations; hence, enormous
amounts of these resources remain unexplored, are stacked in open-air mines, or drained into tailing
reservoirs, resulting in massive waste [9]. Many researchers have adopted leaching or metallurgy

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Processes 2019, 7, 376 2 of 13

beneficiation processes to recover copper, lead, and zinc from such ores [10–15]. Gargul et al.
investigated the leaching of lead and copper from flash smelting slag using citric acid; the results
showed that this hydrometallurgical method could successfully replace the existing treatment of
slag in an electric furnace and converter [16]. Pb-free solder paste containing Sn, Bi, and Cu was
treated by ammonia leaching followed by hydrochloric acid leaching to successfully separate the
target elements [17]. Xu et al. improved copper recovery from refractory copper oxide ores using
high-gradient magnetic separation, followed by secondary grinding and then leaching; the results
demonstrated effective recovery of copper [18]. Asadi et al. [19] leach zinc from a lead–zinc flotation
tailings sample using ferric sulfate and sulfuric acid. The results showed that the degree of influence
on zinc leaching of various experimental parameters was in the order: temperature > stirring > liquid
/solid ratio > acid/ferric sulfate ratio > sulfuric acid concentration. Under optimum conditions, zinc
recovery of 94.3% was achieved. Tkacova et al. [20] researched selective leaching of zinc from a complex
Cu–Pb–Zn concentrate and demonstrated deportment of copper and zinc into the leach solution, while
lead and iron remained in the insoluble residue. Selective recovery of zinc increased with increasing
reaction surface.
The copper–lead–zinc ore found in the Jiama mining area of Tibet has a high mud content,
a high degree of oxidation, and complex properties, so it is extremely difficult to separate copper,
lead, and zinc using a single flotation technology. Therefore, it is necessary to develop an
alternative process to achieve separation of these. In this work, copper, lead, and zinc in a flotation
concentrate obtained by bulk flotation of low-grade ore could be effectively separated by an oxidizing
roasting–leaching–electrowinning process. This process provides helpful technical guidance for the
comprehensive utilization of copper, lead, and zinc from these ores.

2. Materials and Methods

The copper–lead–zinc mixed concentrate sample was obtained by flotation of raw ore from Jiama,
Tibet. Multicomponent chemical analysis showed that the concentrate contained 7.79% Cu, 22.0% Pb,
4.81% Zn, and 8.24% S. Phase analysis showed that it contained large quantities of sulfides. Copper
was mainly in the form of copper sulfide and accounted for 76.79% of total copper, while 22.39% of
copper was present as free copper oxide. Lead was mainly in the form of carbonate, accounting for
53.86% of total lead; lead sulfide comprised 25.55% of total lead, and lead sulfate accounted for 5.27%.
Zinc was mainly present (67.66%) as zinc sulfide, with 29.54% as zinc oxide. Detailed analyses of the
concentrate are presented in Tables 1–3.

Table 1. Phase analysis of copper (mass %).

Free Copper Combined Sulfide and Total

Phase Sulfate
Oxide Copper Oxide Others Copper
Content 0.05 0.85 0.91 6.05 7.86
Occupancy 0.63 10.81 11.58 76.97 100.00

Table 2. Phase analysis of lead (mass %).

Phase Sulfate Carbonate Sulfide Plumbojarosite and Others Total Lead

Content 1.16 11.85 5.62 3.37 22.00
Occupancy 5.27 53.86 25.55 15.32 100.00

Table 3. Phase analysis of zinc (mass %).

Phase Zinc Sulfate Oxide Sulfide Franklinite and Others Total Zinc
Content 0.07 1.48 3.39 0.053 5.01
Occupancy 1.40 29.54 67.66 1.06 100.00
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Oxidizing roasting experiments were conducted in a resistance furnace (Model: SX-6-16, Changsha
Kehui Furnace Technology Co., Ltd., Changsha, China), and 1000 g copper–lead–zinc mixed concentrate
was taken to a corundum dry pot and put into the resistance furnace. The temperature of the resistance
furnace was set to 1200 ◦ C in an oxygen atmosphere. When the temperature of the resistance furnace
rose to the set temperature, timing started. After roasting for 3 h, the oxygen supply was stopped,
and the power supply of the resistance furnace was turned off. Meanwhile, the oxygen-passing tube
was pulled out, and the calcined product was taken out for cooling, manual crushing, and grinding to
−74 µm for leaching.
The concentrated sulfuric acid used in this study was of analytical grade. Pure deionized water
was used for all experiments. The dissolution experiments were conducted in a laboratory apparatus
(DF-II digital display collector type magnetic stirrer, Jintan Shenglan Instrument Manufacturing Co.,
Ltd., Jintan, China), comprising a 250 cm3 wide-mouth beaker batch reactor (Yak Glass Instrument Co.,
Ltd., Chengdu, China) equipped with a condenser to prevent evaporation losses, a digitally controlled
mechanical stirrer, a thermometer to measure the temperature, and a thermostatically controlled water
bath for heating. For each experiment, 20 g roasted calcine was added into the reactor, followed by
deionized water and concentrated sulfuric acid (Chengdu Kelon Chemical Reagent Factory, Chengdu,
China). The slurry was stirred at constant temperature and allowed to react for specified times, after
which it was removed from the reactor, and subjected to solid–liquid separation. The solid residue was
filtered, dried, weighed, and subjected to chemical examination (Zinc was tested by atomic absorption
spectroscopy (Shanghai Pu Analysis Instrument Co., Ltd., Shanghai, China), and copper and lead were
determined by volumetric method). The leaching efficiency, used to evaluate the leaching performance,
was calculated as follows:
M×β
y = (1− ) × 100
Q×α
where Q is the mass of the sample before leaching, M is the mass of the leach residue, and α and β are
the copper, lead, or zinc grade of the calcine before leaching and the leach residue, respectively.

3. Results and Discussion

3.1. Oxidizing Roasting Tests of the Flotation Concentrate

It was necessary to convert the sulfides present to oxides by oxidizing roasting before leaching.
The mixed concentrate was roasted at 1200 ◦ C. The resulting calcine was ground using a grinder,
screened to −74 µm particle size, and well-mixed prior to use in the leaching tests. Multi-element
chemical analysis of this leach feed is shown in Table 4, and its X-ray diffraction (XRD) pattern is shown
in Figure 1. The leaching test sample contained 11.04% Cu, 25.40% Pb, 7.58% Zn, 10.10% CaO, and
0.22% S. The grades of copper, lead, and zinc in the calcine were higher than that those of the mixed
flotation concentrate.
XRD analysis showed no sulfide peaks, which indicated that the sulfide minerals were converted
to oxidized minerals after oxidizing roasting, which was advantageous for development of the
leaching flowsheet.

Table 4. Multi-element chemical analysis of roast calcine (mass %).

Element Cu Pb Zn S CaO MgO Fe

Content 11.04 25.40 7.58 0.22 10.10 2.27 17.32
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1200
1 1 ZnFe3O4
1000 2 Cu2O
3 Pb2SiO4

Inteensity(Counts)
2 4 Ca2ZnSi2O7
800

600
1
1
400
4 4
2 1
200 2
4 1
2 1 3

0
20 40 60 80
2-Theate/deg

Figure1.1.X-ray
Figure X-raydiffraction
diffractionpattern
patternofofroast
roastcalcine.
calcine.

3.2. The Leaching of Copper–Lead–Zinc

3.2. The Leaching of Copper–Lead–Zinc
Leaching is one effective method for treating polymetallic ores, however, the effective leaching
Leaching is one effective method for treating polymetallic ores, however, the effective leaching
extent of metals is affected by many factors, such as temperature, leach reagent concentration,
extent of metals is affected by many factors, such as temperature, leach reagent concentration,
liquid:solid ratio, and leaching time [21,22]. Ye et al. [21] used bioleaching combined with brine
liquid:solid ratio, and leaching time [21,22]. Ye et al. [21] used bioleaching combined with brine
leaching of heavy metals from lead–zinc mine tailings, which was a highly efficient method to recover
leaching of heavy metals from lead–zinc mine tailings, which was a highly efficient method to recover
lead, zinc, and other metals, but this technique required strict control of the slurry pH, and the reaction
lead, zinc, and other metals, but this technique required strict control of the slurry pH, and the
time was long with 5–30 days. Xu et al. [22] leached Cu and Zn in the mixture of calcine and soot by
reaction time was long with 5–30 days. Xu et al. [22] leached Cu and Zn in the mixture of calcine and
two-step countercurrent sulfuric acid leaching, and they studied the effect of leaching temperature,
soot by two-step countercurrent sulfuric acid leaching, and they studied the effect of leaching
sulfuric acid concentration, liquid:solid ratio, and leaching time on the leaching rates.
temperature, sulfuric acid concentration, liquid:solid ratio, and leaching time on the leaching rates.
3.2.1. Effect of Leaching Temperature
3.2.1. Effect of Leaching Temperature
Temperature is an important parameter affecting the leaching of copper and zinc in sulfuric acid
Temperature is an important parameter affecting the leaching of copper and zinc in sulfuric acid
solution. In each test, 20 g calcine was employed in the reaction beaker with a sulfuric acid dosage of
solution. In each test, 20 g calcine was employed in the reaction beaker with a sulfuric acid dosage of
644 g/t at a liquid:solid ratio of 3:1. The leaching time was 1 h under constant temperature stirring at
644 g/t at a liquid:solid ratio of 3:1. The leaching time was 1 h under constant temperature stirring at
25 ◦ C, 35 ◦ C, 45 ◦ C, 55 ◦ C, 65 ◦ C, and 75 ◦ C. The effect of reaction temperature on leaching is shown
25 °C, 35 °C, 45 °C, 55 °C, 65 °C, and 75 °C. The effect of reaction temperature on leaching is shown
in Figure 2; XRD analyses of the leaching residues obtained at different temperatures are shown in
in Figure 2; XRD analyses of the leaching residues obtained at different temperatures are shown in
Figure 3.
Figure 3.
The grades of copper and zinc first increased and then decreased in the leach residue with the
The grades of copper and zinc first increased and then decreased in the leach residue with the
increase of temperature. Similar results were seen for their concentrations in the leaching solution.
increase of temperature. Similar results were seen for their concentrations in the leaching solution.
Copper leaching reached a maximum when the temperature was 65 ◦ C, but leaching of zinc was
Copper leaching reached a maximum when the temperature was 65 °C, but leaching of zinc was
lowest. A similar phenomenon was found when Yang et al. [23] studied the leaching of aluminum
lowest. A similar phenomenon was found when Yang et al. [23] studied the leaching of aluminum
from secondary aluminum dross, and when Hyun et al. [24] investigated the leaching of CaO–SiO2
from secondary aluminum dross, and when Hyun et al. [24] investigated the leaching of CaO–SiO2
resources. Considering the relative extents of copper and zinc leaching, the optimum temperature
resources. Considering the relative extents of copper and zinc leaching, the optimum temperature
was selected as 55 ◦ C. At this temperature, copper and zinc were leached to extents of 70.11% and
was selected as 55 °C. At this temperature, copper and zinc were leached to extents of 70.11% and
61.44%, respectively.
61.44%, respectively.
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20 20
Copper grade
Copper grade Zinc
Zinc grade
grade 90
90

leaching solution/%
Copper leaching
leachingextent Zinc
Zinc leaching extent

solution/%
Copper extent leaching extent
80
80
15 15

Residue grade/%
Residue grade/%
70
70

ofleaching
60
60
10 10
50

extentof
50

Leachingextent
5 40
5 40

Leaching
30
30

0 20
0 20 30 40 50 60 70 80 20
20 30 40
Leaching 50
temperature/ 60
°C 70 80
Leaching temperature/ °C
Figure 2. Results of leaching temperature tests.
Figure2.2. Results
Figure Results of leaching
leachingtemperature
temperaturetests.
tests.

1
1 1 CaSO4·2H2O
PbSO 4·2H2O
12 CaSO
4
23 PbSO
MgFe43O4
3 MgFe3O4
2
2 (a) 25 °C
2 2 12 2
2
2 2 22 3 2 (a) 25 °C
2 2 2 2 1 2 11 2 2 2 3 2
3 222 1 31 32 12 1 2 2 1 2
2 2
2
2 3 2 2 21 2 3
11 2 2 2 260 2 2 1 270
1 2 50
10 3 20 1
30 2 1 40
1
Intensity(Counts)

10 1
20 30 40 50 60 70
Intensity(Counts)

2
2 2 (b) 55 °C
22 1 2
2
2
2 2 2 3 2 (b) 55 °C
2 22 2 1 31 2 2 2 1 2 2 1 2 11 2 2 2 3 2 2
2 1 2
3
2
2 2 3 2 2
2
10
3
20 2 330
1 2 2 240
1 11 2 2 2 3 260
1 2 50 70
2 1 2
1
10 20 30 40 50 60 70
1 2
2
2 2 1 2
2 2
2 2 (c) 75 °C
2
2 3
2
2 2 2
2
2 21 3 2
3 1 2 2 1 1 2 11 2 2 3 2 2 2 1 21
2 (c) 75 °C
2 2
2 2 3
10 20 30 402 50 60 70
2 2 2
31 2 2-Theate/deg 1 2 11 2 2 3 2 2 2 1 21
3 1 2
Figure
Figure 3. X-ray
103. X-ray diffraction
diffraction
20 patterns
patterns
30 ofofleach
leach residues at
40residues different
at50differentleach
60temperatures.
leach temperatures.
70
2-Theate/deg
Comparing
Comparing the XRD
the XRD patterns
patterns ofofthe
thesolids
solidsbefore
before and
and after
afterleaching
leaching at at
different temperatures,
different temperatures,
Figure 3. X-ray diffraction patterns of leach residues at different leach temperatures.
the composition changed obviously. The concentration of lead compounds
the composition changed obviously. The concentration of lead compounds in the residue in the residue increased,
increased,
but no copper or zinc compounds appeared, indicating that most copper and zinc was leached. The
but noComparing
copper or the
zincXRD
compounds
patterns ofappeared,
the solids indicating
before and that
after most copper
leaching and zinc
at different was leached.
temperatures,
Thethecompounds present
composition changedin the calcine were
obviously. the same at 25
The concentration of◦lead ◦ C, and 75 ◦ C, but differences formed
C, 55compounds in the residue increased,
in but
the leach residue
no copper generated
or zinc at different
compounds temperatures.
appeared, indicatingWhen the temperature
that most increased
copper and zinc ◦ C to
from 25The
was leached.
◦ ◦
75 C, the PbSO4 content of the leach residue increased, reaching a maximum at 75 C. Combined with
Processes 2019, 7, 376 6 of 13

the leaching results, it was surmised that PbSO4 may cover the surfaces of the copper and zinc minerals,
resulting in a reduction of their leaching. This phenomenon was also reported by Kim et al. [10], who
investigated the effect of temperature on the selective leaching of Pb and Cu from secondary lead
smelting residues. They showed that the leaching extent of Pb and Cu dramatically decreased with
Processes 2019, 7, x FOR PEER REVIEW 6 of 13
temperature due to PbSO4 formation at higher temperature.
compounds present in the calcine were the same at 25 °C, 55 °C, and 75 °C, but differences formed in
3.2.2. Effect of Concentrated Sulfuric Acid Dosage
the leach residue generated at different temperatures. When the temperature increased from 25 °C to
75 Dosage
°C, the PbSO content of
of the4 lixiviant is athe leach
very residue factor
important increased, reaching
affecting a maximum
leaching. at 75 °C.
Experiments Combined
were conducted
with the leaching results, it was surmised that PbSO may cover the surfaces of
for 1 h to determine the effect of concentrated sulfuric acid dosage on 20 g calcine. The reaction
4 the copper and zinc
minerals, resulting in a reduction of their leaching. ◦
This phenomenon was also
temperature and liquid:solid ratio were kept at 55 C and 3:1, respectively. Sulfuric acid dosages reported by Kim et al. of
552[10], who
kg/t, 644investigated the828
kg/t, 736 kg/t, effect of temperature
kg/t, and 920 kg/ton the considered.
were selective leaching of Pb and Cu from
The experimental secondary
results are shown
lead smelting residues. They showed that the leaching
in Figure 4; XRD analyses of the leach residues are shown in Figure 5. extent of Pb and Cu dramatically decreased
with temperature
Figure 4 showsdue thattothe
PbSO 4 formation at higher temperature.
grades of copper and zinc in the leach residue first decreased and then
increased with the increase of sulfuric acid dosage; however, the solution analysis showed that leaching
3.2.2. Effect of Concentrated Sulfuric Acid Dosage
of copper and zinc first increased and then decreased. When the sulfuric acid dosage was 828 kg/t, the
leaching Dosage of theand
of copper lixiviant is a very
zinc were importantatfactor
maximized, 89.04%affecting leaching.
and 63.86%, Experiments
respectively. werethe
When conducted
dosage of
for 1 h to determine the effect of concentrated sulfuric acid dosage on 20 g calcine.
sulfuric acid was continuously increased to 920 kg/t, the leaching extent of copper and zinc minimized. The reaction
temperature
This is attributedandtoliquid:solid
the difficultyratio
inwere kept at
filtration of 55 °C andproduct
leaching 3:1, respectively. Sulfuric acid
because sulfuric acid dosages of
reacted with
552 kg/t, 644 kg/t, 736 kg/t, 828 kg/t, and 920 kg/t were considered. The experimental
SiO2 in the leaching material to form the polymerization of silica sol, and the polymerization of silica results are
solshown in Figure 4; XRD analyses of the leach residues are shown in Figure 5.
increased with an increased acidity, which will clog the pores of filter paper, making filtration
Figure 4 shows that the grades of copper and zinc in the leach residue first decreased and then
difficult [25]. Therefore, the optimum dosage of sulfuric acid is 828 kg/t.
increased with the increase of sulfuric acid dosage; however, the solution analysis showed that
XRD analyses of the leach residues obtained for different sulfuric acid dosages showed that the
leaching of copper and zinc first increased and then decreased. When the sulfuric acid dosage was
same compounds were present in the leach residue, but their concentrations differed with the increase
828 kg/t, the leaching of copper and zinc were maximized, at 89.04% and 63.86%, respectively. When
of sulfuric acid dosage. When the dosage increased from 552 kg/t to 920 kg/t, the PbSO4 content
the dosage of sulfuric acid was continuously increased to 920 kg/t, the leaching extent of copper and
increased, reachingThis
zinc minimized. a maximum at 920
is attributed kg/t.
to the It is postulated
difficulty thatoftoo
in filtration much PbSO
leaching product4 covered
becausethe surface
sulfuric
of acid
copperreacted with SiO2 in the leaching material to form the polymerization of silica sol, and the of
and zinc minerals and reduced the extents of their leaching. Combined with the results
thepolymerization
leaching test, itofissilica
considered that high
sol increased withsulfuric dosages
an increased were which
acidity, disadvantageous
will clog thetopores
the leaching
of filter of
copper
paper,and zinc. filtration difficult [25]. Therefore, the optimum dosage of sulfuric acid is 828kg/t.
making

20 100
Copper grade Zinc grade
Leaching extent of leaching solution/%

Copper leaching extent Zinc leaching extent

90

15 80
Residue grade/%

70

10 60

50

5 40

30

0 20
500 550 600 650 700 750 800 850 900 950
sulfuric acid dosage/g/t

Figure4.4.Results
Figure Results of
of leaching at
at different
differentsulfuric
sulfuricacid
aciddosage.
dosage.
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1
1 CaSO4·2H20
2 PbSO4
3 MgFe3O4
2

2 12
2 2
2 2 3 (a) 552kg/t
2 2 2 3
31 2
2 2 1 21 1 1 11 2 2 2 3 1

10 20 30 40 50 60 70
1
Intensity(Counts)

2 2
2 2 2
21
2 22 3 2 (b) 828kg/t
2 2 2 1 1 11 2 2 3 2
31 2 1 1 3 1

10 20 30 40 50 60 70
2
2 2 2
2
2 2 2 2
2 3
2 (c) 920kg/t
2 1 2 2 2 3 3 1
1 3 1 1 2 1 1 2 22 2

10 20 30 40 50 60 70
2-Theate/deg

Figure5.5. X-ray
Figure X-ray diffraction
diffractionpatterns
patternsof
ofleach
leachresidues
residuesafter
afterleaching
leachingatatdifferent
differentsulfuric
sulfuricacid
aciddosages.
dosages.

3.2.3. XRD
Effectanalyses
of Liquid:Solid Ratioresidues obtained for different sulfuric acid dosages showed that the
of the leach
sameEach
compounds were 20
test employed present in the
g calcine at aleach residue,
leaching 55 ◦ C and sulfuric
but theirofconcentrations
temperature differed
acidwith
dosage the
increase
of of sulfuric
828 kg/t. acid dosage.
Liquid:solid ratios ofWhen the4:1,
2:1, 3:1, dosage
and increased from 552 kg/t
5:1 were evaluated for atoleaching
920 kg/t, the of
time PbSO
1 h.4
content
The increased,results
experimental reaching
are ashown
maximum at 9206.kg/t.
in Figure XRDItanalyses
is postulated
of thethat too much
leaching PbSOare
residues 4 covered
shown the in
surface7.of copper and zinc minerals and reduced the extents of their leaching. Combined with the
Figure
results
Theofleaching
the leaching test, itand
of copper is considered that highand
zinc first increased sulfuric
thendosages
decreased were
in disadvantageous
the leach residue to the
with
leaching of copper and zinc.
increase of the liquid:solid ratio. The leaching of zinc was maximized at a liquid:solid ratio of 3:1.
Leaching of copper was maximized at a liquid:solid ratio of 4:1, but that of zinc was at a minimum.
3.2.3. Effect of
Considering theLiquid:Solid Ratioof leaching, the optimal liquid:solid ratio was selected as 3:1, under
relative extents
whichEach
conditions the leaching
test employed 20 g extents
calcine of
at copper andtemperature
a leaching zinc were 85.88%
of 55 and 61.27%,
°C and respectively.
sulfuric acid dosage of
XRD analyses showed that the content of the
828 kg/t. Liquid:solid ratios of 2:1, 3:1, 4:1, and 5:1 were PbSO 4 evaluated for a leachingwas
phase in the leach residue timelarger when
of 1 h. The
the liquid:solidresults
experimental ratio was
aresmall.
shown Asinthe liquid:solid
Figure 6. XRD ratio increased,
analyses theleaching
of the PbSO4 content
residuesdecreased,
are shown but ina
high liquid:solid
Figure 7. ratio was disadvantageous to the leaching of metals; therefore, a liquid:solid ratio of
3:1 was considered
The leaching of appropriate.
copper and zinc first increased and then decreased in the leach residue with
increase of the liquid:solid ratio. The leaching of zinc was maximized at a liquid:solid ratio of 3:1.
Leaching of copper was maximized at a liquid:solid ratio of 4:1, but that of zinc was at a minimum.
Considering the relative extents of leaching, the optimal liquid:solid ratio was selected as 3:1, under
which conditions the leaching extents of copper and zinc were 85.88% and 61.27%, respectively.
XRD analyses showed that the content of the PbSO4 phase in the leach residue was larger when
the liquid:solid ratio was small. As the liquid:solid ratio increased, the PbSO4 content decreased, but
a high liquid:solid ratio was disadvantageous to the leaching of metals; therefore, a liquid:solid ratio
of 3:1 was considered appropriate.
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20
20 100
100
Copper
Coppergrade
grade Zinc
Zincgrade
grade

solution/%
leaching solution/%
Copper
Copperleaching
leachingextent
extent Zinc
Zincleaching
leachingextent
extent
90
90

15
15 80
80

grade%
Residue grade%

of leaching
70
70
10
10
Residue

60
60

extent of
Leaching extent
50
50
55

Leaching
40
40

30
30
00
2:1
2:1 3:1
3:1 4:1
4:1 5:1
5:1
liquid:solid
liquid:solidratio
ratio
Figure
6.6.Results
Figure
Figure 6.Results ofofleaching
Resultsof leaching
leachingliquid:solid
liquid:solidratio
liquid:solid ratiotests.
ratiotests.
tests.

22
CaSO4·2H
11CaSO 4·2H2O
2O
22
11 22 22 22PbSO
PbSO4 4
22 33MgFe
22 MgFe3O
3O44
22
22 22
11 22 11
22 (a)
(a)2:1
2:1
22 22
33 3322 22 11 22
22
22 22 33 2
22 22 22 2 22 2222
11 22

10101 2020 3030 4040 5050 6060 7070

1
Intensity(Counts)
Intensity(Counts)

22 22
22 222 22
211
22 2222 11 22
22 33 22 22 (b)
(b)3:1
3:1
22 11 22 22 22 22 33

1010 2020 3030 4040 5050 6060 7070

11

22 2
2 222122 22
1
22 2222 11 22 (c)
(c)5:1
5:1
22 33 22 11 22 22 22 22 22 33 22
1010 2020 3030 4040 5050 6060 7070
2-Theate/deg
2-Theate/deg
Figure
Figure
Figure 7.7.X-ray
7. X-ray X-raydiffraction
diffraction
diffraction patterns ofofleach
patternsof
patterns leach
leachresidue
residueobtained
residue obtained
obtainedatatat
different
differentliquid:solid
differentliquid:solidratios.
ratios.
liquid:solid ratios.

3.2.4. Effect of Leaching Time

The effect of leaching time was evaluated using 20 g roast calcine at a leaching temperature of
55 ◦ C,
sulfuric acid dosage of 828 kg/t, and liquid:solid ratio of 3:1 for times of 0.5 h, 1 h, 1.5 h, and 2 h.
The results are shown in Figure 8; XRD analyses of the leach residue are shown in Figure 9.
 Processes 2019,
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FOR PEER
PEER REVIEW
REVIEW 99 of
of 13
13

3.2.4. Effect
3.2.4. Effect of
of Leaching
Leaching Time
Time
The effect
The effect of
of leaching
leaching time
time was
was evaluated
evaluated using
using 20
20 gg roast
roast calcine
calcine at
at aa leaching
leaching temperature
temperature of
of
552019,
55
Processes °C, sulfuric
°C, sulfuric acid dosage
7, 376 acid dosage of
of 828
828 kg/t,
kg/t, and
and liquid:solid
liquid:solid ratio
ratio of
of 3:1
3:1 for
for times
times of
of 0.5
0.5 h,
h, 11 h,
h, 1.5
1.5 h,
h, and
and 229 of 13
h. The
h. The results
results are
are shown
shown in
in Figure
Figure 8;
8; XRD
XRD analyses
analyses of
of the
the leach
leach residue
residue are
are shown
shown in
in Figure
Figure 9.
9.

20
20 100
100
Copper grade
Copper grade Zinc grade
Zinc grade

solution/%
leachingsolution/%
Copper leaching extent
Copper leaching extent Zinc leaching extent
Zinc leaching extent 90
90

15
15 80
80

grade/%
Residuegrade/%

ofleaching
70
70

10
10
60
Residue

60

extentof
Leachingextent
50
50
55

Leaching
40
40

30
30
00
0.5
0.5 1.0
1.0 1.5
1.5 2.0
2.0
Leaching time/h
Leaching time/h
Figure
Figure 8.Results
8.8.
Figure Results of
Results of leaching
leaching time
leaching time test.
timetest.
test.

11
11 CaSO ·2H2O
CaSO4·2H O
4 2

22 PbSO
PbSO4
4
3 MgFe3O
3 MgFe O4
3 4

22 2 2
2 222 112 22
2
2 222 3 2 (a) 0.5h
0.5h
22
2 2 3 11 22 2 2 22
2
22 33 (a)

10
10 20
20 30
30 40
40 50
50 60
60 70
70
11
Intensity(Counts)
Intensity(Counts)

22
22
22 2 1 22
22 21
22 22
22 22 33
22
22 3311 2 11 22 22 12 22 2 22 33 22 (b) 1.5h
(b) 1.5h
2 12 2
10
10 20
20 30
30 40
40 50
50 60
60 70
70
22
22
22 22
22
22
11 22
22 22 33 22
11
22
22 331 11 22 22 2 22 2 22 33 22 (c) 2h
(c) 2h
1 22 112 2

10
10 20
20 30
30 40
40 50
50 60
60 70
70
2-Theata/deg
2-Theata/deg
Figure
Figure
Figure 9. X-ray
9. X-ray
9. X-ray diffraction
diffraction
diffraction patternsof
patterns
patterns ofleach
of leach residues
leach residues obtained
residues obtained
obtainedfor
for different
different
for leaching
leaching
different times.
times.
leaching times.

The leaching extent of copper and zinc first increased in the leach residue, and then decreased
with an increase of leaching time. The leaching of copper and zinc was maximized in the leaching
solution at 87.43% and 64.38%, respectively, when leaching time was 1.5 h. This phenomenon was also
reported by Zhang et al. [26], who investigated the effect of leaching time on Co leaching from laterite
ore, and the results showed that the leaching extent of Co reached the maximum, and the leaching rate
decreased, when the leaching time was prolonged.
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x FOR PEER REVIEW 10 of 13
10 of 13

The leaching extent of copper and zinc first increased in the leach residue, and then decreased
with XRD analysesofshowed
an increase leachingthat the The
time. PbSO 4 content
leaching ofincreased
copper and withzinc
the was
increase of leaching
maximized time.
in the When
leaching
leaching for 2 h, the content of PbSO
solution at 87.43% and 64.38%, respectively, 4 increased to the maximum, but the leaching
when leaching time was 1.5 h. This phenomenon was rate of copper
and zinc
also decreased.
reported by Zhang It may
et al.be[26],
thatwho
a large amount of
investigated PbSO
the 4 covers
effect the surface
of leaching time on ofCocopper and from
leaching zinc,
hindering
laterite ore,the
andcontact between
the results leaching
showed thatagent and target
the leaching elements,
extent of Co and reduces
reached the leachingand
the maximum, ratethe
of
copper and zinc. Therefore, a leaching time of 1.5
leaching rate decreased, when the leaching time was prolonged. h is more appropriate.
XRD analyses showed that the PbSO4 content increased with the increase of leaching time. When
3.3. Scanning
leaching for 2Electron
hours, theMicroscopy
content of of Leach
PbSOSolids Before and After Leaching
4 increased to the maximum, but the leaching rate of copper

and zinc decreased.

The leaching It may
results andbe XRD that a largediscussed
analyses amount of in PbSO 4 covers sections
the preceding the surface of copper
showed and zinc,
that copper and
hindering the contact between leaching agent and target elements, and reduces
zinc could be effectively leached under certain conditions, and that the compositions and concentrations the leaching rate of
copper and zinc.
of the calcine feedTherefore,
and leach aresidue
leaching time ofconsiderably.
differed 1.5 hours is more appropriate. of the roast calcine and
The morphologies
leach residue were analyzed by SEM, as shown in Figures 10 and 11.
3.3. Scanning
Comparing Electron Microscopy
Figures 10 and of 11Leach
shows Solids
thatBefore and After
significant Leaching
changes occurred on the mineral surface
during the leaching process. Before leaching, the surface of
The leaching results and XRD analyses discussed in the preceding sections the calcine was smooth;showed after leaching,
that copper
the structure of the calcine was destroyed and there were a lot of flocs
and zinc could be effectively leached under certain conditions, and that the compositions and on the surface. Combining
these observations
concentrations with
of the the results
calcine of Figure
feed and leach1,residue
Figure differed
9b, it wasconsiderably.
concluded that Thethemorphologies
flocs may comprise
of the
CaSO and
roast calcine
4 PbSO that covered the surface of the residue after leaching.
and 4leach residue were analyzed by SEM, as shown in Figure 10, Figure 11.

Figure 10. Scanning

Scanning electron
electron micrograph
micrograph of morphology of roast calcine (before leaching).
Processes 2019, 7, 376 11 of 13
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Figure
Figure 11.
11. Scanning
Scanning electron
electron micrograph
micrograph of
of morphology
morphology of
of roast
roast calcine
calcine (after leaching).
(after leaching).

4. Conclusions
Comparing Figure 10 and Figure 11 shows that significant changes occurred on the mineral
surface during
Copper, the and
lead, leaching process.inBefore
zinc present leaching,
a flotation the surface
concentrate couldof be
theeffectively
calcine was smooth;by
separated after
an
leaching, the structure of the calcine was destroyed and there were a lot of flocs on
oxidizing roasting–leaching–electrowinning process, which provides helpful technical guidance for the surface.
Combining these observations
the comprehensive with
utilization of oresthe results
from of Figure
the Jiama 1, Figure
mining area of9b, it was concluded that the flocs
Tibet.
may (1)
comprise CaSO 4 and PbSO4 that covered the surface of the residue after leaching.
Sulfide in the flotation concentrate was transformed into oxide on oxidizing roasting at high
temperature, which facilitated the subsequent leaching of copper and zinc in sulfuric acid solution.
4. Conclusions
Copper and zinc in the roast calcine were leached to extents of 87.43% and 64.38%, respectively, at a
leaching temperature
Copper, lead, andofzinc 55 ◦ C, sulfuric
present in acid dosageconcentrate
a flotation of 828 kg/t, could
liquid:solid ratio of 3:1,
be effectively and leaching
separated by an
time of 1.5roasting–leaching–electrowinning
oxidizing h. It is proposed that copper and zinc in the
process, leachprovides
which solution helpful
could be further separated
technical by
guidance for
electrowinning,
the comprehensive andutilization
lead in theofleach
ores residue
from thecould
Jiamabemining
pyrometallurgy refined.
area of Tibet.
(2) XRD
(1) Sulfideand inSEM analysesconcentrate
the flotation indicated thatwasthe structure ofinto
transformed the calcine
oxide onwas destroyed
oxidizing on subjection
roasting at high
to sulfuric acid
temperature, whichleaching, and its
facilitated thecomposition
subsequent changed.
leaching ofLarge
copperamounts
and zincof in
CaSO 4 andacid
sulfuric PbSO 4 were
solution.
produced
Copper and during
zinc in thethe
leaching processwere
roast calcine and leached
would covered theof
to extents surface
87.43%ofand
the solid,
64.38%, which hindered at
respectively, thea
of copper and
leaching temperature ofzinc.
55 °C,Removal
sulfuric of calcium
acid dosageminerals prior
of 828 kg/t, to the sulfuric
liquid:solid ratioacid leach
of 3:1, andwould be
leaching
advantageous
time of 1.5 h. Ittoisthe subsequent
proposed extraction
that copper andofzinc
copper and
in the zincsolution
leach from calcine.
could be further separated by
electrowinning, and lead in the leach residue could be pyrometallurgy refined.
Author Contributions: Q.Z.; experimental, methodology, software, formal analysis, data curation, writing. Q.F.;
(2) XRD and SEM analyses indicated that the structure of the calcine was destroyed on subjection
resources, guidance review and editing. S.W.; investigate and guide. C.C.; data analysis. J.L.; experimental and
to sulfuric
data analysis.acid leaching, and its composition changed. Large amounts of CaSO 4 and PbSO4 were
produced during the
Acknowledgments: Thisleaching
work wasprocess andsupported
financially would covered theApplied
by Yunnan surfaceBasic
of the solid, which
Research hindered
Project (Grant No.
2018FD035) and China Postdoctoral Science Foundation (Grant No. 2018T111000).
the leaching of copper and zinc. Removal of calcium minerals prior to the sulfuric acid leach would
be advantageous
Conflicts to The
of Interest: the authors
subsequent extraction
declare of copper
no competing and
financial zinc from calcine.
interest.

Author Contributions: Q.Z.; experimental, methodology, software, formal analysis, data curation, writing. Q.F.;
resources, guidance review and editing. S.W.; investigate and guide. C.C.; data analysis. J.L.; experimental and
data analysis

Acknowledgments: This work was financially supported by Yunnan Applied Basic Research Project (Grant No.
2018FD035) and China Postdoctoral Science Foundation (Grant No. 2018T111000).
Processes 2019, 7, 376 12 of 13

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