minerals

Article
Iron Recovery from Discarded Copper Slag in a RHF
Direct Reduction and Subsequent Grinding/Magnetic
Separation Process
Zhicheng Cao 1,2 , Tichang Sun 1, *, Xun Xue 1,2 and Zhanhua Liu 2
1 Key Laboratory of High-Efficient Mining and Safety of Metal Mines, Ministry of Education,
University of Science and Technology Beijing, Beijing 100083, China; caozhicheng@shenwu.com.cn (Z.C.);
xuexun@shenwu.com.cn (X.X.)
2 Beijing Shenwu Environment & Energy Technology Corp., Beijing 102200, China;
liuzhanhua@shenwu.com.cn
* Correspondence: suntc@ces.ustb.edu.cn; Tel.: +86-10-6231-4078

Academic Editor: Massimiliano Zanin

Received: 4 August 2016; Accepted: 20 October 2016; Published: 3 November 2016

Abstract: Studies on the direct reduction of carbon-bearing pellets made from discarded copper slag
have been conducted in this paper. They include the influences of reduction coal content, limestone
content, industrial sodium carbonate content, reduction temperature, reduction time and layers of
carbon-bearing pellets on reduction effect. Finally, the optimum conditions have been obtained.
The pilot scale experiment results show that the optimum conditions are the mass proportion of
discarded copper slag, reduction coal, limestone and industrial sodium carbonate of 100:25:10:3,
the reduction temperature of 1280 ◦ C for the reduction time of 35 min, three layers (approximately
42 mm) of carbon-bearing pellets—this was the basis on which the pilot tests in a rotary hearth
furnace (RHF) were conducted. The iron products obtained from the pilot tests under such conditions
have an iron grade of 90.35% with an iron recovery rate of 89.70%. The mechanism research based
on the analysis results of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy
dispersive spectroscopy (EDS) indicates that fayalite (2FeO·SiO2 ) and magnetite (Fe3 O4 ) in the copper
slag are reduced into metallic Fe in the direct reduction (DR) process, and the mass and heat transfer
become stronger from the bottom to the top layer of the pellets, resulting in a rising iron recovery rate.

Keywords: rotary hearth furnace; discarded copper slag; layers of carbon-bearing pellets;
direct reduction

1. Introduction
At present, copper production in China mainly comes in a pyrometallurgical process. Generally,
for one ton of copper, 2.2 tons of discarded copper slag is generated, and in China, the amount of
discharging copper slag exceeds 10 million tons per year [1], with the accumulated amount of copper
slag over the years exceeding 120 million tons [2]. Iron can reach about 48 million tons in this copper
slag, based on a calculation of 40% Fe content in the slag. No such costs for operations such as mining
or beneficiation (usually required for iron concentrates) have to incur for copper slag as it is discarded
from a copper smelting plant. That is to say, the copper slag is a kind of costless raw material. Thanks to
the rich zinc content in such copper slag, the same can also be recovered in the form of zinc oxide
powder when the iron element is recovered. Therefore, copper slag with 40% Fe content is a better iron
resource economically than conventional iron deposits.
Fe exists in copper slag mainly in the form of fayalite (2FeO·SiO2 ), which is hard to recover.
Current disposal practice adopted by many enterprises is stockpiling, which not only occupies large
pieces of land, but also pollutes the environment. Furthermore, a lot of valuable metals (Fe, Cu, Zn, etc.,)

Minerals 2016, 6, 119; doi:10.3390/min6040119 www.mdpi.com/journal/minerals

Minerals 2016, 6, 119 2 of 11

settled in the slag cannot be effectively utilized. Main methods in use for iron recovery from copper
slag include direct beneficiation for iron recovery [3], oxidative modification [4,5] of iron oxide for iron
recovery, smelting reduction for iron recovery [6,7], and direct reduction (DR) for iron recovery [8,9], etc.
However, iron recovery rates in direct beneficiation and oxidative modification are too low, whereas
energy Minera
consumption
ls 2016, 6, 119 of the smelting reduction is too high. By using DR followed by2 a of magnetic
11
separation process for iron recovery from copper slag, Yang [10] obtained iron powder of 92.05% iron
contentthe slagan
with cannot
ironberecovery
effectivelyrate
utilized. Main methods
of 81.01%, in use for
and Wang iron
[11] recovery from
obtained iron copper
powder slagof
include
92.96% iron
direct beneficiation for iron recovery [3], oxidative modification [4,5] of iron oxide for iron recovery,
content with an iron recovery rate of 93.49%. Both of their tests have achieved good results. However,
smelting reduction for iron recovery [6,7], and direct reduction (DR) for iron recovery [8,9], etc.
the above researches,
However, whichrates
iron recovery areintechnically feasible,
direct beneficiation andhave beenmodification
oxidative done onlyareintoo thelow,
bench test of the
whereas
laboratory,
energy consumption of the smelting reduction is too high. By using DR followed by a magnetic scale.
but a lack of industrial equipment to process copper slag with coal-based DR in large
In practice, coal-based
separation processDR facilities
for iron recoveryinclude tunnelslag,
from copper kilns
Yang[12],
[10]rotary kilns
obtained iron[13],
powderrotary hearth
of 92.05% ironfurnaces
content with
(RHF) [14,15], etc. anThe iron recovery
tunnel kilnrate of 81.01%,
features and capacity,
a low Wang [11]highobtained iron consumption,
energy powder of 92.96% andirona severe
content with an iron recovery rate of 93.49%. Both of their tests have achieved good results. However,
production environment, while the rotary kiln for the DR process is usually applied in large-scale to
the above researches, which are technically feasible, have been done only in the bench test of the
laterite laboratory,
nickel orebut reduction, which has negative effects on operation due to ringlet formation resulting
a lack of industrial equipment to process copper slag with coal-based DR in large scale.
from high temperature. Therefore,
In practice, coal-based DR facilities theinclude
reduction
tunnelfacilities with
kilns [12], lowkilns
rotary energy consumption
[13], rotary are in urgent
hearth furnaces
demand(RHF)for the large-scaled
[14,15], treatment
etc. The tunnel of industrial
kiln features production.
a low capacity, This paper
high energy takes copper
consumption, slag from a
and a severe
domestic production environment,
copper smelting plantwhile
as the theobject
rotaryofkiln for In
study. the
theDR processthe
studies, is basic
usually
andapplied in
pilot plant tests
have beenlarge-scale
conducted to laterite nickel the
following ore RHF
reduction, which
DR and has negative effects separation
grinding/magnetic on operationprocess
due to ringlet
flow, and the
formation resulting from high temperature. Therefore, the reduction facilities with low energy
reduction mechanism has been analyzed.
consumption are in urgent demand for the large-scaled treatment of industrial production. This paper
takes copper slag from a domestic copper smelting plant as the object of study . In the studies, the basic
2. Experimental
and pilot plant tests have been conducted following the RHF DR and grinding/magnetic separation
process flow, and the reduction mechanism has been analyzed.
2.1. Materials
2. Experimental
The raw material in the tests is the discarded copper slag (hereinafter referred to as copper slag)
of a domestic copper smelting plant. Its particle size is of −0.045 mm accounts for 74.48% of the total.
2.1. Materials
The major chemical composition of the copper slag is listed in Table 1 as below. The Fe content in the
The raw material in the tests is the discarded copper slag (hereinafter referred to as copper slag)
copper slag is up to 40.78% and Zn content in it is 1.35%. Both of them have certain recovery values.
of a domestic copper smelting plant. Its particle size is of −0.045 mm accounts for 74.48% of the total.
The major chemical composition of the copper slag is listed in Table 1 as below. The Fe content in the
Table 1. Chemical composition of discarded copper slag.
copper slag is up to 40.78% and Zn content in it is 1.35%. Both of them have certain recovery values.

Elements TFe Table

FeO1. Che
Cu mical
CaO MgO of
composition SiO 2 Ald
discarde 2O 3 Na
coppe O K2 O Pb
r 2slag. Zn S
Content (wt %) 40.78 38.52 0.25 1.74 2.08 33.20 2.29 0.40 0.61 0.51 1.35 0.19
Elements TFe FeO Cu CaO MgO SiO2 Al2 O3 Na 2O K2 O Pb Zn S
Content (wt %) 40.78 38.52 0.25 1.74 2.08 33.20 2.29 0.40 0.61 0.51 1.35 0.19
Figure 1 is the X-ray diffraction (XRD) patterns of the selected copper slag. With reference
Figurecomposition
to the chemical 1 is the X-ray diffraction
of Table 1, (XRitD)can
patterns
be seenof the selected
that copper
the iron slag. With
mineral reference
in the to mainly
slag is
the chemical composition of Table1, it can be seen that the iron mineral in the slag is mainly fayalite
fayalite (2FeO·SiO2 ), which is generally hard to recover in those conventional beneficiation processes.
(2FeO·SiO2 ), which is generally hard to recover in those conventional beneficiation processes. The
The anthracite, with
anthracite, witha afixed
fixed carbon contentofof
carbon content 82.47%,
82.47%, a volatile
a volatile matter
matter of 6.51%
of 6.51% and anand
ash an ash content
content of of
11.35%,11.35%,
is usedisas a reducing
used agent
as a reducing for for
agent thethe
tests. The
tests. Thelimestone
limestone with
with aa CaCO
CaCO 3 content
3 content of 90%,
of 90%, and and the
pure industrial alkali with
the pure industrial a sodium
alkali carbonate
with a sodium content
carbonate of 98%
con tent of 98%are
areused
used as the
theadditives.
additives.

Figure1.1.XRD
Figure XRD patterns
patte rns of
ofthe
therereceived
ce ive d coppe r slag.
copper slag.
Minerals 2016, 6, 119 3 of 11

2.2. Theoretical Analysis

Mixed with the reducing agent and the additives, the copper slag is made into the carbon-bearing
pellets (12–16 mm), which should be dried before being charged into a RHF. After passing the
preheating zone, middle temperature zone, high temperature zone and cooling zone, 85% of the
iron oxides in the pellets are reduced into metallic Fe. Furthermore, the ZnO in the pellets are
reduced into metallic Zn, which is collected by a bag-filter system. In order to speed up the reactions,
an appropriate amount of limestone and industrial sodium carbonate are added to the pellets, and
major chemical reactions taking place are shown as below.

2.2.1. Reduction Mechanism of Fayalite

Reduction reactions of fayalite can be obtained from the combination of Equations (1) and (2) and
its result is shown in Equation (3).

2FeO(s) + 2C(s) → 2Fe(s)+2CO(g) ∆r Gm θ = 295808 − 300.44T (J·mol−1 ) (1)

2FeO(s) + SiO2 (s) → Fe2 SiO4 (s) ∆r Gm θ = −36200 + 21.09T (J·mol−1 ) (2)

Fe2 SiO4 (s) + 2C(s) → 2Fe(s) + SiO2 (s) + 2CO(g) ∆r Gm θ = 354140 − 341.59T (J·mol−1 ) (3)

From the calculations, it can be seen that Fe2 SiO4 is more difficult to reduce than FeO because the
dissociation temperature of the former is higher than that of the latter. Since both Equations (1) and (3)
are intensely endothermic, to raise the roasting reduction temperature will help accelerate the reducing
reaction rate. Besides, Equation (1) can be formed from the combination of the following two reactions:

C(s) + CO2 (g) → 2CO(g) (4)

FeO(s) + CO(g) → Fe(s) + CO2 (g) (5)

2.2.2. Recovery Mechanism of Zn

ZnO in the dust is reduced at high temperature into the metallic Zn, which is vaporized and
separated in the form of metal vapor before being reoxidized while flowing along with the flue gas in
the flue duct, and being collected in the form of oxides. The mechanism includes several reactions
under high temperature:
ZnO(s) + C(s) → Zn(g) + CO(g) (6)

ZnO(s) + CO(g) → Zn(g) + CO2 (g) (7)

ZnFe2 O4 (s) + 2Fe(s/l) → Zn(g) + 4FeO(s) (8)

The above reactions are endothermic, so the higher the temperature, the more conducive to
reduction the reactions are. At higher temperature, thermodynamic conditions for Zn vaporization
will be greatly improved.

2.2.3. Reaction Mechanism of Additives

Since copper slag is a kind of acidic slag, the addition of calcium oxide in the DR process results
in the following reactions:

Fe2 SiO4 (s)+2CaO(s) +2C(s) →Ca2 SiO4 (s) + 2Fe(s) + 2CO(g) ∆r Gm θ = 235347 − 310.71T (J·mol−1 ) (9)

Na2 CO3 (s) + SiO2 (s) → Na2 SiO3 (s) + CO2 (g) (10)

From the above reactions, it can be seen that the higher temperature is, the more conducive to
reduction the reactions are. Fe2 SiO4 can also be reduced into metallic iron at the higher reducing
Minerals 2016, 6, 119 4 of 11

temperature. By adding CaO in the DR process, the reduction temperature of Fe2 SiO4 can be effectively
Minera lsthus
lowered, 2016, the
6, 119
DR capability has been increased and the DR of Fe2 SiO4 has been enhanced. 4Silicates,
of 11

formed by the addition of sodium carbonate as basic oxides to be combined with SiO2 , can destroy the
temperature. By adding CaO in the DR process, the reduction temperature of Fe2SiO4 can be
iron olivine structure of the copper slag and increase FeO activity, thus accelerating the reduction of
effectively lowered, thus the DR capability has been increased and the DR of Fe2SiO4 has been
iron oxides.
enhanced. Silicates, formed by the addition of sodium carbonate as basic oxides to be combined
with SiO2, can destroy the iron olivine structure of the copper slag and increas e FeO activity, thus
2.3. Experimental Procedure
accelerating the reduction of iron oxides.
The testing order is followed with the basic tests, carried out first before the results being verified
2.3.pilot
at the Experimental Procedure
plant tests. The procedures are as follows: mixing of raw materials → pelleting → drying
→ DR roasting → order
The testing followed→
wateriscooling grinding/magnetic
with separation
the basic tests, carried → final
out first before the DR product.
results The focus
being verified at is
on the pilot
quality of the final DR product and the iron recovery rate, with the calculation method
plant tests. The procedures are as follows: mixing of raw materials → pelleting → drying → DR used
roasting → water cooling → grinding/magnetic separation → final DR product. The focus is on the
as follows:
= (W
quality of the final DR product andεthe iron × β)/(Wrate,
1 recovery × α) × the
with 100% calculation method used as follows: (11)

Where ε is the iron recovery rate,ε W = (W 1 × β)/(W × α) × 100% (11)

1 is the weight of magnetically separated iron powder, β is
the Fe content
Where εofisiron powder,
the iron W israte,
recovery the Wweight
1 is theof discarded
weight copper slag,
of magnetically and α isiron
separated thepowder,
iron content
β is of
copper slag,
the Fe respectively.
content of iron powder, W is the weight of discarded copper slag, and α is the iron content of
copper slag, respectively.
3. Results and Discussions
3. Results and Discussions
The early tests indicated that when one layer of pellets were under roasting, the highest reduction
The early
temperature couldtests
onlyindicated
be keptthat when◦ C,
at 1200 one layer ofthe
because pellets were
higher under roasting,
temperature couldthecause
highest reduction
pellets melting,
temperature
which could onlyto
is not conducive bethe
keptRHF
at 1200 °C, becauseWhen
production. the higher
twotemperature could cause
layers of pellets were pellets melting,
laid for roasting,
which is
reduction not conducive
temperature to the
could RHF production.
be increased and no When
pelletstwo layerstook
melting of pellets
place,were
thus alaid for pellet
good roasting,
shape
can be maintained. Under this condition, many factors that affect Fe content and recovery ratecan
reduction temperature could be increased and no pellets melting took place, thus a good pellet shape of the
ironbepowder
maintained.
wereUnder this condition,
also examined, suchmany
as thefactors
amountthatofaffect Fe content
reduction coal,and recovery
quantity of rate of the iron
additives, such as
powder were also examined, such as the amount of reduction coal, quantity of additives, such as
limestone and industrial sodium carbonate, reduction temperature and reduction time.
limestone and industrial sodium carbonate, reduction temperature and reduction time.
3.1. Effect of Reduction Coal Dosage on the DR Process
3.1. Effect of Reduction Coal Dosage on the DR Process
The exploratory experiments show that 5% of bentonite should be added into the copper slag
The exploratory experiments show that 5% of bentonite should be added into the copper slag
pellets, with a drop strength (number of non-breakage of a pellet drop at the height of 0.5 m onto a
pellets, with a drop strength (number of non-breakage of a pellet drop at the height of 0.5 m onto a
steel plate)
steel of carbon-containing
plate) of carbon-containing pellets
pelletsbeing
beingreached
reachedover
over six
six times, thus meeting
times, thus meetingthe
therequirement
requirement of
the of
RHF the process. The examinations
R HF process. of theofeffect
The examinations of reduction
the effect coal dosage
of reduction on the
coal dosage on product’s Fe content
the product’s Fe
andcontent
recovery rates were carried out under the following conditions: limestone dosage
and recovery rates were carried out under the following conditions: limestone dosage of of 15%, sodium
carbonate dosage
15%, sodium of 0.5%,
carbonate reduction
dosage of 0.5%,temperature of 1250 ◦ C,of reduction
reduction temperature time of time
1250 °C, reduction 30 min,
of 30grinding
min,
fineness
grindingof − 0.074 mm
fineness accounting
of −0.074 for 72.1% for
mm accounting of the copper
72.1% of theslag mix slag
copper and mix
magnetic field strength
and magnetic field of
143.31 kA/m.
strength The result
of 143.31 kA/m.is The
shown in is
result Figure
shown2 in
below.
Figure 2 below.

95 95

90 90
Fe re cocery /%
Fe grade /%

85 85

Fe grade
80 80
Fe re covery

75 75
16 19 22 25 28 31
Re duction coal dosage/%

Figure 2. Effe
Figure ct of
Effect ofre duction coal
reduction coaldosage
dosageon
onthe
theDR
DRproce ss.
process.
Minerals 2016, 6, 119 5 of 11

Minerals 2016, 6, 119 5 of 11

Figure 2 shows that, with the increase of the dosage of the reduction coal, the Fe content of the
iron Minerals
powder lies
2016,
Figure between
26,shows
119 that,85%
withand
the 87%, and
increase ofthe
the iron
dosagerecovery rate firstly
of the reduction slightly
coal, the Fe rises then
content declines,
of5 the
of 11
therefore the optimum
iron powder dosage85%
lies between of reduction
and 87%,coalandisthe
setiron
at 25%. With rate
recovery the lower
firstly dosage
slightlyofrises
the reduction
then
Figure 2 shows that, with the increase of the dosage of the reduction coal, the Fe content of the
coal,declines,
parts of the iron
therefore theoxides
optimumremain unreduced,
dosage of reductionwhereas the
coal is set a t higher dosage
25%. With of the
the lower reduction
dosage of the coal
iron powder lies between 85% and 87%, and the iron recovery rate firstly slightly rises then
willreduction
hinder the coal, parts of the iron
agglomeration of theoxides remain
reduced ironunreduced,
grain, thuswhereas
causingthethehigher
negativedosage of the
impacts on the
declines, therefore the optimum dosage of reduction coal is set a t 25%. With the lower dosage of the
reduction
subsequent coal will hinder
grinding/magnetic the agglomeration of the reduced iron grain, thus causing the negative
reduction coal, parts of the separation
iron oxides for iron recovery.
remain unreduced, whereas the higher dosage of the
impacts on the subsequent grinding/magnetic separation for iron recovery.
reduction coal will hinder the agglomeration of the reduced iron grain, thus causing the negative
3.2. Effect of the Limestone Dosage on the DR Process
impacts
3.2. Effecton theLimestone
of the subsequent grinding/magnetic
Dosage separation for iron recovery.
on the DR Process
The examination of the effect of the limestone dosage on the product’s Fe content and recovery
The examination of the effectonofthe
the limestone dosage on the product’s Fe content and recovery
rates3.2.
wereEffect of the Limestone
conducted. Dosage
The proportion ofDR Processslag,
copper reduction coal and industrial sodium carbonate
rates were conducted. The proportion of copper slag, reduction coal and industrial sodium
was fixed atexamination
The 100:25:0.5, with
of the the other
effect of the conditions of reduction
limestone dosage and grinding/magnetic
on the product’s separation
Fe content and recovery
carbonate was fixed at 100:25:0.5, with the other conditions of reduction and grinding/magnetic
rates
remaining were conducted.
unchanged. The proportion of copper slag, reduction coal and industrial sodium
separation remainingThe result isThe
unchanged. shownresultinisFigure
shown 3inbelow.
Figure 3 below.
carbonate was fixed at 100:25:0.5, with the other conditions of reduction and grinding/magnetic
separation remaining unchanged.
100 The result is shown in Figure 3 below.
90

100 90
85

/% /%
95
/% /%

Fe re covery
85
Fe grade

Fe grade 80
95

Fe re covery
Fe recovery
Fe grade

90 Fe grade 80
75
Fe recovery
90
75
85 70
0 5 10 15 20 25
85 Lime stone dosage/% 70
0 5 10 15 20 25

Figure 3.
Figure 3.Effe
Effect Lime
ct ofoflime stonedosage
stone
limestone dosage/%
dosageononthe
theDR
DRproce ss.
process.

Figure
Figure 3 shows that, with3.the
Effeincrease
ct of lime stone
in thedosage
dosageonofthe DRlimestone,
the proce ss. the iron grade has a
Figure 3 shows that, with the increase in the dosage of the limestone, the iron grade has a tendency
tendency to rise, and the iron recovery rate rises first then declines. Furthermore, with the limestone
to rise, and the 3iron
Figure recovery
shows rate rises
that, with first then
the increase in declines.
the dosageFurthermore, withthe
of the limestone, theiron
dosage of 10% of the copper slag, the iron grade can reach 8 8.79% with the iron recovery rate of
limestone dosage
grade has a of
tendency
10%86.75%. to rise,
of the copper andthe
slag, theiron
iron grade
recoverycanrate rises
reach first then declines.
ironFurthermore, with 86.75%.
the limestone
However, with the limestone dosage of88.79%
15% andwith thepartial
20%, recovery
melting ofrate
theofupper However,
layer of
dosage of 10% ofdosage
withcarbon-containing
the limestone the copper
of slag,
15% the20%,
and iron partial
grade can reach of
melting 8 8.79%
the with the
upper ironofrecovery
layer rate of
carbon-containing
pellets obstructs the heat transfer to the lower layers of pellets, thus the reducing
86.75%.
pellets However,
obstructs withtransfer
the heat the limestone
to thedosage
lower of 15% and
layers 20%, partial
of pellets, melting of theeffect
upperislayer of
effect is negatively impacted. Therefore, the optimal dosage of thethus the reducing
limestone is set at 10%. negatively
carbon-containing pellets obstructs the heat transfer to the lower layers of pellets, thus the reducing
impacted. Therefore, the optimal dosage of the limestone is set at 10%.
effect
3.3. is negatively
Effect impacted.
of the Industrial Therefore,
Sodium Carbonatethe optimal
Dosage dosage
on the of the limestone is set at 10%.
DR Process
3.3. Effect of the Industrial Sodium Carbonate Dosage on the DR Process
Examinations
3.3. Effect of the Sodium
of the Industrial effect ofCarbonate
industrial sodium
Dosage carbonate
on the dosage on the product’s Fe content
DR Process
and recovery rate were conducted. The proportion of
Examinations of the effect of industrial sodium carbonate dosage copper slag, reduction coal and Fe
on the product’s industrial
content and
Examinations of the effect of industrial sodium carbonate dosage on the product’s Fe content
sodium
recovery ratecarbonate
were was
conducted. fixed
The at 100:25:10,
proportion ofwith
copper the other
slag, conditions
reduction coal of
andreduction and
industrial sodium
and recovery rate were conducted. The proportion of copper slag, reduction coal and industrial
grinding/magnetic
carbonate separation remaining unchanged. The result is shown in Figure 4.
sodiumwas fixed atwas
carbonate 100:25:10,
fixed with the otherwith
at 100:25:10, conditions
the otherof reduction
conditionsandof grinding/magnetic
reduction and
separation remaining separation
grinding/magnetic unchanged. 95 The
remainingresult is shown
unchanged. in
The Figure
result is4.shown
95 in Figure 4.

95 95
/% /%

90 90
/% /%

Fe re cocery
Fe grade

90 90
Fe re cocery
Fe grade

85 Fe grade 85

85 Fe
Ferecovery
grade 85

80 Fe recovery 80
0 1 2 3 4 5 6
80 Industrial sodium carbonate dosage/%80
0 1 2 3 4 5 6
Industrial
Figure 4. Effe ct of industrial sodium
sodium carbonate
carbonate dosage/%
dosage on the DR proce ss.

Figure4.
Figure 4. Effect
Effe ct of
of industrial
industrialsodium
sodiumcarbonate
carbonatedosage
dosageonon
the DR
the proce
DR ss.
process.
Minerals 2016, 6, 119 6 of 11
Minera ls 2016, 6, 119 6 of 11

Figure
Figure 44 shows
shows that,
that, both
both the
the iron
iron grade andand the
the iron
iron recovery
recovery rate
rate show
show a tendency
tendency toto increase
increase
at
at first
first and then decrease with
with the increase in the dosage
dosage of of the industrial sodium carbonate. This is
because
because more
more and
and more silicates
silicates are formed
formed fromfrom the
the combination
combination of of sodium
sodium carbonate
carbonate with
with SiO 22,,
which destroys
destroys the
theiron
ironsilicate
silicatemineral
mineralstructure
structureofof the
the copper
copper slag,
slag, andand enhances
enhances thethe reduction
reduction of
of the
the
ironiron oxides.
oxides. However,
However, a higher
a higher dosagedosage of sodium
of sodium carbonate
carbonate leads
leads to the to
topthe top carbon-containing
carbon-containing pellets
pellets
melting, melting, thus obstructing
thus obstructing further further
reductionreduction of thelayers
of the lower loweroflayers of pellets.
pellets. As athe
As a result, result, the
optimal
dosage of
optimal the industrial
dosage sodium carbonate
of the industrial is set at 3%.
sodium carbonate is set at 3%.

3.4. Effect
3.4. Effect of
of the
the Roasting
Roasting Temperature
Temperature on the DR
on the DR Process
Process
From all
From all the
the above
above tests,
tests, the
the optimal
optimal proportion
proportion ofof the
the copper
copper slag,
slag, the
the reduction
reduction coal,
coal, the
the
limestone and the industrial sodium carbonate was fixed at 100:25:10:3. Tests on the
limestone and the industrial sodium carbonate was fixed at 100:25:10:3. Tests on the reduction reduction
temperature were
temperature were conducted
conducted on
on such
such aa basis,
basis, with
with the
the details
details shown
shown inin Figure
Figure 5.
5.

95 95

90

Fe re cocery /%
Fe grade /%

90

85

Fe grade 85
80
Fe recovery

75 80
1200 1220 1240 1260 1280 1300 1320 1340
Roasting te mperture/ oC

Figure 5. 5.
Figure Effe ct ofofrereduction
Effect duction tetemperature
mpe rature on
on the
the DR
DR process.
proce ss.

Figure 5 shows that, with the increase in the reduction temperature, the iron grade and the
Figure 5 shows that, with the increase in the reduction temperature, the iron grade and the
recovery rate have a tendency to first rise before declining, and at the reduction temperature ◦of
recovery rate have a tendency to first rise before declining, and at the reduction temperature of 1280 C,
1280 °C, an iron grade of 90.18% can be obtained at the highest iron recovery rate of 89.91%. As the
an iron grade of 90.18% can be obtained at the highest iron recovery rate of 89.91%. As the temperature
temperature continues rising, the thermodynamic conditions for mass and heat transfer in the lower
continues rising, the thermodynamic conditions for mass and heat transfer in the lower pellet layer
pellet layer deteriorate. Therefore, the optimal reduction temperature is 1280 °C.
deteriorate. Therefore, the optimal reduction temperature is 1280 ◦ C.
3.5. Effect of the Reduction Time on the DR Process
3.5. Effect of the Reduction Time on the DR Process
With
With the proportioning and
the proportioning and grinding/magnetic
grinding/magnetic separation
separation conditions
conditions of
of the
the raw
raw materials
materials
remaining unchanged, the tests on reduction time were conducted at a reduction temperature of
remaining unchanged, the tests on reduction time were conducted at a reduction temperature of
1280 ◦°C, and the iron grade and iron recovery rate showed a tendency to increase. With the
1280 C, and the iron grade and iron recovery rate showed a tendency to increase. With the reduction
reduction
time set attime set atan35iron
35 min, min, an iron
grade grade of
of 90.85% 90.85%
and an ironand an iron rate
recovery recovery rate of
of 90.49% 90.49%
could could be
be obtained.
obtained. Further increase in the reduction time did not result in any considerable improvement,
Further increase in the reduction time did not result in any considerable improvement, and the optimal
and the optimal
reduction time isreduction timefrom
set at 35 min, is setaatcost-saving
35 min, from a cost -saving
perspective. perspective.
Details are shownDetails are 6.
in Figure shown in
Figure 6.
3.6. Effect of the Layers of the Carbon-Bearing Pellets on the DR Process
All the above tests were conducted on two layers of carbon-bearing pellets, with such conditions
as the proportion, the reduction temperature, the reduction time and the grinding/magnetic separation
remaining unchanged. Further tests were carried out on the impacts of the pellet layers from 1 to 4 on
the reduction. The details are shown in Figure 7.
 95 95

Fe re cocery /%
90 90

Fe grade /%
Minerals
Minera 6,119
2016, 6,
ls 2016, 119 77of
of11
11

95 Fe grade 95
85 85

Fe recovery

Fe re cocery /%
90 90

Fe grade /%
80 80
15 25 35 45
Re duction time /min
85 Fe grade 85
Figure 6. Effe ct of re duction time on the DR proce ss.
Fe recovery
3.6. Effect of the Layers of the Carbon-Bearing Pellets on the DR Process
80 80
All the above tests were 15conducted 25on two layers 35 of carbon
45 -bearing pellets, with such
conditions as the proportion, the reduction temperature,
Re duction time /min the reduction time and the
grinding/magnetic separation remaining unchanged. Further tests were carried out on the impacts
Figure 6.6.Effe
Figure ct ofofrereduction
Effect duction time
timeon the
onare DR
DR proce
the shown ss.
process.
of the pellet layers from 1 to 4 on the reduction. The details in Figure 7.

3.6. Effect of the Layers of the Carbon-Bearing

95 Pellets on the DR Process 95

All the above tests were conducted on two layers of carbon -bearing pellets, with such
conditions as the proportion, the reduction temperature, the reduction time and the

Fe re cocery /%
grinding/magnetic separation90remaining unchanged. Further tests were 90 carried out on the impacts
Fe grade /%

of the pellet layers from 1 to 4 on the reduction. The details are shown in Figure 7.

95 Fe grade 95
85 85

Fe recovery Fe re cocery /%

90 90
Fe grade /%

80 80
0 1 2 3 4 5
Carbon-containing pe lle ts layers
85 Fe grade 85
Figure 7. Effe ct of carbon-containing pe lle ts laye rs on the DR proce ss.
Figure 7. Effect of carbon-containing pellets layers on the DR process.
Fe recovery
It can be seen from Figure 7 that the distribution thickness of three layers (about 42 mm) of the
It can be seen from
carbon-containing Figure
pellets can80 7have
that the
the distribution thickness
best reduction effect of three
with layers
80 the (about
highest 42 grade
iron mm) ofandthe
carbon-containing pellets can 0 the best
have 1 2
reduction 3 effect 4with the 5 highest iron grade and recovery
recovery rate obtainable. When the carbon-containing pellets are in four layers, heat transfer to the
rate obtainable.
lower When the with
layers deteriorates Carbon-containing
carbon-containing
reduction pellets
results are pe
being in lle ts layers
four
negativelylayers, heat transfer
affected, and theto iron
the lower
gradelayers
and
deteriorates with reduction
the recovery rate Figure results
greatly7.declining. being negatively affected, and the iron grade and
Effe ct of carbon-containing pe lle ts laye rs on the DR proce ss.
the recovery rate
greatly declining.
4. The Pilot-Scale
It can be seen Tests via RHF
from Figure 7 that the distribution thickness of three layers (about 42 mm) of the
4. The Pilot-Scale Tests via RHF
carbon-containing pellets can have the best reduction effect with the highest iron grade and
The optimal conditions obtained from the basics tests are the proportion of the copper slag, the
The rate
recovery optimal conditions
obtainable. When obtained from the basicspellets
the carbon-containing tests are
are the proportion
in four of the
layers, heat coppertoslag,
transfer the
reduction coal, the limestone, the industrial sodium carbonate fixed as 100:25:10:3, at a distribution
the reduction
lower coal, the limestone,
layers deteriorates the industrial
with reduction results sodium
being carbonate
negativelyfixed as 100:25:10:3,
affected, at a distribution
and the iron grade and
thickness of three pellet layers, and a reduction temperature of 1280 °C for a reduction time of 35 min.
thickness
the recoveryof three pellet layers,
rate greatly and a reduction temperature of 1280 ◦ C for a reduction time of 35 min.
declining.
These conditions were applied to the pilot-scale tests on a RHF having an outer diameter of 10 m,
These conditions were applied to the pilot-scale tests on a RHF having an outer diameter of 10 m,
and a processing capability of 2 t/h.
4. The
and Pilot-Scale capability
a processing Tests via RHF
of 2 t/h.
The metallization pellets discharged from the R HF went through a grinding/magnetic
The metallization
The optimal pellets
conditions discharged
obtained fromfrom
theofthe RHF went
basics through a grinding/magnetic separation
separation process, with a grinding fineness −0.074tests
mmare the proportion
accounting of theofcopper
for 72.10% slag,
the total andthea
process,
reduction with a
coal, grinding
the fineness
limestone, the of − 0.074
industrial mm accounting
sodium for
carbonate 72.10%
fixed of
as the total and
100:25:10:3, a
at magnetic
a field
distribution
magnetic field strength of 143.31 kA/m in the first stage, and a grinding fineness of −0.074 mm
strength of
thickness of143.31 kA/mlayers,
three pellet in the and
first astage, and atemperature
reduction grinding fineness
of 1280 −0.074
of °C for amm accounting
reduction for35
time of 50.89%
min.
of the rest and a magnetic field strength of 95.54 kA/m in the second stage.
These conditions were applied to the pilot-scale tests on a RHF having an outer diameter of 10 The iron content of the
m,
obtained iron products is 90.3%
and a processing capability of 2 t/h. with an iron recovery rate of 89.70%.
The metallization pellets discharged from the R HF went through a grinding/magnetic
separation process, with a grinding fineness of −0.074 mm accounting for 72.10% of the total and a
magnetic field strength of 143.31 kA/m in the first stage, and a grinding fineness of −0.074 mm
Minera ls 2016, 6, 119 8 of 11

accounting for 50.89% of the rest and a magnetic field strength of 95.54 kA/m in the second stage.
Minerals 2016, 6, 119 8 of 11
The iron content of the obtained iron products is 90.3% with an iron recovery rate of 89.70%.

5. Studies
5. Studies of
of Mechanisms
Mechanisms and
and Product
Product Analysis
Analysis

5.1.
5.1. Analysis of the
the Mechanism
Mechanism of
of the
the Distribution
Distribution Thickness
Thickness (Pellets
(Pellets Layers)
Layers)
In
In order
ordertotoexplore
explore thethe
mechanism
mechanism of theofeffect
the of layers
effect of oflayers
the carbon-bearing pellets (thickness
of the carbon-bearing pellets
of layers) on
(thickness ofthe DR process,
layers) on the DRXRD analysis
process, XRwas conducted
D analysis wasonconducted
the copperonslag
theand the metallization
copper slag and the
pellets at different
metallization locations
pellets of a locations
at different 4-layer distribution
of a 4-layerthickness.
distribution The details are
thickness. Theshown
detailsinare
Figure
shown8.
The first, the
in Figure second,
8. The first,the
thethird and the
second, the fourth layer,
third and respectively,
the fourth layer, indicate the pellets
respectively, from the
indicate the upper
pellets
(top)
from to the
the lower
upper (bottom).
(top) to the lower (bottom).

Figure
Figure8.8.XRD
XRDpatte rns of
patterns of coppe
copperr slag
slagand
andmetallization
me tallizationpellets.
pe lle ts.

In Figure 8, four changes can be observed: (1) The phases of fayalite (Fe 2SiO4 ) and
In Figure 8, four changes can be observed: (1) The phases of fayalite (Fe2 SiO4 ) and magnetite
magnetite (Fe3O4 ) do not exist anymore after DR in a R HF; (2 ) Differences in the major peak
(Fe3 O4 ) do not exist anymore after DR in a RHF; (2) Differences in the major peak heights of metallized
heights of metallized pellets from layer 1 to layer 4 mean differences in their Fe contents, namely,
pellets from layer 1 to layer 4 mean differences in their Fe contents, namely, layer 1 > layer 2 > layer
layer 1 > layer 2 > layer 3 > layer 4; (3) Occurrence of the diffraction peak values of the dissociate
3 > layer 4; (3) Occurrence of the diffraction peak values of the dissociate SiO2 in pellets layer 1, 2
SiO2 in pellets layer 1, 2 and 3 indicates a complete and effective reduction, with all SiO 2 released
and 3 indicates a complete and effective reduction, with all SiO2 released from the fayalite phase that
from the fayalite phase that is conducive to an increase in the iron recovery rate through the
is conducive to an increase in the iron recovery rate through the grinding and magnetic separation;
grinding and magnetic separation; (4) Apparent appearance of the diffraction peak of the impurities
(4) Apparent appearance of the diffraction peak of the impurities (augite Ca(Fe,Mg)Si2 O6 ) in the
(augite Ca(Fe,Mg)Si 2O6 ) in the metallization pellets of layer 4 also indirectly indicates that the
metallization pellets of layer 4 also indirectly indicates that the reduction effect of the pellets in the
reduction effect of the pellets in the distributed layer 4 is not as good as those in layer 1, 2 and 3.
distributed layer 4 is not as good as those in layer 1, 2 and 3.
Therefore, it can be concluded that the iron reduction of the pellets in a distribution thickness
Therefore, it can be concluded that the iron reduction of the pellets in a distribution thickness of
of three layers is comparatively more complete, which is beneficial for the iron recovery in the
three layers is comparatively more complete, which is beneficial for the iron recovery in the subsequent
subsequent grinding/magnetic separation process.
grinding/magnetic separation process.
Figure 9 shows the results of the analysis by using SEM and EDS conducted at different
Figure 9 shows the results of the analysis by using SEM and EDS conducted at different locations
locations of the metallization pellets, with a, b, c, d respectively indicating layer 1, 2, 3 and 4. It can
of the metallization pellets, with a, b, c, d respectively indicating layer 1, 2, 3 and 4. It can be clearly
be clearly seen that the iron crystal chains are formed from iron agglomeration in layer 1, 2 and 3,
seen that the iron crystal chains are formed from iron agglomeration in layer 1, 2 and 3, which is
which is conducive to iron recovery in subsequent grinding/magnetic separation operations. The
conducive to iron recovery in subsequent grinding/magnetic separation operations. The pellets of
pellets of layer 4, however, show scattered iron particles in the pellets, indicating a less effective
layer 4, however, show scattered iron particles in the pellets, indicating a less effective reduction, with
reduction, with a lower iron recovery than those in the first three layers.
a lower iron recovery than those in the first three layers.
Minerals 2016, 6, 119 9 of 11
Minerals 2016, 6, 119 9 of 11

Figure9.9.SEM
Figure SEMimages
images and
and EDS
EDS analysis
analysis results
resultsof
ofthe
themetallization
metallizationpellets.
pellets.(a)(a)
layer 1; (b)
layer layer
1; (b) 2; 2;
layer
(c) layer 3; (d) layer
(c) layer 3; (d) layer 4.4.

5.2. Product Analysis

5.2. Product Analysis
The chemical analysis of the iron powder obtained from the pilot plant tests is shown in Table 2,
The chemical analysis of the iron powder obtained from the pilot plant tests is shown in Table 2,
and the chemical analysis of ZnO-rich dust obtained from the bag filter system is shown in Table 3.
and thebe
It can chemical
seen thatanalysis of ZnO-rich
the metallic iron (MFe) dust obtained
accounts from
for the the bag
majority of filter system is shown
the magnetically separatedin Table
iron 3.
It powder,
can be seen that the metallic iron (MFe) accounts for the majority of the magnetically
with a metallization rate of 99.09%, and less contents of impurities such as sulfur and separated
iron
phosphorous,with
powder, whicha metallization rate reduced
is a good quality of 99.09%,
ironand less contents
powder. The zincofoxide
impurities
contentsuch
of theasZnO-rich
sulfur and
phosphorous, which is a good quality reduced iron powder. The zinc oxide content of the
dust, obtained from the bag filter system, is 68.53%, which can be a good raw material for zinc smelters.ZnO-rich
dust, obtained from the bag filter system, is 68.53%, which can be a good raw material for zinc smelters.
Table 2. Chemical composition of obtained iron powder from grinding/magnetic separation.
Table 2. Chemical composition of obtained iron powder from grinding/magnetic separation.
Elements Tfe Mfe CaO MgO SiO2 Al2O3 Cu C Mn P S
Content
Elements (wt %) 91.03
Tfe 90.20
Mfe 0.14
CaO 0.67
MgO 0.40
SiO2 1.87 0.35
Al2 O3 Cu 0.61C 0.07Mn0.02 P0.08 S
Content (wt %) 91.03 90.20 0.14 0.67 0.40 1.87 0.35 0.61 0.07 0.02 0.08
Table 3. Chemical composition of obtained ZnO rich dust.

Elements TFe CaO

Table 3. MgO
Chemical SiO2 Al2of
composition O3obtained
K2O Na 2O PbO ZnO
ZnO rich dust. C S P
Content (wt %) 1.84 0.84 3.21 1.47 0.60 0.54 0.17 14.21 68.53 0.11 3.54 0.13
Elements TFe CaO MgO SiO2 Al2 O3 K2 O Na2 O PbO ZnO C S P
Figure 10 is the XRD patterns and SEM image of the iron powder from the grinding/magnetic
Content (wt %) 1.84 0.84 3.21 1.47 0.60 0.54 0.17 14.21 68.53 0.11 3.54 0.13
separation. It can be seen that iron in the iron powder obtained from the grinding/magnetic
separation exhibits a high diffraction peak, with certain impurities in the pyroxene phase. The SEM
Figure
image shows10 islarger
the XRD
ironpatterns
particlesand SEM
in the image of theiron
metallization ironpowder
powderfrom
fromthe
thegrinding/magnetic
grinding/magnetic
separation.
separation,Itwith
can be seen impurity
certain that iron in the augite
iron powder obtained within.
phase wrapped from the grinding/magnetic separation
exhibits a high diffraction peak, with certain impurities in the pyroxene phase. The SEM image shows
larger iron particles in the metallization iron powder from the grinding/magnetic separation, with
certain impurity in the augite phase wrapped within.
Minerals 2016, 6, 119 10 of 11
Minerals 2016, 6, 119 10 of 11

(a) (b)
Figure 10. XRD patte rns (a) and SEM image (b) of the iron powde r from the grinding/magne tic se paration.
Figure 10. XRD patterns (a) and SEM image (b) of the iron powder from the grinding/magnetic separation.

6. Conclusions
6. Conclusions
(1) Basic tests and pilot scale plant tests have been conducted on the discarded copper slag from a
(1) Basic testscopper
Chinese and pilot scale plant
smelting plant,tests have been
by adopting conducted
a direct on the
reduction in discarded
a RHF andcopper slag from
a subsequent
a grinding/magnetic
Chinese copper smelting plant, by adopting a direct reduction in a RHF
separation process, from which optimal conditions are acquired as follows:and a subsequent
grinding/magnetic separationcopper
the proportion of discarded process,slag,
from which optimal
reduction conditions
coal, limestone areindustrial
and acquired as follows:
sodium
the proportion
carbonates of discarded
of 100:25:10:3, copper slag,
the reduction reduction
temperature coal,°Climestone
of 1280 and industrial
for the reduction time of 35sodium
min,
carbonates of 100:25:10:3,
and the pellets the reduction
in three layers (about 42temperature
mm thick). of The1280 ◦ C for the
pilot-scale reduction
tests in a RHF time
haveof been
35 min,
carried
and out under
the pellets such conditions
in three and the
layers (about 42 mmobtained ironThe
thick). powder products
pilot-scale have
tests in an iron grade
a RHF of
have been
90.35%out
carried with an iron
under suchrecovery rate of
conditions and89.70%.
the obtained iron powder products have an iron grade of
(2) 90.35%
Analysis
withof an
theiron
mechanism
recoveryshows
rate ofthat fayalite and magnetite in the copper slag are reduced
89.70%.
into metallic Fe in the direct reduction
(2) Analysis of the mechanism shows that fayalite andprocess, and magnetite
the mass and heatcopper
in the transfer become
slag strongerinto
are reduced
from the bottom layer to the top layer, exhibiting a higher diffraction peak.
metallic Fe in the direct reduction process, and the mass and heat transfer become stronger In addition, the iron
from
in the metallization pellets turns into iron crystal chains from a dispersion state, resulting in a
the bottom layer to the top layer, exhibiting a higher diffraction peak. In addition, the iron in the
rising iron recovery rate.
metallization pellets turns into iron crystal chains from a dispersion state, resulting in a rising
iron recovery rate.
Ackno wledgments: This work was financially supporte d by Be ijing Scie nce and Technology Spe cial Project
(Grant No. Z151100001615027).
Acknowledgments: This work was financially supported by Beijing Science and Technology Special Project
Author
(Grant No.Contributions: Zhiche ng Cao, Tichang Sun and XunXue conce ive d and designe d the e xperiments;
Z151100001615027).
Zhiche ng Cao and Zhanhua Liu pe rforme d the e xperime nts; Zhiche ng Cao and Tichang Sun analyze d the data;
Author
ZhicheContributions:
ng Cao wrote theZhicheng
paper. Cao, Tichang Sun and XunXue conceived and designed the experiments;
Zhicheng Cao and Zhanhua Liu performed the experiments; Zhicheng Cao and Tichang Sun analyzed the data;
Zhicheng Cao
Conflicts wrote theThe
of Interest: paper.
authors de clare no conflict of inte re st.
Conflicts of Interest: The authors declare no conflict of interest.
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