metals

Article
Improving Beneficiation of Copper and Iron from
Copper Slag by Modifying the Molten Copper Slag
Zhengqi Guo *, Deqing Zhu *, Jian Pan, Tengjiao Wu and Feng Zhang
School of Mineral Processing and Bioengineering, Central South University, Changsha 410083, China;
pjcsu@csu.edu.cn (J.P.); wwwwtjcom@126.com (T.W.); zhangfengcsu@126.com (F.Z.)
* Correspondence: guozqcsu@csu.edu.cn (Z.G.); dqzhu@csu.edu.cn (D.Z.);
Tel.: +86-185-7313-1417 (Z.G.); +86-731-8883-6041 (D.Z.); Fax: +86-731-8883-6942 (Z.G. & D.Z.)

Academic Editor: Hugo F. Lopez

Received: 26 February 2016; Accepted: 7 April 2016; Published: 14 April 2016

Abstract: In the paper, a new technology was developed to improve the beneficiation of copper and
iron components from copper slag, by modifying the molten slag to promote the mineralization
of valuable minerals and to induce the growth of mineral grains. Various parameters, including
binary basicity, dosage of compound additive, modification temperature, cooling rate and the end
point temperature of slow cooling were investigated. Meanwhile, optical microscope, scanning
electron microscope and energy dispersive spectrometer (SEM-EDS) was employed to determine the
mineralogy of the modified and unmodified slag, as well as to reveal the mechanisms of enhancing
beneficiation. The results show that under the proper conditions, the copper grade of rougher
copper concentrate was increased from 6.43% to 11.04%, iron recovery of magnetic separation
was increased significantly from 32.40% to 63.26%, and other evaluation indexes were changed
slightly, in comparison with unmodified copper slag. Moreover, matte and magnetite grains in the
modified slag aggregated together and grew obviously to the mean size of over 50 µm, resulting in
an improvement of beneficiation of copper and iron.

Keywords: copper slag; slag modification; flotation; magnetic separation; mineral grain size
growth; recycling

1. Introduction
Pyrometallurgy is the dominant technology for current copper extraction, by which almost
80% of total copper in the word has been generated [1]. Approximately 2.0–3.0 tons of copper slag
are generated per ton of copper production, depending on the properties of copper concentrates
and operating conditions in the pyrometallurgical process [2–5]. It has been roughly estimated that
approximately 12 million tons of copper slag is produced every year, and the amount of accumulated
waster copper slag reached 140 million ton by 2015 in China [6]. Generally, copper slag contains
about 35–45 wt. % iron and 0.5–1.5 wt. % copper, indicating that it is a valuable secondary resource
for recycling and utilization [3]. However, more than 80% of copper slag has not been effectively
utilized, which not only wastes the valuable resources, but also potentially causes severe damages to
the ecological environment, such as heavy metal pollution to surrounding soils and watercourses [7,8].
Hence, it is extremely urgent to develop appropriate technology for comprehensive utilization of
copper slag characterized as hazardous materials, due to the increasing environmental concern for
disposal of copper slag.
In recent years, extensive studies have been carried out to recover the valuable metals from copper
slag. Basically, they can be classified into three main categories, namely physical separation process,
pyrometallurgical process and hydrometallurgical process, such as flotation [9–12], roasting [13,14]
and leaching [15,16]. Indeed, these are effective routes to recover and utilize the copper and other

Metals 2016, 6, 86; doi:10.3390/met6040086 www.mdpi.com/journal/metals

Metals 2016, 6, 86 2 of 17

non-ferrous metals. Particularly, it is considerably successful to recovery copper from slow-cooled

copper slag by flotation process. However, these methods may suffer secondary pollutants or a
difficulty in further treatments, and the recovery of iron is neglected.
An earlier work noted that magnetic separation is a feasible way to recover iron from the tailings of
waste copper slag flotation. Unfortunately, the iron grade of magnetic products and the recovery of iron
by the magnetic separation process is relatively low, only 52.21% and 38.09%, respectively, due to the
fact that iron constituents mainly exist in the form of fayalite (Fe2 SiO4 ) [17]. Therefore, regarding the
recovery of iron from copper flotation slag, more prior works focused mostly on the pyrometallurgical
process, such as roasting-magnetic process and smelting reduction process. The roasting-magnetic
separation process is the route to convert the metals into a desired phase, which can be easily separated
from the slag through mixing copper slag with calcium oxide as fluxes and carbon as a reducing agent,
then roasting the mixture at a temperature of about 1200–1300 ˝ C, followed by magnetic separation to
recover iron from the copper flotation slag [18–22]. The smelting reduction process is a method where
waste slag is carbothermally smelted to acquire molten iron by reducing “FeO” to metallic iron at very
high temperatures (above 1350 ˝ C) [23]. However, these processes have some disadvantages such as
high temperature, energy consumption and production cost. In brief, it is difficult to recover copper
and iron in the slag technically, effectively and economically by traditional separation technologies,
and much latent heat is wasted when discharging the molten slag from the furnace at 1250–1300 ˝ C
to slowly cool for recovery copper as well as other non-ferrous metals by flotation and heating the
tailings again to recover iron. In addition, previous researchers have only focused on cold copper slag
when slag-recycling issues are studied; however, once the slag cools down from its molten state to
its solidification, the cold slag and its physical properties are often considered to be fixed. Generally,
there is a significantly potential to affect the functional properties of the cold slag during the hot
stage of slag processing [24]. If the high temperature slag treatment process is applied to molten slag,
the properties of slag can be tailored to the requirements of the targeted application.
Herein, an innovative technology has been developed to transform fayalite to magnetite and
to induce the grain growth of copper matte and magnetite by modifying the molten copper slag.
As a result, it is effective to improve recovery and separation of copper and iron from the copper
slag; meanwhile, the latent heat energy of the molten slag was effectively utilized and the energy
consumption is also reduced. Therefore, the employment of the new technology promises many
significant benefits, such as a reduction in the wastes or recycling byproducts in non-ferrous metallurgy
process, and provides solutions for future metal security.

2. Materials and Methods

2.1. Materials

2.1.1. Copper Slag

The copper slag used in the experiments is a byproduct generated during the cleaning of electric
furnace slag and refining of copper in Tongling Non-ferrous Metals Group Holding Co., Ltd (Tongling,
China). As shown in Table 1, the main chemical compositions contained in the waste slag are 42.85 wt. %
FeO and 31.11 wt. % SiO2 , and the content of Cu reached 0.80 wt. %. The X-ray diffraction (XRD)
spectrum of an average sample is shown in Figure 1, indicating that the main crystal phases in the slag
are fayalite (Fe2 SiO4 ) and magnetite (Fe3 O4 ).

Table 1. Chemical compositions of copper slag (wt. %).

Element TFe FeO SiO2 CaO MgO Al2 O3 Cu Pb S P LOI

Percentage 39.10 42.85 31.11 2.44 1.79 2.29 0.80 0.13 0.45 0.10 0.88
  2016, 6, 86  Metals 2016, 6, 86 3 of 17 3

F
800
F
M
F
F
Intensity/CPS

600 F
M F F
F F M
FF
FF M FM

400
10 20 30 40 50 60 70
Two-theta(deg)  
Figure 1. X-ray diffraction patterns of copper slag (F—fayalite; M—magnetite).
Figure 1. X‐ray diffraction patterns of copper slag (F—fayalite; M—magnetite). 
Chemical phase analysis of the sample was determined to measure the quantitative distribution
characteristic of iron and copper in the copper slag, and the results are illustrated in Tables 2 and 3
Chemical phase analysis of the sample was determined to measure the quantitative distribu
respectively. Iron mainly exists in the form of fayalite and magnetite, which will result in relatively
acteristic of iron and copper in the copper slag, and the results are illustrated in Tables 2 an
low recovery of iron by traditional magnetic separation process, and copper mainly occurs in the form
of copper sulfide and metallic copper, and combined copper oxide fraction is also as high as 17.50%.
ectively. Iron mainly exists in the form of fayalite and magnetite, which will result in relat
recovery  of  iron  by  traditional  magnetic 
Table 2. The separation 
distribution of iron in associatedprocess, 
minerals (wt.and 
%). copper  mainly  occurs  in
 of copper sulfide and metallic copper, and combined copper oxide fraction is also as hig
Mineral Ferric Sulfate Magnetite Iron Sulfide Hematite Fayalite Fetotal

%.  Content 0.41 12.85 0.01 3.75 22.08 39.10

Fraction 1.05 32.86 0.03 9.59 56.47 100.00

Table 2. The distribution of iron in associated minerals (wt. %). 
Table 3. The distribution of copper in associated minerals (wt. %).

Mineral Copper Oxide Metallic Copper Copper Sulfide Combined Copper Oxide Cutotal
Mineral  Ferric Sulfate
Content 0.02
  Magnetite  Iron Sulfide  Hematite  Fayalite
0.18 0.46 0.14 0.80
  Fetotal 
Content  0.41 
Fraction 2.50 12.85 
22.50 0.01 
57.50 3.75 
17.50 22.08 
100.00 39.10 
Fraction  1.05  32.86  0.03  9.59  56.47  100.00
Figure 2 presents the micrographs of copper slag, which confirms that fayalite and magnetite are
the main minerals in the copper slag, and they are closely combined with copper matte and glassy
phase.Table 3. The distribution of copper in associated minerals (wt. %). 
It is also observed that matte, as the copper-bearing mineral, and magnetite are characterized
by super fine particle size of a few micro inclusions being homogeneously dispersed in the slag.
Mineral  Copper Oxide  Metallic Copper Copper Sulfide Combined Copper Oxide  Cutota
Content  0.02  0.18  0.46  0.14  0.80 
Fraction  2.50  22.50  57.50  17.50  100.00

Figure 2 presents the micrographs of copper slag, which confirms that fayalite and magn
he main minerals in the copper slag, and they are closely combined with copper matte and g
e. It is also observed that matte, as the copper‐bearing mineral, and magnetite are character
uper fine particle size of a few micro inclusions being homogeneously dispersed in the slag
 Metals 2016, 6, 86 4 of 17
Metals 2016, 6, 86  4 of 17 

 
Figure 2. Microstructure of copper slag. 
Figure 2. Microstructure of copper slag.

2.1.2. Flux 
2.1.2. Flux

CaO  of CaO of analytic

analytic  grade
grade  was used
was  used asas fluxflux 
in this work
in  towork 
this  adjust the
to binary basicity
adjust  (ratio of CaO/SiO
the  binary  basicity 2 )(ratio  of 
of mixture, and its particle size is less than 74 µm.
CaO/SiO2) of mixture, and its particle size is less than 74 μm. 
2.1.3. Compound Additive
2.1.3. Compound Additive 
The compound additive containing hematite, sulfide and viscosity reducer was produced by
The Central South University,
compound  in a powder form
additive  containing  with over
hematite,  80% passing
sulfide  43 µm, and
and  viscosity  the major
reducer  chemical
was  produced  by 
constituents as shown in Table 4.
Central South University, in a powder form with over 80% passing 43 μm, and the major chemical 
constituents as shown in Table 4. 
Table 4. Chemical compositions of compound additive (wt. %).

Element TFe 2SiO CaO MgO Al O

2 3 MnO Cu S
Table 4. Chemical compositions of compound additive (wt. %). 
Percentage 52.44 2.09 0.77 0.68 1.63 9.3 1.23 12.13
Element  TFe  SiO2  CaO  MgO  Al2O3  MnO  Cu  S 
2.2. Experimental Methods
Percentage  52.44  2.09  0.77  0.68  1.63  9.3  1.23  12.13 
As depicted in Figure 3, the proposed procedure mainly includes the steps of: (1) crushing copper
slag; (2) mixing the slag with additives; (3) subjecting the mixture to modification reactions at high
2.2. Experimental Methods 
temperature and then slowly cooling; (4) recovering copper from the cooled slag obtained in Step 3 by
As  flotation;
depicted  in (5)
and Figure  3,  the 
separating ironproposed  procedure 
from the tailings of Step 4mainly  includes 
by wet magnetic the  steps  of:  (1)  crushing 
separation.
copper slag; (2) mixing the slag with additives; (3) subjecting the mixture to modification reactions at 
high temperature and then slowly cooling; (4) recovering copper from the cooled slag obtained in 
Step 3 by flotation; and (5) separating iron from the tailings of Step 4 by wet magnetic separation. 
Metals 2016, 6, 86 5 of 17
Metals 2016, 6, 86  5 of 17 

 
Figure 3. Schematic flow sheet of the modification-beneficiation process of copper slag.
Figure 3. Schematic flow sheet of the modification‐beneficiation process of copper slag. 

2.2.1. 2.2.1. Modification of Copper Slag 
Modification of Copper Slag
The  modification  and  slow  cooling  of  copper  slag  was  conducted  in  a  MoSi2  electric  furnace 
The modification and slow cooling of copper slag was conducted in a MoSi2 electric furnace
under the high purity N2 (nitrogen) flow of 10 L/min. In the study, the copper slag was crushed to 
under the high purity N2 (nitrogen) flow of 10 L/min. In the study, the copper slag was crushed to
below 0.15 mm by a hammer and a pulverizer. Then, the raw slag was mixed with a certain quantity 
belowof 0.15 mm by(burnt 
additives  a hammer and compound 
lime  and  a pulverizer. Then, the
additive)  raw slag
according  to was mixed with
the  required  a certain
amount  quantity of
in  alumina 
additives (burnt lime and compound additive) according to the required amount in alumina crucible.
crucible. The raw mixture was completely mixed manually for about 15 min. After that, the uniformly 
The raw mixture was completely mixed manually for about 15 min. After that, the uniformly mixed raw
mixed raw materials were charged into an electric resistance furnace and were heated up in nitrogen 
materials were charged into an electric resistance furnace and were heated up in nitrogen atmosphere.
atmosphere. After reaching the target temperature, the furnace was kept at that temperature for 120 
min so that the temperature inside the furnace and the slag had enough time to become uniform and 
After reaching the target temperature, the furnace was kept at that temperature for 120 min so that
constant,  and 
the temperature then  it 
inside thewas  slowly and
furnace cooled 
theto  a  certain 
slag temperature 
had enough time (end  point  temperature 
to become uniform and of  slow 
constant,
cooling)  at  different  cooling  rates.  Once  the  slow  cooling  stage  was  concluded, 
and then it was slowly cooled to a certain temperature (end point temperature of slow cooling) the  samples  were  at
taken out of the furnace and cooled to ambient temperature under the protection of nitrogen for the 
different cooling rates. Once the slow cooling stage was concluded, the samples were taken out of
subsequent beneficiation processes. 
the furnace and cooled to ambient temperature under the protection of nitrogen for the subsequent
beneficiation processes.
2.2.2. Flotation and Magnetic Separation 
In this research, direct one stage flotation (rougher) and magnetic separation (rougher) has been 
2.2.2. Flotation and Magnetic Separation
used. The experimental results were evaluated by modification efficiency and phase transformation 
In this research, direct one stage flotation (rougher) and magnetic separation (rougher)
degree. 
has been Prior to grinding, the modified copper slag was crushed to a particle size below 1 mm. Then, a 
used. The experimental results were evaluated by modification efficiency and phase
100 g batch of slag (as crushed) was mixed with 100 mL of water and ground in a small stainless steel 
transformation degree.
ball mill (model: XMQ240×90, Wuhan Rock Crush & Grand Equipment Manufacture Co., Wuhan, 
Prior to grinding, the modified copper slag was crushed to a particle size below 1 mm. Then,
a 100 China). 
g batchGrind 
of slagestablishment 
(as crushed)tests 
was determined 
mixed withthe  100time 
mL required to 
of water andproduce a P90 
ground in a smallof 45  μm.  After steel
stainless
grinding, flotation experiment was conducted in a 0.5 L RK/FD‐60 cell with 2500 rpm impellor speed. 
ball mill (model: XMQ240ˆ90, Wuhan Rock Crush & Grand Equipment Manufacture Co., Wuhan,
Meanwhile,  air  was  delivered  to  the  cell  at  8  dm3/min  and  pulp  pH  at  9–9.5.  In  the  flotation,  the 
China). Grind establishment tests determined the time required to produce a P90 of 45 µm. After
collector  and  frother  used  were  a  commercial  sodium  butyl  xanthate  (KBX)  and  terpineol, 
grinding, flotation experiment was conducted in a 0.5 L RK/FD-60 cell with 2500 rpm impellor speed.
 
Meanwhile, air was delivered to the cell at 8 dm3 /min and pulp pH at 9–9.5. In the flotation, the
collector and frother used were a commercial sodium butyl xanthate (KBX) and terpineol, respectively.
The flotation process involved the addition of KBX (200 g/t, 3 min conditioning), followed by the
Metals 2016, 6, 86 6 of 17

addition of terpineol (20 g/t, 3 min conditioning), after which flotation concentrates were collected for
5 min.
After flotation, a 30 g batch of dry waste slag (flotation tailings) was subjected to wet magnetic
separation using a magnetic field intensity of 0.17 Tesla for 10 min in a Davis Tube (model: XCGS-73,
Changsha Research Institute of Mining and Metallurgy Co., Changsha, China). Iron concentrate was
produced as product, and the non-magnetic part of the tailings would probably be utilized as a material
for cement manufacture.
These dosages of reagent and parameters were fixed based on various previous experiments to
achieve a copper and iron recovery in the laboratory.
In order to demonstrate the effect of modification process on the beneficiation of copper and iron,
the unmodified copper slag was beneficiated in parallel by floatation-magnetic separation under the
same conditions as for modified slag.

2.2.3. Mechanism of Modification

X-ray diffraction (XRD) patterns were recorded by a diffractometer (RIGAKU D/Max 2500,
Rigaku Co., Tokyo, Japan). Microstructures of slag were performed by Leica DMLP optical microscopy,
FEI Quata-200 scanning electron microscope (FEI Company, GG Eindhoven, The Netherlands) and
EDAX32 genesis spectrometer (Ametek Inc., Paoli, CO, USA). Scanning electron microscope (SEM)
images were recorded in backscatter electron modes operating in low vacuum mode at 0.5 Torr and
20 keV.

2.3. Evaluation Indexes

The modification results were assessed by the recovery of copper and iron, but copper recovery
was the main priority in the present research.
In the flotation process, the yield of copper concentrate and recovery of copper were calculated
according to Equations (1) and (2), respectively.

γ “ m{m0 ˆ 100% (1)

ε “ γ ˆ β{α ˆ 100% (2)

where γ is the yield of cooper concentrate (%); m0 is the feed mass of modified slag subjected to
flotation (g); m is the mass of obtained copper concentrate (g); ε is the recovery of copper (%); α is the
copper grade in the feed (%); and β is the copper grade in the concentrate (%).
Similarly, the yield of magnetite concentrate and recovery of iron were calculated like Equations (1)
and (2), respectively.

3. Results and Discussion

3.1. Thermodynamic Analysis

In the modification process, the calcium oxide and compound additive were added because they
help reconstruct the mineral phase of copper slag.
It has been found that calcium oxide can preferentially combine with “SiO2 ” to form “CaSiO3 ”
and readily replace the “FeO” in the fayalite resulting in an increase in the activity of “free” FeO in
the slag [25–28]. Hence, with more “FeO” released, the Fe2 O3 reacted with that to form more Fe3 O4 ,
as shown in Equations (3) and (4).

CaO ` 2FeO¨ SiO2 Ñ CaO¨ SiO2 ` 2FeO (3)

FeO ` Fe2 O3 Ñ Fe3 O4 (4)

Metals 2016, 6, 86 7 of 17

In addition, on account of partial copper presenting as copper oxide and combine copper oxide
(as seen in Table 3), the sulfuring treatment of copper slag to recover copper sulfide is necessary by
adding compound additive. The most likely sulfuration reactions in the modification process in the
presence of compound additive are listed as Equations (5) and (7) [25,27]:
Metals 2016, 6, 86  7 of 17 
FeS ` Cu2 O Ñ FeO ` Cu2 S (5)
adding compound additive. The most likely sulfuration reactions in the modification process in the 
GTθ “ ´ 144750 ` 13.05T, J{mol
presence of compound additive are listed as Equations (5) and (7) [25,27]:  (6)

FeS FeS + Cu
` 3Fe3 O 4 Ñ 10FeO `2S 
2O → FeO + Cu SO2 (5)  (7)

G∆G
θ  = − 144750 + 13.05T, J/mol 
Tθ
T “ 654720 ´ 381.95T, J{mol
(6)  (8)
FeS + 3Fe3O4 → 10FeO + SO2  (7) 
The equilibrium constant for Equation (5) can be calculated at various modification temperatures
from 1250 to 1350 ˝ C by Equation (6),∆G Tθ = 654720 − 381.95T, J/mol 
and the results are shown in Table 5. (8) 
The equilibrium constant for Equation (5) can be calculated at various modification temperatures 
Table 5. Equilibrium constants for Equation (5) at different modification temperatures.
from 1250 to 1350 °C by Equation (6), and the results are shown in Table 5. 

Modification Temperature/˝ C 1250 1300 1350 1400

Table 5. Equilibrium constants for Equation (5) at different modification temperatures. 
Equilibrium constant 1.91 4 4 104   0.69 1400
ˆ 104 
Modification Temperature/°C   ˆ 1012501.33
  ˆ 10
1300  0.94 ˆ1350
Equilibrium constant  1.91 × 104  1.33 × 104  0.94 × 104  0.69 × 104 
It is inferred from Table 5 that Cu2 O (or other oxidized copper, such as CuO and CuO¨ Fe2 O3 )
It is inferred from Table 5 that Cu
is completely sulfurized to Cu2 S by FeS 2O (or other oxidized copper, such as CuO and CuO∙Fe2O3) is 
readily at modification temperature from the view of
completely  sulfurized  to  Cu2S  by  FeS  readily  at  modification  temperature  from  the  view  of 
thermodynamics as the equilibrium constant is relative high.
thermodynamics as the equilibrium constant is relative high. 
At SO 2 partial
At SO
pressure of 10´2 atm, the relationship between aFeS and aFe3O4 in molten slag with
2 partial pressure of 10−2 atm, the relationship between aFeS and aFe3O4 in molten slag with 
different value of aFeO FeO 
different value of a was calculated by Equation (5), and the result is plotted in Figure 4.
was calculated by Equation (5), and the result is plotted in Figure 4. 
As shown
As  shown  in  Figure  4, an
in Figure 4, with increase
with  in aFeS , in 
an  increase  theaaFeSFe3O4
,  the decreases obviously;
aFe3O4  decreases  moreover,
obviously;  increasing
moreover, 
temperature tends to inhibit generating of Fe3 O4 .
increasing temperature tends to inhibit generating of Fe 3O4. 

1.0

1 a(FeO)=0.5 1623K
2 a(FeO)=0.5 1573K
0.8
3 a(FeO)=0.4 1623K
4 a(FeO)=0.4 1573K

0.6
Fe3O4

0.4
a

0.2

0.0
0.0 0.2 0.4 0.6 0.8
aFeS
 
Figure 4. Relationship between a
4. Relationship between aFeS FeS and a
and aFe3O4 in molten slag. 
Figure Fe3O4 in molten slag.

3.2. Modification of Molten Copper Slag 
3.2. Modification of Molten Copper Slag
3.2.1. Reconstruction Phase of Copper Slag through Modifying 
3.2.1. Reconstruction Phase of Copper Slag through Modifying
Effects of Binary Basicity on Recovery of Copper and Iron 
Effects of Binary Basicity on Recovery of Copper and Iron
The effect of binary basicity on modification of copper slag is presented in Figure 5. As can be 
The effect of binary basicity on modification of copper slag is presented in Figure 5. As can be
seen in Figure 5, it is clear that with an increase in binary basicity from 0.25 to 0.65, the total iron 
seen in Figure 5, it is clear that with an increase in binary basicity from 0.25 to 0.65, the total iron grade
grade of concentrate increases from 55.79% to 56.27% and iron recovery significantly increases from 
of concentrate increases from 55.79% to 56.27% and iron recovery significantly increases from 53.32% to
53.32% to 77.68%. On the contrary, the copper grade of copper concentrate decreases from 7.25% to 
3.16%  and  the  copper  recovery  obviously  decreases  from  59.78%  to  31.21%.  This  means  that  by 
adjusting the binary basicity, more iron‐bearing mineral was transformed from fayalite to magnetite, 
resulting  in  higher  magnetic  separation recovery.  This  effect  can  be  explained  by  the fact  that  the 
 
Metals 2016, 6, 86 8 of 17

77.68%. On the contrary, the copper grade of copper concentrate decreases from 7.25% to 3.16% and the
copper recovery obviously decreases from 59.78% to 31.21%. This means that by adjusting the binary
Metals 2016, 6, 86 
basicity, more iron-bearing mineral was transformed from fayalite to magnetite, resulting in higher 8 of 17 

magnetic separation recovery. This effect can be explained by the fact that the presence of calcium
presence of calcium oxide in the sample benefited the decomposition of 2FeO∙SiO2 through replacing 
oxide in the sample benefited the decomposition of 2FeO¨ SiO2 through replacing the “FeO”, which led
the  “FeO”,  which  led  to  an  increase  of  the  activity  of  free  “FeO”  in  the  slag  and  promoted  more 
to an increase of the activity of free “FeO” in the slag and promoted more magnetite generation,
magnetite generation, as illustrated in Equations (3) and (4). 
as illustrated in Equations (3) and (4).

60
80
TFe
56
70

52 Fe Recovery
60
Grade/%
Grade/%

Recovery/%
Recovery/%
48
Cu Recovery 50

6 TCu
40

4
30

2
20
0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70
Basicity  
Figure 5. Effects of binary basicity on recovering of copper and iron (Modifying at 1350 ˝ C for 120 min
Figure 5. Effects of binary basicity on recovering of copper and iron (Modifying at 1350 °C for 120 
with 6% of compound additive and cooling at 1.5 ˝ C/min from 1350 to 900 ˝ C).
min with 6% of compound additive and cooling at 1.5 °C/min from 1350 to 900 °C). 

However, with
However, with more
more  magnetite 
magnetite generated 
generated andand  firstly 
firstly precipitated 
precipitated in  modification 
in modification and slowand  slow 
cooling
cooling process, the viscosity of copper slag was increased sharply, which has extremely negative 
process, the viscosity of copper slag was increased sharply, which has extremely negative influence on
influence on aggregation and growth of the particles of the copper bearing minerals, leading to more 
aggregation and growth of the particles of the copper bearing minerals, leading to more fine copper
fine copper minerals formation. Thus, it is very difficult to recover the copper by flotation separation. 
minerals formation. Thus, it is very difficult to recover the copper by flotation separation. After
After comprehensive consideration of recovery of iron and copper, the binary basicity was fixed at 
comprehensive consideration of recovery of iron and copper, the binary basicity was fixed at 0.45 in
0.45 in the subsequent experimental series. 
the subsequent experimental series.

Effects of Compound Additive Dosage on the Recovery of Copper and Iron

Effects of Compound Additive Dosage on the Recovery of Copper and Iron 
The flotation and magnetic separation results of cooper slag modified with variable dosages of
The flotation and magnetic separation results of cooper slag modified with variable dosages of 
compound additive (ranging between 3% and 15%) are shown in Figure 6.
compound additive (ranging between 3% and 15%) are shown in Figure 6. 

60 90

TFe
56 80

52 70
Fe Recovery
%
60/
Grade/%
Grade/%

48 y
r
e
Cu Recovery v
o
10 c
50e
R
8

6 40
TCu
4

2 30
0
2 4 6 8 10 12 14 16
Compound additive dosage/%  
Figure  6.  Effects  of  compound  additive  dosage  on  recovering  of  copper  and  iron  (0.45  of  binary 
Figure 6. Effects of compound additive dosage on recovering of copper and iron (0.45 of binary basicity,
basicity, modifying at 1350 °C for 120 min and cooling at 1.5 °C/min from 1350 to 900 °C). 
modifying at 1350 ˝ C for 120 min and cooling at 1.5 ˝ C/min from 1350 to 900 ˝ C).

It can be seen in Figure 6 that as the compound additive increases from 3% to 15%, the total 
copper grade of copper concentrate and copper recovery increases obviously, the total iron grade of 
magnetite  concentrate  changes  slightly,  and  the  iron  recovery  decreases  sharply  from  73.03%  to 
54.85%. 
Metals 2016, 6, 86  9 of 17 

As described above, the compound additive contains sulfide, which played an important role in 
Metals 2016, 6, 86 9 of 17
the  modification  process:  The  sulfide,  as  a  kind  of  reducing  agent,  lowered  the  production  of 
magnetite  through  reducing 
It can be seen in Figurethe  Feas3Othe
6 that 4  to  FeO  (as 
compound shown 
additive in  Equation 
increases from 3% to(7) 
15%,and  Figure 
the total copper 4),  while 
benefiting  from 
grade the  viscosity 
of copper concentrateof 
andthe  molten 
copper slag increases
recovery decreasing  obviously. 
obviously, In  addition, 
the total iron sulfide  can  be 
grade of magnetite
concentrate changes slightly, and the iron recovery decreases sharply from 73.03% to 54.85%.
added for another purpose as it helps to ensure sulfidation of all copper present in the sample so that 
As described above, the compound additive contains sulfide, which played an important role in
it enters into the matte phase, since Cu 2O is very easy to sulfurized to Cu2S by FeS. Thus, the content 
the modification process: The sulfide, as a kind of reducing agent, lowered the production of magnetite
of copper sulfide, as the favorable mineral for flotation, was improved in the modified slag. 
through reducing the Fe3 O4 to FeO (as shown in Equation (7) and Figure 4), while benefiting from
In other words, adjusting the dosage of the compound additive can improve recovery of copper 
the viscosity of the molten slag decreasing obviously. In addition, sulfide can be added for another
through accelerating the generation of matte particles, yet the iron recovery is inhibited. Therefore, 
purpose as it helps to ensure sulfidation of all copper present in the sample so that it enters into the
matte phase, since Cu2 O is very easy to sulfurized to Cu2 S by FeS. Thus, the content of copper sulfide,
in order to comprehensively recovery copper and iron, the dosage of 12% is recommended under the 
as the favorable mineral for flotation, was improved in the modified slag.
experimental conditions. 
In other words, adjusting the dosage of the compound additive can improve recovery of copper
through accelerating the generation of matte particles, yet the iron recovery is inhibited. Therefore,
3.2.2. Heating Treatment System 
in order to comprehensively recovery copper and iron, the dosage of 12% is recommended under the
experimental conditions.
Effects of Modification Temperature on the Recovery of Copper and Iron 
3.2.2. Heating Treatment System
The effect of modification temperature on modification of copper slag is illustrated in Figure 7. 
As  seen Effects of Modification Temperature on the Recovery of Copper and Iron
in  Figure  7,  the  total  copper  grade  of  copper  concentrate  and  copper  recovery  increased 
The effect of modification temperature on modification of copper slag is illustrated in Figure 7.
dramatically when the modification temperature increased from 1250 to 1400 °C, whereas the total 
As seen
iron  grade  in Figure 7, the
of  magnetite  total copperand 
concentrate  grade of copper
iron  concentrate
recovery  and copper
decreased  slightly recovery increased
in  the  range  of  test 
dramatically when the modification temperature increased from 1250 to 1400 ˝ C, whereas the total iron
temperatures. 
grade of magnetite concentrate and iron recovery decreased slightly in the range of test temperatures.

60 80
TFe
76
56
72
Cu Recovery
68
52
64
Recovery/%
Grade/%

48
Fe Recovery
60

56
10
52
TCu
8 48

44
6
40
1250 1300 1350 1400
Modification temperatur/℃  
Figure 7. Effects of slag modification temperature on recovering of copper and iron (0.45 of binary
Figure 7. Effects of slag modification temperature on recovering of copper and iron (0.45 of binary 
basicity, blending with 12% of compound additive, modifying for 120 min and cooling at 1.5 ˝ C/min
basicity, blending with 12% of compound additive, modifying for 120 min and cooling at 1.5 °C/min 
from 1350 to 900 ˝ C).
from 1350 to 900 °C). 
With increasing temperature, bonded silicate anions were broken, which caused a decrease in the
With increasing temperature, bonded silicate anions were broken, which caused a decrease in 
viscosity and an increase in fluidity of the molten slag, which contributed to collision and aggregation
the  viscosity  and 
of matte an  increase 
particles. Moreover,in  fluidity 
with of  the 
an increase molten 
in the slag, the
temperature, which  contributed 
interfacial to  collision 
tension between two and 
phases (copper matte and slag) ascended; on the contrary, the adhesion force of two phases
aggregation of matte particles. Moreover, with an increase in the temperature, the interfacial tension  descended,
leading to the decrease in the dissolution and mechanical inclusion of copper in slag [25].
between two phases (copper matte and slag) ascended; on the contrary, the adhesion force of two 
Therefore, from a practical point of view, the reducing temperature is fixed at 1350 ˝ C in the
phases descended, leading to the decrease in the dissolution and mechanical inclusion of copper in 
subsequent experimental series.
slag [25]. 
Therefore, from a practical point of view, the reducing temperature is fixed at 1350 °C in the 
subsequent experimental series. 

Effects of Cooling Rate on the Recovery of Copper and Iron 
 Metals 2016, 6, 86 10 of 17

Metals 2016, 6, 86  10 of 17 
Effects of Cooling Rate on the Recovery of Copper and Iron

21.79%,  the Figure 8 demonstrates

iron  recovery  the effect
reduced  of slow cooling
gradually  from  rate on recovery
64.29%  of copperand 
to  61.07%  and iron. It can be
the  total  seengrade  of 
iron 
that as the slow cooling rate elevated from 1 to 5 ˝ C/min, the total copper grade of copper concentrate
magnetite concentrates remained stable. A possible explanation for this is that slow cooling of slag 
decreased from 10.68% to 7.63%, the recovery of copper prominently decreased by 21.79%, the iron
from its molten state to its solidification ensures full growth for the particles of valuable mineral and 
recovery reduced gradually from 64.29% to 61.07% and the total iron grade of magnetite concentrates
increases  the  size 
remained of  the 
stable. particles, 
A possible thereby 
explanation forcreating 
this is thatideal 
slow mineralogy 
cooling of slagconditions  for state
from its molten subsequent 
flotation toand  magnetic  separation. 
its solidification In  contrast, 
ensures full growth fast  cooling 
for the particles may mineral
of valuable produce  andan  amorphous 
increases the sizephase  to 
of the particles, thereby creating ideal mineralogy conditions for subsequent flotation
prevent  diffusion and aggregation  of  particles, and hence  the slag  is  more  homogeneous in  metal  and magnetic
separation. In contrast, fast cooling may produce an amorphous phase to prevent diffusion and
distribution  and  more  super  fine  grains  of  valuable  minerals  would  be  generated,  which  is 
aggregation of particles, and hence the slag is more homogeneous in metal distribution and more super
detrimental for physical separation. 
fine grains of valuable minerals would be generated, which is detrimental for physical separation.

76
60
TFe
72
56

68
52 Cu Recovery

Recovery/%
Fe Recovery
64
Grade/%

48

TCu
60
10

8 56

6 52

1 2 3 4 5
Cooling rate/(℃/min)  
Figure 8. Effects of slow cooling rate on recovering of copper and iron (0.45 of binary basicity, blending
Figure 8. Effects of slow cooling rate on recovering of copper and iron (0.45 of binary basicity, blending 
with 12% of compound additive, modifying at 1350 ˝ C for 120 min and cooling down to 900 ˝ C).
with 12% of compound additive, modifying at 1350 °C for 120 min and cooling down to 900 °C). 

In brief, the above results show that the slow cooling rate significantly influences the modification
In  brief,  the  above  results  show  that  the  slow  cooling  rate  significantly  influences  the 
of copper slag, and the lower the cooling rate, the larger the mineral phases grow and the more
modification of copper slag, and the lower the cooling rate, the larger the mineral phases grow and 
valuable metals are recovered. However, in view of production efficiency, the slow cooling rate of
the more valuable metals are recovered. However, in view of production efficiency, the slow cooling 
1.5 ˝ C/min is recommended.
rate of 1.5 °C/min is recommended. 
Effects of the End Point Temperature on the Recovery of Copper and Iron
The effect of the end point temperature of slow cooling on recovery of copper and iron was
Effects of the End Point Temperature on the Recovery of Copper and Iron 
conducted and the results are shown in Figure 9. The results show that with the increase of end point
The temperature
effect  of  the  end 
of slow point from
cooling temperature 
800 to 1000 ˝of  slow iscooling 
C, there on change
no obvious recovery 
in all of  copper indexes.
evaluation and  iron  was 
˝
However, when the end point temperature was beyond 1000 C, the total copper grade of the rough
conducted and the results are shown in Figure 9. The results show that with the increase of end point 
copper concentrate and copper recovery decreased dramatically; concurrently, the total iron grade of
temperature of slow cooling from 800 to 1000 °C, there is no obvious change in all evaluation indexes. 
magnetite concentrate and iron recovery change slightly. Because of high phase transition temperature
However, when the end point temperature was beyond 1000 °C, the total copper grade of the rough 
and strong crystallizability of magnetite, the influence of the end point temperature of cooling in the
copper concentrate and copper recovery decreased dramatically; concurrently, the total iron grade of 
range of tests on growth of magnetite grain is very small [28].
magnetite  concentrate  and  iron  recovery  change  slightly.  Because  of  high  phase  transition 
temperature and strong crystallizability of magnetite, the influence of the end point temperature of 
cooling in the range of tests on growth of magnetite grain is very small [28]. 
 Metals 2016, 6, 86 11 of 17
Metals 2016, 6, 86  11 of 17 

64
Cu Recovery
72
60
TFe
56 68

52
Fe Recovery 64

Recovery/%
Grade/%

48

60
13

12
56
TCu
11

10 52

9
750 800 850 900 950 1000 1050 1100 1150
End point temperature of slow cooling/(℃)  
Figure 9. Effects of end point temperature of slow cooling on the recovering of copper and iron (0.45 of
Figure 9. Effects of end point temperature of slow cooling on the recovering of copper and iron (0.45 
binary basicity, blending with 12% of compound additive, modifying at 1350 ˝ C for 120 min and
of binary basicity, blending with 12% of compound additive, modifying at 1350 °C for 120 min and 
cooling at 1.5 ˝ C/min).
cooling at 1.5 °C/min). 
It is generally considered that the copper matte mainly consists of 35%–70% Cu, 20%–26% S and
It is generally considered that the copper matte mainly consists of 35%–70% Cu, 20%–26% S and 
10%–30% Fe, which possesses different melting point for various compositions. And the Cu-Fe-S
10%–30%  Fe,  which 
ternary diagrampossesses  different 
indicates that the phasemelting 
transitionpoint  for  various 
temperature compositions. 
of the copper And 
matte with that the  Cu‐Fe‐S 
consists
is approximately range from 950 to 1100 ˝ C [25]. Table 6 demonstrates the phase transition temperature
ternary diagram indicates that the phase transition temperature of the copper matte with that consists 
of the major valuable minerals.
is  approximately  range  from  950  to  1100  °C  [25].  Table  6  demonstrates  the  phase  transition 
temperature of the major valuable minerals. 
Table 6. Phase transition temperature of the main valuable minerals (˝ C).

Mineral FeS Cu2 S Cu Cu2 S-FeS (Matte)

Table 6. Phase transition temperature of the main valuable minerals (°C). 
temperature 1190 1126 1083 950–1100
Mineral  FeS Cu2S Cu Cu2S‐FeS (Matte) 
The moltentemperature  1190 
phase is responsible for the1126  1083 
rapid grain coarsening,950–1100 
where smaller particles will go
into solution preferentially and precipitate on larger particles, accelerating the transport rate and
The molten phase is responsible for the rapid grain coarsening, where smaller particles will go 
fluidity as liquid diffuse much faster than solid [29,30]. Therefore, in order to ensure full aggregation
and growth
into  solution  of mineral particles
preferentially  from moltenon 
and  precipitate  state to solidification,
larger  particles, the end point temperature
accelerating  of slowrate  and 
the  transport 
cooling should be below the lowest phase transition temperature of valuable minerals. Thus, it is
fluidity as liquid diffuse much faster than solid [29,30]. Therefore, in order to ensure full aggregation 
reasonable that the end point temperature of slow cooling is fixed at 900 ˝ C.
and growth of mineral particles from molten state to solidification, the end point temperature of slow 
3.2.3. Comparison
cooling  should  of the 
be  below  Separation
lowest Indexes
phase between Modified
transition  Slag and Unmodified
temperature  Slagminerals.  Thus,  it  is 
of  valuable 
reasonable that the end point temperature of slow cooling is fixed at 900 °C. 
Based on the above results, a modified slag was obtained under the conditions of 0.45 of binary
basicity, blending with 12% of compound additives, modifying at 1350 ˝ C for 120 min and cooling
at 1.5 ˝ C/min from 1350 to 900 ˝ C. The conditions of flotation and magnetic separation process for
3.2.3. Comparison of Separation Indexes between Modified Slag and Unmodified Slag 
unmodified copper slag is similar to modified copper slag, and the results compared with each other
Based on the above results, a modified slag was obtained under the conditions of 0.45 of binary 
are shown in Figure 10.
basicity, blending with 12% of compound additives, modifying at 1350 °C for 120 min and cooling at 
1.5  °C/min  from  1350  to  900  °C.  The  conditions  of  flotation  and  magnetic  separation  process  for 
unmodified copper slag is similar to modified copper slag, and the results compared with each other 
are shown in Figure 10. 
 Metals 2016, 6, 86 12 of 17
Metals 2016, 6, 86  12 of 17 

80

U
n
m
o
d
i
f
i
e
d
s
l
a
g

7
2
.
9
3
%
M
o
d
i
f
i
e
d
s
l
a
g

7
1
.
4
5
%
70

6
3
.
2
6
%
5
6
.
8
8
%
5
6
.
3
1
%
60

Percent/% 50

40
3
2
.
4
0
%
30

20

1 %
1
.
0
4
%
6
.
4
3
10

0
Iron recovery Iron grade Copper recovery Copper grade  
Figure 10. Comparison of beneficiation indexes of copper and iron between two kinds of slags. 
Figure 10. Comparison of beneficiation indexes of copper and iron between two kinds of slags.

As seen in Figure 10, the iron recovering from flotation tailings of two types of slag, presents a 
As seen in Figure 10, the iron recovering from flotation tailings of two types of slag, presents
great 
a difference  in  the 
great difference magnetic 
in the separation 
magnetic separationprocess. The  iron recovery
process. The iron recovery waswas  increased 
increased significantly 
significantly
from 32.40% to 63.26%, while the iron grade of the magnetite concentrates was similar. The improved 
from 32.40% to 63.26%, while the iron grade of the magnetite concentrates was similar. The improved
magnetic separation efficiency of the copper slag is a result of the simultaneous increase of the
magnetic separation efficiency of the copper slag is a result of the simultaneous increase of the content 
content and grain size of magnetite in the slag during the modification, as the fayalite had been
and grain size of magnetite in the slag during the modification, as the fayalite had been broken and 
broken and
converted  into converted
magnetite intoand 
magnetite and hedenbergite,
hedenbergite,  which which
can  can
be  be confirmed by 
confirmed  by XRD
XRD pattern and and 
pattern 
Metals 2016, 6, 86 
microstructure characterization of copper slag (as shown in Figures 11 and 12). 13 of 17 
microstructure characterization of copper slag (as shown in Figures 11 and 12). 
It can also be seen in Figure 10 that, through the modification of molten copper slag, the total 
FM
F

copper grade of rougher copper concentrate was increased from 6.43% to 11.04%. Meanwhile, the 
Unmodified slag
F

F F

copper recovery was changed slightly. 
F
F

M
M

F
F
F
F

In addition, the chemical compositions of magnetic concentrates are shown in Table 7. It can be 
F
F

seen that, although the SiO2 content is a little high, impurities components such as copper and other 
M
Intensity /C PS

heavy metals (Pb) are not too high. Therefore, the iron concentrates could be used to sinter blending 
Modified slag
with low SiO2 fine for iron making. 

Table 7. Chemical compositions of iron concentrate (mass fraction, %). 
M
H

M
F

Element  TFe  SiO2  CaO  MgO  Al2O3  S  P  Cu  Pb  Zn 

M
F

M
F

F
M
F
H

F
F

F
H

H
F

Percentage  56.31  7.22  2.59  0.64  2.75  0.03  0.04  0.15  0.03  0.03 

10 20 30 40 50 60 70
3.3. Intensification Mechanisms of Modification of Copper Slag on Cu and Fe Separation 
Two-theta /deg  
3.3.1. Phase Transformation by Modification 
Figure 11. XRD patterns of the copper slag (0.45 of binary basicity, blending with 12% of compound
Figure 11. XRD patterns of the copper slag (0.45 of binary basicity, blending with 12% of compound 
additive, modifying at 1350 ˝ C for 120 min and cooling at 1.5 ˝ C/min from 1350 to 900 ˝ C) (F—fayalite;
In order to find the function of the modification process on phase transformation, XRD analysis 
additive, modifying at 1350 °C for 120 min and cooling at 1.5 °C/min from 1350 to 900 °C) (F—fayalite; 
M—magnetite; H—hedenbergite).
was  carried  out  to  reveal  the  difference  between  modified  copper  slag  and  unmodified  slag.  The 
M—magnetite; H—hedenbergite). 
results are shown in Figure 11. 
Generally,  analysis  of  XRD  assumes  that  the  ratio  of  the  peak  heights  in  the XRD  patterns  is 
It can be seen from Figure 11 that in the unmodified slag, the major minerals constituents are 
proportional to the mineral content, and that, for the same mineral, the variation in the diffraction 
fayalite  (Fe2SiO4)  and  magnetite  (Fe3O4).  With  the  modification  process,  the  peak  intensity  of 
intensity can approximately reflect the change in its content [31]. Thus, this implies that the amount 
magnetite  increased  significantly,  and  that  of  fayalite  decreased  obviously;  simultaneously, 
of magnetite increases significantly in the modified copper slag, leading to an obvious improvement 
hedenbergite, as a new phase, was detected in modified slag. When the binary basicity is low (less 
of iron recovery in magnetic separation. 
than  1),  the  CaO  is  reactive  with  fayalite  (Fe2SiO4)  to  form  hedenbergite  (CaFeSi2O6)  instead  of 
Hence, the results above further indicate recycling potential may be enhanced by post‐process 
wollastonite (CaSiO 3) [26], which is not helpful with recovering of iron. 

additions  to  the  high  temperature  slag  to  change  its  composition  (that  is,  modifying  stage  of  slag 
processing) for obtaining the target minerals—without interfering with the metallurgical process. 
Metals 2016, 6, 86 13 of 17
Metals 2016, 6, 86  14 of 17 

 
Figure 12. Microstructures of the copper slag (0.45 of binary basicity, blending with 12% of compound 
Figure 12. Microstructures of the copper slag (0.45 of binary basicity, blending with 12% of
additive,  modifying  at  1350  °C  for  120  min  and  cooling  at  1.5  °C/min  down  to  900  °C):  (A,B) 
compound additive, modifying at 1350 ˝ C for 120 min and cooling at 1.5 ˝ C/min down to 900 ˝ C):
unmodified slag; and (C,D) modified slag. 
(A,B) unmodified slag; and (C,D) modified slag.

It can also be seen in Figure 10 that, through the modification of molten copper slag, the total
copper grade of rougher copper concentrate was increased from 6.43% to 11.04%. Meanwhile, the
copper recovery was changed slightly.
In addition, the chemical compositions of magnetic concentrates are shown in Table 7. It can be
seen that, although the SiO2 content is a little high, impurities components such as copper and other
heavy metals (Pb) are not too high. Therefore, the iron concentrates could be used to sinter blending
with low SiO2 fine for iron making.

Table 7. Chemical compositions of iron concentrate (mass fraction, %).

Element TFe SiO2 CaO MgO Al2 O3 S P Cu Pb Zn

Percentage 56.31 7.22 2.59 0.64 2.75 0.03 0.04 0.15 0.03 0.03

3.3. Intensification Mechanisms of Modification of Copper Slag on Cu and Fe Separation

3.3.1. Phase Transformation by Modification

In order to find the function of the modification process on phase transformation, XRD analysis
was carried out to reveal the difference between modified copper slag and unmodified slag. The results
are shown in Figure 11.
It can be seen from Figure 11 that in the unmodified slag, the major minerals constituents are
fayalite (Fe2 SiO4 ) and magnetite (Fe3 O4 ). With the modification process, the peak intensity of magnetite
increased significantly, and that of fayalite decreased obviously; simultaneously,  hedenbergite, as a
new phase, was detected in modified slag. When the binary basicity is low (less than 1), the CaO is
Figure 13. Scanning electron microscope and energy dispersive spectrometer (SEM‐EDS) analyses of 
reactive with fayalite (Fe2 SiO4 ) to form hedenbergite (CaFeSi2 O6 ) instead of wollastonite (CaSiO3 ) [26],
the modified slag (0.45 of binary basicity, blending with 12% of compound additive, modifying at 
1350 °C for 120 min and cooling at 1.5 °C/min down to 900 °C). 
which is not helpful with recovering of iron.
Generally,
  analysis of XRD assumes that the ratio of the peak heights in the XRD patterns is
proportional to the mineral content, and that, for the same mineral, the variation in the diffraction
intensity can approximately reflect the change in its content [31]. Thus, this implies that the amount of
 Metals 2016, 6, 86 14 of 17

magnetite increases significantly in the modified copper slag, leading to an obvious improvement of
iron recovery in magnetic separation.
Hence, the results above further indicate recycling potential may be enhanced by post-process
additions to the high temperature slag to change its composition (that is, modifying stage of slag
processing) for obtaining the target minerals—without interfering with the metallurgical process.

3.3.2. Microstructure Character of Copper Slag

Although beneficiation of copper and iron may be improved by modifying process from a
perspective of mineral phases, the effects of physical separation also depend on embedded characters
of slag and the size of target mineral particles. To further reveal the mechanism of the modification
Figure 12. Microstructures of the copper slag (0.45 of binary basicity, blending with 12% of compound 
on improvement of mineralography and the growing character of valuable mineral particles, the
additive,  modifying  at  1350  °C  for  120  min  and  cooling  at  1.5  °C/min  down  to  900  °C):  (A,B) 
microstructures of the slag were studied using an optical microscope, scanning electron microscope
unmodified slag; and (C,D) modified slag. 
and energy dispersive spectrometer (SEM-EDS). The results are shown in Figures 12 and 13.

 
Figure 13. Scanning electron microscope and energy dispersive spectrometer (SEM‐EDS) analyses of 
Figure 13. Scanning electron microscope and energy dispersive spectrometer (SEM-EDS) analyses
of the modified slag (0.45 of binary basicity, blending with 12% of compound additive, modifying at
the modified slag (0.45 of binary basicity, blending with 12% of compound additive, modifying at 
1350 ˝ C for 120 min and cooling at 1.5 ˝ C/min down to 900 ˝ C).
1350 °C for 120 min and cooling at 1.5 °C/min down to 900 °C). 
 
Figure 12A,B is the microstructure of unmodified slag. It can be seen that the matte phase
occurs as brilliant yellow prill within the silicates, which is finely disseminated throughout the slag.
In addition, all prills have the same spheroidal shape, and their size has a wide range between about
5 and 30 µm with an average of approximately 15 µm. Meanwhile, magnetite was seen to be present as
 Metals 2016, 6, 86 15 of 17

patches or tiny laths, showing dendritic texture and stars of various shapes with fine sizes embedded
in the silicates. However, the fine dissemination of the minerals responds very poorly to flotation
and magnetic separation due to the insufficient mineral liberation from the gangue mineral through
grinding. Therefore, the main purpose of modifying the copper slag in molten stage is that the particles
Metals 2016, 6, 86 
of valuable minerals were induced to grow up. As seen in Figure 12C,D most of the matte particles 15 of 17 
in the slag aggregate together as well as grow obviously; the size of which is mostly over 50 µm.
Moreover, the liberation of minerals is important for flotation and magnetic separation. Thus, 
Moreover, the magnetite not only presents a very large particle size but also has agglomeration to
liberation  degree 
some extent, which of  valuable  metal 
is extremely minerals 
beneficial under  different 
to magnetite grinding  sizes  for  modified  slag  was 
separation.
determined, and the results are shown in Table 8, indicating that when the grinding fineness of the 
Moreover, the liberation of minerals is important for flotation and magnetic separation. Thus,
liberation degree of valuable metal minerals under different grinding sizes for modified slag was
slag is up to 70% passing through 74 μm, copper matte and magnetic minerals are liberated enough 
determined, and the results are shown in Table 8, indicating that when the grinding fineness of the
and the grain size is favorable to the separation process. 
slag is up to 70% passing through 74 µm, copper matte and magnetic minerals are liberated enough
and the grain size is favorable to the separation process.
Table 8. Liberation degree of metal minerals under different grinding sizes for modified slag/%. 

Table 8. Liberation degree of metal minerals under different

Grinding Size/( grinding sizes
−0.074 mm %)for  modified slag/%.
Minerals 
53  58  64  70  76  82  85 
Grinding Size/(´0.074 mm %)
Minerals 76.34  84.34  88.65  93.21  95.68  97.12  98.03 
Copper matte 
53 58 64 70 76 82 85
Magnetic  89.63  93.23  94.56  95.78  96.82  97.51  98.32 
Copper matte 76.34 84.34 88.65 93.21 95.68 97.12 98.03
Magnetic 89.63 93.23 94.56 95.78 96.82 97.51 98.32
Mineral compositions of modified slag were determined by spot analysis of minerals using SEM‐
EDS, and the results are shown in Figure 13. The analysis on point 1 indicates that it predominantly 
Mineral compositions of modified slag were determined by spot analysis of minerals using
consists of Fe and O (magnetite) along with traces of Al, Mg and Zn. According to EDS analysis of 
SEM-EDS, and the results are shown in Figure 13. The analysis on point 1 indicates that it
point  2  in  Figure  13, 
predominantly the  major 
consists gangue 
of Fe and minerals  along
O (magnetite) mainly  consist 
with tracesof 
ofhedenbergite 
Al, Mg and Zn. (CaO∙FeO∙2SiO
According 2), 
which  is  in  agreement  with  the  XRD  results  in  Figure  11.  Meanwhile,  the  point 
to EDS analysis of point 2 in Figure 13, the major gangue minerals mainly consist of hedenbergite analysis  of  the 
spherical 
(CaO¨ shaped 
FeO¨ 2SiO phase  (point 
2 ), which is in3)  contains with
agreement high  copper 
the percentage 
XRD results with 
in Figure 11. little  iron  and 
Meanwhile, the sulfur, 
point as 
analysis of the spherical shaped phase (point 3) contains high copper percentage
anticipated, which exhibits Cu bearing phase similar to matte (Cu2S‐FeS). As can be seen in Figure with little iron and
sulfur, as anticipated, which exhibits Cu bearing phase similar to matte (Cu2 S-FeS).
14, that FeS has a high affinity with copper to form a solid solution with Cu As can be seen
2S of a limited solubility. 
in Figure 14, that FeS has a high affinity with copper to form a solid solution with
Taken together with the thermodynamic analysis, adding the additives with FeS is favorable to form  Cu 2 S of a limited
solubility. Taken together with the thermodynamic analysis, adding the additives with FeS is favorable
matte in the slag, leading to promoted recovery of copper. 
to form matte in the slag, leading to promoted recovery of copper.

 
Figure 14. Cu
Figure 14. Cu22S‐FeS
S-FeS1.08  binary phase diagram. 
1.08 binary phase diagram.

4. Conclusions 
The feasibility of an integrated technological route to improve beneficiation of copper and iron 
components  from  copper  slag  through  modification  of  molten  slag  was  investigated,  and  the 
following conclusions were achieved: 
(1)  Iron element in the copper slag mainly existed in the form of fayalite and magnetite, and the 
Metals 2016, 6, 86 16 of 17

4. Conclusions
The feasibility of an integrated technological route to improve beneficiation of copper and iron
components from copper slag through modification of molten slag was investigated, and the following
conclusions were achieved:

(1) Iron element in the copper slag mainly existed in the form of fayalite and magnetite, and the
copper is present in sulfide form with fine size as well as being closely embedded in the fayalite
matrix, revealing that traditional physical beneficiation process may result in poor valuable
metal recovery.
(2) The modification process for copper slag was conducted to improve the recovery of copper and
iron with the optimized conditions at 0.45 binary basicity, 12% compound additive, modifying
at 1350 ˝ C for 120 min, and cooling at 1.5 ˝ C/min down to 900 ˝ C. The physical beneficiation
studies showed that compared with unmodified slag, copper grade of rougher copper concentrate
was increased from 6.43% to 11.04%; meanwhile, the copper recovery was kept about 72%,
the corresponding iron recovery was increased significantly from 32.40% to 63.36%, and the total
iron grade of magnetite concentrate was similar.
(3) XRD analysis showed that the reconstruction of mineral phases for copper slag is effective because
more fayalite was transformed to magnetite, which is beneficial to magnetic separation. Optical
microscopy and ESEM-EDS analysis of modified slag indicated that valuable mineral (matte and
magnetite) particles in the slag aggregate together and grow obviously, and the size is mostly
over 50 µm, which is extremely favorable to the beneficiation of copper and iron.

Acknowledgments: The authors wish to express their thanks to the National Key Technology R & D Program of
China (NO. 2013BAB03B04) for the financial support of this research, and also would like to thank Co-Innovation
Center for Clean and Efficient Utilization of Strategic Metal Mineral Resources of Hunan Province, which supplied
us the facilities and funds to fulfill the experiments.
Author Contributions: Deqing Zhu, Zhengqi Guo and Jian Pan conceived and designed the experiments;
Zhengqi Guo, Feng Zhang and Tengjiao Wu performed the experiments; Zhengqi Guo wrote the paper; and
Deqing Zhu and Jian Pan modified the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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