Clean Technologies and Environmental Policy

https://doi.org/10.1007/s10098-018-1501-y

ORIGINAL PAPER

Novel method for iron recovery from hazardous iron ore

tailing with induced carbothermic reduction-magnetic
flocculation separation
Shao-Jun Bai1,2 · Chun-Long Li2 · Xiang-Yu Fu1 · Chao Lv1 · Shu-Ming Wen1,2

Received: 15 August 2017 / Accepted: 2 February 2018

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
In this paper, a novel method to recover iron from iron ore tailing (IOT) was studied. The method was induced with car-
bothermic reduction, followed by magnetic flocculation separation (MFS) and conventional magnetic separation (CMS).
The effects of reduction temperature, as well as the amount of coal and sodium carbonate on iron recovery efficiency, were
chiefly introduced according to the experimental mechanism. Results of carbothermic reduction showed that iron minerals
in the IOT were transformed to metallic iron at the reduction temperature of 1100 °C for 120 min, with a C/Ore mass ratio
of 25% and a mass ratio of Na2CO3 to ore of 8%. The reduction activity of FeO increased and a deep reduction from FeO
to metallic iron was observed with the addition of Na2CO3. The metallization mean of induced reduction ores reached
32.53%. Results of magnetic separation showed that the MFS concentrate grade was 74.02% Fe, with the recovery rate at
79.51% when the reduced samples were ground to 87.4% below 38 μm. This iron recovery increased by 4.19% compared
with that of CMS, whereas the iron concentrate grade slightly changed. In addition, the microstructure and phase
transformation of the carbothermic reduction process were studied by X-ray powder diffraction, scanning electron
microscope, and energy-disperse spectroscopy, thereby complying with the main force analysis of magnetic flocculation in
the MFS to help understand the mechanism of the novel method.

 Shao-Jun Bai
baishaojun830829@126.com
 Shu-Ming Wen
shmwen@126.com
1
Faculty of Land Resource Engineering, Kunming University
of Science and Technology, Kunming 650093, Yunnan,
China
2
State Key Laboratory of Complex Nonferrous Metal
Resources Clean Utilization, Kunming University of
Science and Technology, Kunming 650093, China

13
 S.-J. Bai et
al.
Graphical Abstract

Keywords Iron ore tailing · Induced carbothermic reduction · Metallic iron · Magnetic flocculation separation

Introduction completely utilize available supplies of IOT as secondary

resources. According to statistics, the generation of IOT is
Iron ore tailing (IOT) is a typical industrial solid waste
estimated to be 20 billion, with the annual IOT emission of
from iron production, where approximately 2.5–3 t of IOT
13 million t. Assuming the tailings contain an average of
are generated for 1 t of iron product in China (Zhang et al.
11% iron, the total metallic iron in the IOT reaches up to
2006). In recent years, steel production has significantly
2.2 billion t with 1.43 million t of metallic iron losses in
increased to satisfy construction industry demands, which
the tailings every year (Kim et al. 2001). Thus, the
has resulted in the generation of a considerable amount of
recovery and utilization of iron from IOT are very
IOT. Official statistics showed that a total of 59.7 billion t
important to mitigate the risk of iron ore shortage.
of tailings have been discarded as waste in China, where
Currently, many studies have reported on utilizing IOT
IOT generation being estimated to be one-third of the total
for the recycling of useful metals, such as Fe, Co, Ni, and
tailings (of which only less than 7% is recycled as
Cu (Sirkeci et al. 2006). IOT can also serve as a raw build-
resources) (Ma et al. 2016; Li et al. 2010a). These
ing material, such as a cement clinker and an additive in
untreated IOT not only pollute land, water, and air, but
the preparation of cement, concrete, or bricks (Li et al.
also pose threat to the safety of human beings (Shettima et
2010b; Cheng et al. 2016; Das et al. 2000). Moreover, IOT
al. 2016; Luo and Nguyen 2017). With the continuous
is involved in the production of lightweight ceramisite and
exhaustion of mineral resources, many countries are facing
magnetite powder and can also serve as filling goaf and
the risk of shortage in raw materials, thereby creating an
soil conditioner (Yang et al. 2015; Liu et al. 2010; Li et al.
awareness on the need to
Novel method for iron recovery from hazardous iron ore tailing with induced
carbothermic…
2010a). In previous studies, reduction roasting-magnetic
separation is an important method for recycling iron from
IOT or other wastes containing iron. During reduction roast-
ing, weak magnetic minerals are converted into strongly
magnetic minerals, while the magnetism of the gangue
minerals does not significantly change; thus, this promotes
the separation of the iron and slag. However, the low iron
grade and high contents of SiO2 and Al2O3 in the raw ore
add significant difficulty for the growth and aggregation of
strongly magnetic minerals during the reduction roasting
process. Recycling these strongly magnetic fine minerals
by following magnetic separation is also difficult (Li et al.
2013; Wang et al. 2011; Suthers et al. 2014; Han et al.
2015). In addition, previous studies have indicated that
alkali metal oxides play an important role in the reduction
of iron oxides. The carbothermic reduction of iron oxides
can be reinforced by adding Na2O, and the mass and heat
transfer during the reduction reaction can be optimized by
adding CO2 (Huang et al. 2005; Bai et al. 2012; Li et al.
2013; Yu et al. 2013). Motivated by these observations,
sodium car- bonate is selected as the alkaline additive in
this study for the induced carbothermic reduction of IOT to
attempt the pro- motion of growth and reconstruction of
magnetic minerals.
At present, the effective recovery of fine iron minerals
remains a significantly challenging task; thus, recycling
fine minerals have been emphasized by many research
works. Under actual conditions, a considerable amount of
fine minerals falls into tailings due to the lack of effective
recovery methods (Shibata and Fuerstenau 2003; Wang
et al. 2014). One of the promising separation methods for
fine minerals is the application of coagulation or floccula-
tion (Singh et al. 2015; Rao and Narasimhan 1985; Ozkan
2003; Zahrim et al. 2010). Compared with other methods,
magnetic flocculation is characterized by higher selectivity
and larger resistance against floc-rupturing forces. These
characteristics are important for the recovery of fine mag-
netic particles by magnetic flocculation separation (MFS),
because flocs in a magnetic separator must sustain strong
floc-rupturing forces from feeding flows and washing
water before leaving the magnetic fields. Moreover, selec-
tivity is important to produce qualified iron concentrate.
In this process, loose flocs are broken and dropped from
the separator in magnetic fields, and collected as tailings.
Table 1 Main chemical composition of IOT
Components Fe SiO2
Content (%) 23.51 28.6
Components K2O P S
Content (%) 1.21 0.05
a −1
The content unit was g ton
Reinforcing the selective aggregation of fine magnetic
minerals is important for their effective recovery in the
MFS processing.
In this study, the recovery of iron from IOT using
induced carbothermic reduction-MFS was conducted, and
the following reaction process was analyzed. The objec-
tives of this study are as follows: (1) investigate the effects
of sodium carbonate on the induced carbothermic reduc-
tion of iron minerals (clinochlore and hematite), including
reduction temperature, C/Ore mass ratio, and mass ratio of
Na2CO3 to ore; and (2) determine the possible application
of MFS to reinforce the recovery of fine iron minerals,
including the effects of grinding fineness and magnetic
separation methods. The proposed protocol and flow sheet
presented in this study will support the exploitation of
similar iron-containing waste.
Experimental
Materials
The IOTs used in this study were from Luoci dressing
plant, which is affiliated with Kunming Iron and Steel
Ltd., Yunnan, China. The main chemical composition of
IOT is provided in Table 1. The total iron content was
approximately 23.51%; however, the SiO2 content, which
is detrimental to iron recovery, was relatively high. The
contents of copper and silver reached 0.31% g ton−1 and
23.42 g ton−1, respectively, and were both recycled. Mean-
while, the content of hazardous lead was 0.54%, which was
subjected to the environmental pollution. The mineralogi-
cal analysis of the IOT was investigated by X-ray powder
diffraction (XRD). Figure 1 indicates that the iron ore
predominantly comprised clinochlore [(Mg, Fe, Al)6(Si,
Al)4O10(OH)2] and hematite (Fe2O3). The gangue mineral
was mainly quartz and dolomite. The pulverized coal was
used as the reductant with a particle size of < 1 mm. The
industrial and fusibility analyses results, as well as the
reactivity of pulverized coal, are listed in Tables 2 and 3,
respectively. The Na2CO3 used as the alkaline additive in
the experiments was of analytical reagent grade.
Al2O3 CaO MgO Na2O
5.92 13.4 7.63 1.08
Cu Pb Aga
0.21 0.31 0.54 23.42
 S.-J. Bai et
al.
Table 3 Reactivity of pulverized coal

Temperature (°C) 1000 1050 1100 1105 1200

α (%) 13.46 22.68 38.65 68.95 88.65

The reactivity of pulverized coal is the chemical reaction capability

between pulverized coal and carbon dioxide at certain temperatures.
α is the reduction degree of carbon dioxide

Fig. 1 XRD pattern of IOT

Experimental procedure

Original samples were thoroughly mixed with pulverized

coal and Na2CO3 according to specific proportions. The
mix- ture was put in a graphite crucible (ø 60 × 80 mm)
with a sealed cover, and then placed in the muffle furnace
preheated to the required temperature. Following the
completed reduc- tion roasting, the samples were taken out
from the furnace and cooled down to ambient temperature Fig. 2 Schematic of MFS column
with N2 protective atmosphere (1 L min−1).
The reduced ores were physically crushed to a diameter
of 10 mm to 20 mm in an iron pot and were then ground by the column to reach the magnetic fields. The sample was
ball milling (MM400, Retsch, Germany) at different times then stirred with at 150 r min−1 to remove entrainments
with the same vibration frequency of 900 min−1. Two dif- in the magnetic flocs. The iron concentrate was collected
ferent magnetic separation equipments were used for the through the concentrate outlet after demagnetization. The
magnetic separation of the reduced ore. The first equip- metallization ratio of reductive samples, MFS iron grade,
ment, an MFS column as shown in Fig. 2, was devised and and iron recovery were considered the main indexes for
produced by the researchers of this experiment. The main evaluating the test results. The secondary equipment, con-
technical parameters of the equipment include an inner ventional magnetic separation (CMS), was a wet drum-
cylinder diameter of 80 mm, a column height of 400 mm, type magnet separator (XCRS-14, Lei yun test instrument
Manufacturing Co., Ltd, Shanghai) with a magnetic field
a magnetic field intensity of 47.8 KA m−1, and a magnetic
field gradient of approximately 1.6 KA m−1 cm−1. Water intensity of 48.6 KA m−1. Each experiment was performed
was injected through the tangential flow inlet from the bot- in triplicate, and the mean was reported as the final value.
Standard deviations, which are presented as error bars,
tom of the column (tangential water flow was 1.5 L min −1),
were calculated from the triplicate measurements using
whereas the raw ore, with a separation concentration of
statistical computation and graphics software R v5.0.
30%, was fed through the feed pulp flow from the top of

Table 2 Industrial and ash

Industrial analysis (wt%) Ash fusibility (°C) S (wt%)
fusibility analyses of pulverized
coal Mad Ad Vd FCd DT ST HT MT

2.45 9.45 6.45 82.56 1250 1325 1344 1346 0.45

Mad, moisture (dry basis); Ad, ash (dry basis); Vd, volatile matter (dry basis); FCd, fixed carbon (dry basis)
DT, distortion temperature; ST, softening temperature; HT, hemispherical temperature; MT, melting tem-
perature
Novel method for iron recovery from hazardous iron ore tailing with induced
carbothermic…
Analysis and characterization
The reductive ores were divided into two portions: one
portion was crushed and milled to below 75 μm for XRD
analyses, and the other portion was used for microtopo-
graphic analysis. Fracture surfaces of reduced samples
were cut to a thin slice of double-sided polished samples
for the SEM–EDS analysis. The microtopographic
analyses were
conducted by the Kunming Institute of Precious Metals.
The XRD patterns of the raw material and the reductive
samples were acquired with a Rigaku diffractometer using
Cu Ka
radiation, and the scanning angle was varied from 10° to
90° (2θ) at a speed of 1.2° min−1. The microstructure of the
reduction product was observed with a scanning electron
microscope (FEI Holland, Philip).
Theoretical fundamental
Induced carbothermic reduction process
The reduction sequence of hematite can be described as
fol- lows: Fe2O3 → Fe3O4 → FeO → Fe (T > 570 °C). As
the reducing agent, the carbon in the coal played a key role
in the carbothermic reduction roasting. The main
reduction reactions in the carbothermic reduction, owing
to the lim- ited contact between the solid Fe 2O3 and the
solid carbon, as well as the easy diffusion of CO gases
from the carbon to the Fe2O3 surface, are the reactions
between the solid iron oxide and the CO gas. The effects of
CO and temperature on the products of the reduction
reactions are depicted in Fig. 3 (Yu and Qi 2011; Lei et al.
2017). The reduction of Fe2O3 to magnetite Fe3O4 is easy
due to the extremely low equilibrium concentration of CO
at any temperature. In addi- tion, increasing the
concentration of CO and temperature
can promote the Fe3O4 and FeO to a deep reduction,
thereby forming metallic iron. The metallic iron can be
easily recy- cled by magnetic separation; consequently, an
iron concen- tration with high iron content can be obtained.
The solid reactions among FeO, SiO2, and Al2O3 are
inev- itable during carbothermic reduction with high
concentra- tion of CO and temperature (Rath et al. 2016,
2017). The reaction theory can be expressed by the
following equations:
2FeO + SiO2 → Fe2SiO4 (1)
FeO + Al2O3 → FeAl2O4 (2)
The thermodynamic analysis of the ∆GΘ − t graphs of
FeO–Al 2O 3–SiO –Na
2 O2 system during the carbothermic
reduction process based on previous studies is shown in
Fig. 4 (Huang et al. 2005; Bai et al. 2016). The inevita-
ble solid reactions among FeO, SiO2, and Al2O3 are due to
their negative Gibbs free energy, which prevents the FeO
from undergoing a deep reduction into metallic iron to
form the fayalite (2FeO·SiO2) and hercynite (FeO·Al2O3).
These weakly magnetic minerals report in the tailings
during magnetic separation, thereby resulting in the loss
of iron recovery. In the addition of Na2CO3, however, the
Na2O that was formed through the dissociation of Na2CO3
can sup- press the formation of fayalite (2FeO·SiO2) and
hercynite (FeO·Al2O3). Moreover, Na2O can replace the
FeO in these minerals; it also increases the reduction
activity of FeO and promotes a considerable amount of
FeO to form metallic iron. The carbothermic reduction of
Fe2O3 to metallic iron can then be induced and reinforced
with the addition of Na2CO3. In addition, the results of
XRD data and chemical analysis indicated that dolomite
has considerable quantity in the IOT. The CaO and MgO
formed through the dissociation of dolomite will have a
similar positive influence with Na2O
 S.-J. Bai et
Fig. 3 Effects of CO and temperature on the products of the reduction al.
reactions Fig. 4 ∆GΘ − t graphs of FeO–Al2O3–SiO2–Na2O system

in the carbothermic reduction process. Although the con-

tent of SiO2 in the IOT is high, the addition of low-dosage Results and discussion
Na2CO3 may realize the induced carbothermic reduction of
iron oxide while considering the influence of dolomite. Characteristics of induced carbothermic reduction
Hence, temperature, amount of coal, and Na 2CO3 are the and MFS of reduced samples
key factors influencing the induced carbothermic reduction
process. Effect of reduction temperature

Magnetic flocculation separation Different reduction temperature experiments were studied

to investigate the optimum reduction temperature under the
In a magnetic separation system, the magnetic force (Fm) reduction duration of 120 min, C/Ore mass ratio of 20%,
on a mineral particle with increasing field intensity is mass ratio of Na2CO3 to ore of 6%, and a grinding fineness
expressed as follows (Luo et al. 2005): of reduced sample of 90.6% passing 74 μm. The effect of
reduction temperature on product quality and iron recovery
F =E V HH =3mHH (3) is shown in Fig. 6.
m pPi grad ppi grad Figure 6 shows that the increase in reduction temperatures
where Fm is the magnetic force on a particle, Ep is the volu- in the range of 900–1100 °C is beneficial for the increase
metric magnetic susceptibility, Vp is the volume of a in metallization ratio of reduced samples, iron concentrate,
particle, 3p is the specific magnetic susceptibility, mp is the
mass of a particle, Hi is the magnetic field intensity, and
Hgrad is the magnetic field gradient of the separator.
Equation (3) indicates that the magnetic force is increased
when the iron mineral fines are in the form of flocs during
the MFS pro- cess. The main force analysis of the
magnetic floc in the MFS column is presented in Fig. 5.
Magnetic force (Fm) and drag force (Fd) originate from
the stirring process in a horizontal direction, whereas
gravity (Fg) and convec- tive force (Fc) from tangential
water flow are in a vertical direction for the magnetic
floc, as shown in Fig. 5a. The magnitude and vertical
angle (θ) of the resultant force (Fr) on the magnetic floc
were determined by the resultant force vectors (F1) and
(F2) in the horizontal and vertical direction, respectively
(Fig. 5b). Undoubtedly, grinding fineness is a key factor
affecting the force (Fr) on the magnetic floc and the MFS
indexes. Fig. 6 Effect of reduction temperature on product qualities (metalli-
zation ratio and iron concentrate grade) and iron recovery
Novel method for iron recovery from hazardous iron ore tailing with induced
carbothermic…
Fig. 5 Main force analysis of magnetic floc in the MFS column
and iron recovery. This result can be attributed to the high
reactivity of pulverized coal at high temperatures, which
increases the ratio of CO/CO2 in the crucible. The quali-
ties of product and iron recovery tend to decrease with the
further increase of temperature up to 1250 °C. This is due
to the high reduction temperature urge of abundant low
melting point material formation, which hinders the
internal diffu- sion of gas reduction in the indirect
reduction process (Zhu et al. 2012). Hence, the reduction
temperature significantly influenced the present IOT
reduction, and high temperature was necessary for the
reduction of iron minerals to metallic iron. Furthermore,
the reduction temperature was fixed at 1100 °C in the
subsequent experimental series.
Effect of C/Ore mass ratio
The effect of C/Ore mass ratio on the reduction behavior of
IOT was examined by carbothermic reduction experiments.
The reduction experiments were performed at 1100 °C for
120 min with a mass ratio of Na 2CO3 to ore of 6%, and a
grinding fineness of approximately 90% passing 74 μm of
the reduced sample. The results are presented in Fig. 7.
The figure shows that the C/Ore mass ratio increased
from 5 to 25%, the iron metallization of reduced samples
increased from 10.84 to 32.03%, and the iron concentrate
grade and iron recovery of MFS increased from 48.12 to
64.52% and from 52.45 to 85.11%, respectively. The low
iron recovery and metallization at a low addition of coal
could be explained by the insufficient carbon and the
incom- plete reduction reaction. When the C/Ore mass
ratio was increased, the Boudouard reaction proceeded at a
rapid rate to provide the reductant CO, which then
increases the ratio of CO/CO2 and accelerates the reduction
process. Based on the results of Fig. 3, increasing the
concentration of CO can promote the deep reduction of
Fe3O4 and FeO to form the
metallic iron. Consequently, the iron concentrate grade and
iron recovery in the magnetic concentrate increased. There-
fore, the high mass ratio of C/Ore is necessary for the
reduc- tion of iron minerals to metallic iron, with the
recommended C/Ore mass ratio of 25%.
Effect of mass ratio of Na2CO3 to ore
Figure 8 shows the effect of Na2CO3 on the reduction
behav- ior of IOT. The reduction experiments were
performed at 1100 °C for 120 min with a C/Ore mass ratio
of 25%, and a grinding fineness approximately 90%
passing 74 μm of reduced sample.
Figure 8 shows that an increase in mass ratio of Na2O3
to ore from 0 to 10% causes a sharp increase in the
metalliza- tion ratio of reduced samples, iron concentrate
grade, and iron recovery. Specifically, the metallization
ratio of reduced samples increases from 18.84 to 33.58%,
and the iron con- centrate grade and iron recovery of MFS
can be improved by
7.33 and 24.38%, respectively. This finding can be
attributed to the formation of Na2O through the
dissociation of Na2CO3 and its participation in solid
reactions with quartz (SiO2), aluminum oxide (Al2O3),
fayalite (2FeO·SiO2), and hercyn- ite (FeO·Al2O3). As
shown in Fig. 4, the reduction activity of FeO increased,
and the reduction of iron minerals in the IOT was induced
and reinforced. From a practical viewpoint, the mass ratio
of Na2CO3 to ore of 8% is recommended.
Analysis of reduced sample
Phase transformation of iron minerals during induced
carbothermic reduction
In the induced carbothermic reduction experiments with
IOT, XRD was used to characterize the reduced samples

Fig. 7 Effect of C/Ore mass ratio on product qualities (metallization
ratio and iron concentrate grade) and iron recovery
(reduction at 1100 °C for 120 min with a C/Ore mass ratio
of 25%). As shown in Fig. 9a, the patterns indicated that
the iron phase was mainly ringwoodite [(Mg,Fe) 2SiO4] and
partly occurred as metallic iron in the reduced sample
with- out Na2CO3 addition. The diffraction peak of metallic
iron markedly increased with a corresponding decrease in
the diffraction peak of ringwoodite when a mass ratio of
Na2O3 to ore of 8% was added (Fig. 9b). Meanwhile, the
diffraction peak of the clinochlore and hematite in the
reduced samples disappeared, whereas the gangue
minerals in the reduced ores were mainly akermanite
(Ca2MgSi2O7) and quartz (SiO2). A new phase of
nepheline (NaAlSiO4) emerged with the addition of
Na2CO3 in the reduced sample. During the reduction
roasting, results indicated that not only the iron minerals in
the IOT were reduced to metallic iron without Na 2CO3
addition, but also solid reactions among FeO, SiO2, and
Al2O3 occurred. These solid reactions prevented FeO to
undergo deep reduction to metallic iron, which results in a
relatively low iron metallization. Conversely, the reduction
of iron minerals can be induced by adding Na 2CO3. More
FeO was reduced to metallic iron, and the iron
metallization was relatively high.
Metallic grain characteristics of reductive samples
The microstructures of the reductive samples (reduction
at 1100 °C for 120 min with a C/Ore mass ratio of 25%)
were studied using an optical microscope to characterize
the growing features of metallic iron grains during
reduction roasting, with results shown in Fig. 10.
Figure 10a, a-1 is the microstructure of the reductive
sample and the particle size distribution in the absence of
Na2CO3, respectively. Many brilliant metallic iron grains
can be observed in the reduced sample. However, the
metallic
S.-J. Bai et
al.
Fig. 8 Effect of mass ratio of Na2CO3 to ore on product qualities
(metallization ratio and iron concentrate grade) and iron recovery
iron grains with sizes of 0.88–15.01 μm and an average
par- ticle size (D0.5) of 2.35 μm have not been combined
and are still closely associated with gangue minerals.
Results show that growth and aggregation are difficult for
iron grains due to the high content of SiO2 and Al2O3,
which hinders the separation of the iron and gangue
phases. Thus, the recov- ery of iron by following milling-
magnetic separation is imperfect.
Figure 10b, b-1 shows the microstructure of the
reductive sample and the particle size distribution in the
presence of Na2CO3, respectively. Most of the metallic iron
grains in the reductive sample aggregate together and
evidently grow: the size of metallic iron grains reaches up
to 1.54–74.37 μm, and the average particle size (D0.5) is
6.19 μm. In addition, the borderline between metallic iron
grains and gangues becomes clear. Previous studies have
confirmed that sodium salts can enhance the reduction of
iron oxide and facilitate the growth of metallic iron grains
(Li et al. 2010c, 2013; Yu et al. 2013). In this work, the
role of Na2CO3 has simi- lar effects on the metallic iron
grain characteristics, and the addition of Na 2CO3 can
induce the carbothermic reduction of iron minerals in the
IOT.
Full-energy spectrum analysis was performed in the
regions marked in the SEM image to identify the phase
of the aggregated grains, as shown in Fig. 10. Results of
ternary composition distribution chart between Al, Si, and
Fe are shown in Fig. 11. As shown in Fig. 11a, the metallic
iron grains are small, and the Al–Si–Fe components are
embedded close to each other without Na2CO3 additive.
The phase rich in iron is also rich in Al and Si. When a
mass ratio of Na2O3 to ore of 8% was added (Fig. 11b), the
metallic iron grains became coarser and more aggregated
than the metallic iron grains in the reduced ore without
Na2CO3. Meanwhile, the ternary composition distribution
Novel method for iron recovery from hazardous iron ore tailing with induced
carbothermic…

Fig. 9 XRD patterns of samples reduced at 1100 °C for 120 min with a C/Ore mass ratio of 25% a No Na2CO3 addition; b Na2CO3 addition at a
mass ratio of Na2O3 to ore of 8%
Fig. 10 Microstructure of the reductive sample and particle size distribution chart (reduced at 1100 °C for 120 min with a C/Ore mass ratio of
25%): a and a-1 No Na2CO3 addition; b and b-1 Na2CO3 addition at a mass ratio of Na2O3 to ore of 8%

chart between Al Si, and Fe has a certain distinction—the

Magnetic separation of induced carbothermic
phase rich in iron was relatively deficient in Al and Si.
reduction samples
This observation indicated a high degree of metallization
and segregation of iron and gangue in the reduced sample.
Effect of grinding fineness
Results indicated that Na2CO3 enhanced the segregation of
iron and gangue during the carbothermic reduction. The
The magnetic separation of the reduced samples will be
liberation of a single iron phase from the slag is easy due
difficult due to their complex dissemination characteristics
to the presence of the Na2O formed from Na2CO3 in the
(reduction at 1100 °C for 120 min and addition of 25% C/
liquid phase, thereby aiding in the diffusion and aggrega-
Ore mass ratio and 8% Na 2O3/Ore mass ratio), so ultrafine
tion of metallic iron. However, the formed metallic iron
grinding was conducted first before MFS. The effect of
grains are still small; hence, ultrafine grinding is highly
grinding fineness on MFS indexes is shown in Fig. 12.
necessary for obtaining a qualified iron concentrate.
Fig. 11 Results of ternary composition distribution chart between Al, Si, and Fe: a No Na2CO3 addition; b Na2CO3 addition at a mass ratio of
Na2O3 to ore of 8%

Figure 12 shows that the iron concentrate grade

unfavorable effect on the iron recovery of MFS. Therefore,
increases from 63.12 to 78.54% and the iron recovery
the recommended grinding fineness is 87.4% below 38 μm.
decreases from 87.59 to 68.35% when the grinding fine-
ness is raised from 75.8% (74 μm) to 89.2% (26 μm). The
liberation of metallic iron grains and gangue minerals are
Effect of magnetic separation methods
known to be thorough with the increase in grinding
fineness, but the content of fine-grained magnetic miner-
The effect of magnetic separation methods on the indexes
als will increase during the ultrafine grinding process of
of the products was examined through MFS and CMS pro-
reduced ores. Figure 5 indicates that the magnitude and
cessing. The reduction ores were used for both magnetic
vertical angle of the resultant force (Fr) on the magnetic
separation processes, which were then reduced under the
floc decreased with the increase in grinding fineness. Con-
optimum carbothermic reduction conditions (reduction at
sequently, the fine-grained magnetic minerals will lose to
1100 °C for 120 min with a C/Ore mass ratio of 25% and a
the tailings, whereas extremely small fineness will show an
mass ratio of Na2CO3 to ore of 8%). Figure 13 shows that
an iron concentrate with 75.12% Fe can be obtained at an
iron recovery of 75.72% using CMS processing. Compared
with the indexes of the CMS product, the iron recovery
obtained by MFS processing increased by 4.19%, whereas
the iron concentrate grade only slightly changed. Thus, the
beneficiation of magnetic mineral fines can be real- ized by
MFS and CMS processing. Moreover, the recovery of the
magnetic mineral fines can be reinforced by MFS
processing, and this reinforced effect may be attributed to
the magnetic flocculation effects of the metallic iron on the
magnetic mineral fines. The apparent granularity of the
magnetic mineral fines increased when the magnetic
mineral fines flocculated; thus, a large magnetic force was
exerted on the magnetic mineral before leaving the mag-
netic fields, and the iron recovery was improved.
Fig. 12 Effect of grinding fineness on MFS indexes
Analysis of MFS product characteristics
XRD and chemical analyses were used to determine the
characteristics of the MFS products obtained under the
recommended separation conditions, with the results
shown in Fig. 14 and Table 4. The iron concentrate, which
can serve as raw material in iron production, was 73.86%
with low content of harmful impurities. The XRD patterns
indicated that the iron phase in the iron concentrate was
mainly metallic iron, with a few non-magnetic minerals
entrained (Fig. 14a). The phase in the MFS tailings was
mainly akermanite and a few metallic irons, as shown in
Fig. 14b. This phenomenon may be attributed to the inad-
equate liberation of metallic iron and its entrainments in
the gangues. The contents of valuable metals (Cu, Pb, and
Ag) in the MFS tailings have a significant enrichment, and
these valuable metals (Cu, Pb, and Ag) in the tailings
should be recycled in future research. By using several
simple methods, such as flotation or thermal treatment, the
prevention of environmental pollution of total process and
comprehensive utilization of IOT can be realized (Liu et al.
2013; Hoffmann et al. 2007; Lutandula and Maloba 2013).

Fig. 13 Effect of magnetic sepa-

ration methods on the indexes (a) 100 (b 100
of products: a iron grade, b iron MFS CMS ) MFS CMS
recovery 80

Iron recovery (%)

80
Iron grade (%)

60 60

40 40

20 20

0 0
Magnetic separation Magnetic separation methods
methods

Fig. 14 XRD pattern of magnetic flocculation products: a iron concentrate; b tailing

Table 4 Typical chemical Products C omponents (wt

compositions of MFS products
%) Al2O3 CaO P S Cu Pb Aga
TFe SiO2
Iron concentrate 73.86 5.35 1.25 1.75 0.01 0.12 0.03 0.12 12.45
Tailing 9.14 46.70 10.96 17.4 0.11 0.31 0.46 0.69 29.67
a
The content unit was g ton−1
Discussion
In this technology, the iron minerals (clinochlore and
hema- tite) in the IOT were reduced to metallic iron by
induced carbothermic reduction with Na2CO3 addition.
During the reduction process, the metallic iron grains grow
and aggre- gate, thereby facilitating the easy recovery of
iron through the low-intensity magnetic separation
method. After ultrafine grinding–MFS processing, the
iron concentrate with high iron content and low content of
harmful impuri- ties was obtained. Clinochlore and
hematite have become important iron components in
available IOT. However, deep reduction with high contents
of SiO2 and Al2O3 is difficult, thus having strict reduction
conditions. Therefore, literature on the carbothermic
reduction method to recycle iron from IOT is limited.
Technologies for iron recovery from tailings have
already been studied in the laboratory, but their industrial
applica- tion is limited due to high production cost.
Specifically, the content of iron in the IOT is very low and
contains a few harmful metals, both of which present major
difficulties for recycling iron from IOT. Moreover, the
residues after iron recovery are massive, thereby leading to
storage problems and secondary pollution. Research on
recycling valuable metals and producing value-added
products from magnetic separation tailings should be
conducted to comprehensively utilize IOT. Thus, if iron
will be recycled in the process of recycling valuable metals
and use IOT to prepare cementi- tious material, then a
good future in the industrial applica- tion may be expected.
Conclusions
In this paper, a novel method to recover iron from IOT was
studied with induced carbothermic reduction followed by
MFS and CMS. Major chemical compositions of IOT were
SiO2, Fe, CaO, and Al2O3. Clinochlore, hematite, quartz,
and dolomite existed in IOT as the main phases. The
theoret- ical fundamental principle of induced
carbothermic reduc- tion indicated that increasing the
concentration of CO and temperature, as well as adding
Na2CO3, promoted a deep reduction of Fe3O4 and FeO to
form the metallic iron. The main force analysis of the
magnetic floc in the MFS column indicated that the
magnetic force increases when the iron mineral fines form
in the flocs during the MFS process and that grinding
fineness is an important factor affecting the force (Fr) on
the magnetic floc and the MFS indexes.
Through several groups of experiments, optimum car-
bothermic reduction conditions were as follows: reduc-
tion at 1100 °C for 120 min, addition of 25% C/Ore mass
ratio, and 8% mass ratio of Na 2CO3 to ore. Under the opti-
mum reduction conditions, iron minerals in the IOT were
transformed to metallic iron, the reduction activity of FeO
was increased, and a deep reduction from FeO to metallic
iron was observed with the addition of Na2CO3. The
metalli- zation mean of induced reduction ores also
reached 32.53%. When the reduced samples were ground
to 87.4% below 38 μm, the MFS concentrate grade was
74.02% Fe, and the recovery rate was 79.51%. This iron
recovery increased by 4.19% compared with that of
CMS, whereas the iron concentrate grade slightly
changed. Research on recycling valuable metals and
producing value-added products from magnetic separation
tailings should be conducted in future works to
comprehensively utilize IOT. Thus, if we stand on the
innovative idea that recycling iron in the process of
recycling valuable metals and using IOT to prepare
cementi- tious material, then such stand may lead to a good
future in the industrial application.
Acknowledgements This research project was supported by the
finan- cial support from Regions of the National Natural Science
Foundation of China (Grant No. 51664027) and National Science
Foundation for Young Scientists of China (Grant No. 51404118), and
the authors are grateful to the Kunming Institute of Precious Metals
for its technical support.
References
Bai SJ, Wen SM, Liu DW, Zhang WB, Cao QB (2012) Beneficiation
of high phosphorus limonite ore by sodium-carbonate-added car-
bothermic reduction. ISIJ Int 52:1757–1763
Bai SJ, Wu M, Lv C, Wen SM (2016) Microstructure characteristic
and phase evolution of refractory siderite ore during sodium-
carbonate-added catalyzing carbothermic reduction. J Iron Steel
Res Int 23:891–899
Cheng YH, Huang F, Li WC, Liu R, Li GL, Wei JM (2016) Test
research on the effects of mechanochemically activated iron tail-
ings on the compressive strength of concrete. Constr Build
Mater 118:164–170
Das SK, Kumar S, Ramachandrarao P (2000) Exploitation of iron
ore tailing for the development of ceramic tiles. Waste Manage
20:725–729
Han JW, Liu W, Qin WQ, Peng B, Yang K, Zheng YX (2015)
Recovery of zinc and iron from high iron-bearing zinc calcine by
selective reduction roasting. J Ind Eng Chem 22:272–279
Hoffmann G, Schirmer M, Bilitewski B, Kaszas Savos M (2007)
Ther- mal treatment of harzardous waste for heavy metal
recovery. J Hazard Mater 145:351–357
Huang ZC, Cai LB, Zhang YB, Yang YB, Jiang T (2005) Reduction
of iron oxides of red mud reinforced by Na2CO3 and CaF2. J
Cent South Univ Sci Technol 41:838–884 (in Chinese)
Kim KK, Kim KW, Kim JY, Kim IS, Cheong YW, Min JS (2001)
Characteristics of tailings from the closed metal mines as
potential contamination source in South Korea. Environ Geol
41:358–364
Lei C, Yan B, Chen T, Xiao XM (2017) Recovery of metals from the
roasted lead-zinc tailings by magnetizing roasting followed by
magnetic separation. J Clean Prod 158:73–80
Li C, Sun HH, Bai J, Li LT (2010a) Innovative methodology for com-
prehensive utilization of iron ore tailings part 1: the recovery of
iron from iron ore tailings using magnetic separation after
magnet- izing roasting. J Hazard Mater 174:71–77
Li C, Sun HH, Yi ZL, Li LT (2010b) Innovative methodology for
com- prehensive utilization of iron ore tailings part 2: the
residues after iron recovery from iron ore tailings to prepare
cementitious mate- rial. J Hazard Mater 174:78–83
Li GH, Xie CM, Zhang YB, Li Q, Jiang T (2010c) Influence of addi-
tives on dephosphorization of oolitic hematite by direct reduc-
tion process. In: 1st International symposium on high-
temperature metallurgical processing. Wiley Online Library, pp
505–513
Li GH, Zhang SH, Rao MJ, Zhang YB, Jiang T (2013) Effects of
sodium salts on reduction roasting and Fe–P separation of high-
phosphorus oolitic hematite ore. Int J Miner Process 124:26–34
Liu YS, Du F, Yuan L, Zeng H, Kong SF (2010) Production of light-
weight ceramisite from iron ore tailings and its performance
investigation in a biological aerated filter (BAF) reactor. J
Hazard Mater 178:999–1006
Liu J, Wen SM, Chen Y, Liu D, Bai SJ, Wu DD (2013) Process opti-
mization and reaction mechanism of removing copper from an
fe-rich pyrite cinder using chlorination roasting. J Iron Steel Res
Int 20:20–26
Luo LQ, Nguyen AV (2017) A review of principles and applications
of magnetic flocculation to separate ultrafine magnetic particles.
Sep Purif Technol 172:85–99
Luo LQ, Zhang JS, Yu YF (2005) Recovering limonite from
Australia iron ores by flocculation-high intensity magnetic
separation. J Cent South Univ Sci Technol 12:682–687
Lutandula MS, Maloba B (2013) Recovery of cobalt and copper
through reprocessing of tailings from flotation of oxidised ores.
J Environ Chem Eng 1:1085–1090
Ma BG, Cai LX, Li XG, Jian SW (2016) Utilization of iron tailings as
substitute in autoclaved aerated concrete: physico-mechanical and
microstructure of hydration products. J Clean Prod 127:162–171
Ozkan A (2003) Coagulation and flocculation characteristics of talc
by different flocculants in the presence of cations. Miner Eng
16:59–61
Rao KH, Narasimhan KS (1985) Selective flocculation applied to
Bar- suan iron ore tailings. Int J Miner Process 14:67–75
Rath SS, Rao DS, Mishra BK (2016) A novel approach for reduction
roasting of iron ore slime using cow dung. Int J Miner Process
157:216–226
Rath SS, Rao DS, Tripathy A, Biswal SK (2017) Biomass briquette
as an alternative reductant for low grade iron ore resources. Bio-
mass Bioenergy. https://doi.org/10.1016/j.biombioe.2017.10.045
(in press)
Shettima AU, Hussin MW, Ahmad Y, Mirza J (2016) Evaluation of
iron ore tailings as replacement for fine aggregate in concrete.
Constr Build Mater 120:72–79
Shibata J, Fuerstenau DW (2003) Flocculation and flotation charac-
teristics of fine hematite with sodium oleate. Int J Miner Process
72:25–32
Singh S, Sahoo H, Rath SS, Sahu AK, Das B (2015) Recovery of iron
minerals from Indian iron ore slimes using colloidal magnetic
coating. Powder Technol 269:38–45
Sirkeci AA, Gul A, Bulut G, Arslan F, Onal G, Yuce AE (2006)
Recov- ery of Co, Ni, and Cu from the tailings of Divrigi iron
ore concen- trator. Miner Process Extr Metall Rev 27:131–141
Suthers SP, Nunna V, Tripathi A, Douglas J, Hapugoda S (2014)
Experimental study on the beneficiation of low-grade iron ore
fines using hydrocyclone desliming, reduction roasting and mag-
netic separation. Miner Process Extr Metall 123:212–227
Wang L, Li J, Li BW, Wang J (2011) Extraction of niobium from the
Bayan obo tailings by “flotation-microwave magnetic roasting-
magnetic separation”. Adv Manuf Technol 314–316(1–3):823–828
Wang C, Harbottle D, Liu QX, Xu ZH (2014) Current state of fine
mineral tailings treatment: a critical review on theory and practice.
Miner Eng 58:113–131
Yang CM, Cui C, Qin J (2015) Recycling of low-silicon iron tail-
ings in the production of lightweight aggregates. Ceram Int
41:1213–1221
Yu Y, Qi C (2011) Magnetizing roasting mechanism and effective ore
dressing process for oolitic hematite ore. J Wuhan Univ Technol
Sci Ed 26:176–181
Yu W, Sun TC, Kou J, Wei YX, Xu CY, Liu ZZ (2013) The function
of Ca(OH)2 and Na2CO3 as additive on the reduction of high-
phos- phorus oolitic hematite-coal mixed pellets. ISIJ Int
53:427–433
Zahrim AY, Tizaoui C, Hilal N (2010) Evaluation of several commer-
cial synthetic polymers as flocculant aids for removal of highly
concentrated CI Acid Black 210 dye. J Hazard Mater 182:624–630
Zhang S, Xue X, Liu X, Duan P, Yang H, Jiang T, Wang D, Liu R
(2006) Current situation and comprehensive utilization of iron
ore tailing resources. J Min Sci 42:403–408
Zhu DQ, Cui Y, Vining K, Hapugoda S, Douglas J, Pan J, Zheng GL
(2012) Upgrading low nickel content laterite ores using selective
reduction followed by magnetic separation. Int J Miner Process
106:1–7