applied
sciences
Article
Pyrometallurgical Technology for Extracting Iron and Zinc from
Electric Arc Furnace Dust
Nina V. Nemchinova 1, * , Alexey E. Patrushov 2 and Andrey A. Tyutrin 1
Citation: Nemchinova, N.V.;
Patrushov, A.E.; Tyutrin, A.A.
Pyrometallurgical Technology for
Extracting Iron and Zinc from
Electric Arc Furnace Dust. Appl. Sci.
2023, 13, 6204. https://doi.org/
10.3390/app13106204
Academic Editor: Cem Selcuk
Received: 19 April 2023
Revised: 8 May 2023
Accepted: 16 May 2023
Published: 18 May 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Appl. Sci. 2023, 13, 6204. https://doi.org/10.3390/app13106204
1 Department of Non-Ferrous Metals Metallurgy, Irkutsk National Research Technical University,
664074 Irkutsk, Russia; an.tu@inbox.ru
2 LLC ITEM Engineering, 664075 Irkutsk, Russia; apatrushov@38.mtrci.ru
* Correspondence: ninavn@yandex.ru
Abstract: This study is aimed at developing a technology for processing electric arc furnace dust
(EAFD) into granulated cast iron and a zinc-containing product. The study object was the dust
from the EAF of PJSC Magnitogorsk Iron and Steel Works (Magnitogorsk, Chelyabinsk region).
It has been established that the dust contains valuable components in the form of ZnFe2 O4 and
ZnO. The processing of EAFD involves the reduction of Fe and Zn in a charge from their oxygen-
containing forms with C and CO. The content of the charge components was calculated in % as follows:
EAFD—17.44; scale—51.33; hard coal—20.61; quartz sand—4.71; lime—5.91. The experiments in
the high-temperature LHT 08/17 furnace (Germany) allowed for defining the optimal temperature
regime for reduction melting. As a result of laboratory tests, granulated pig iron samples were
obtained, containing in wt%: Fe—95.27; C—4.4; S—0.07, and others. Captured zinc-containing
product after calcination (to remove halogens) contained 90.21 wt% ZnO. The resulting granulated
pig iron is recommended as one of the charge components in electrometallurgical steel production.
The zinc-containing product is recommended as a raw material for Zn production and others.
Keywords: electric arc furnace dust; flux; reduction; pig iron; distillation; zinc sublimates; zinc oxide
1. Introduction
Steel production occupies a leading position in the metallurgical sector worldwide [1–5].
The rapid growth of steel production on a global scale over the past 20–30 years has
attracted the attention of experts to the increasingly harmful environmental impact of
ferrous metallurgy enterprises [6–8], including the generation of hard-to-recycle human-
made waste [9–12].
Researchers and manufacturers are engaged in the recycling of metallurgical waste in
accordance with waste management laws adopted in their countries [5,6,13,14]. In Russia,
the development of domestic technology and organization of iron-containing waste recy-
cling into a product with 100% metallization and Fe content > 96% comprises an important
R&D direction in the field of ferrous metallurgy, recommended for implementation in the
period up to 2030 [15].
Despite the growing cost of the storage of this raw material at landfills and slag fields,
the multi-million-ton dumps from the ferrous metallurgy production activity (oily scale,
gas-cleaning dust, sludge, slag) are continuously increasing [16–18]. Such hard-to-enrich
and low-grade materials include electric arc furnace dust, which can be not only an iron-
containing raw material for iron and steel production but allows for extracting zinc into a
commercial product since the dust contains zinc compounds in sufficient quantities [19–21].
The growing global demand for steel and zinc makes scale processing and EAFD a very
urgent problem. In this regard, developing technologies for processing EAFD to extract
valuable components (in particular, Fe and Zn) while obtaining commercial products is
relevant [12,18,22–25].
https://www.mdpi.com/journal/applsci
 extract valuable components (in particular, Fe and Zn) while obtaining commercial p
ucts is relevant [12,18,22–25].
This study is aimed at developing a technology for processing electric arc fur
Appl. Sci. 2023, 13, 6204 dust into granulated cast iron and a zinc-containing product. 2 of 12

2. Research Objective
This study is aimed at developing a technology for processing electric arc furnace dust
In Russia, more than 70 million tons of steel are produced annually, of which 22
into granulated cast iron and a zinc-containing product.
lion tons are in the electrothermal process. The main enterprises manufacturing steel e
trothermally
2. are vertically integrated companies with a total share of about 90% in R
Research Objective
sian Insteel production:
Russia, more than 70 EvrazHolding
million tons ofLLC, Severstal
steel are produced PJSC, Magnitogorsk
annually, Iron and S
of which 22 mil-
lion tons are in the electrothermal process. The main enterprises
Works PJSC, Novolipetsk Iron and Steel Works PJSC, Mechel PJSC, MC Metalloin manufacturing steel
electrothermally are vertically Company
LLC, United Metallurgical integrated companies with Metallurgical
JSC, and Pipe a total share of Company
about 90% in PJSC [26
Russian steel production: EvrazHolding LLC, Severstal PJSC, Magnitogorsk Iron and Steel
Arc furnace enterprises generate about 650 thousand tons of technogenic dust
Works PJSC, Novolipetsk Iron and Steel Works PJSC, Mechel PJSC, MC Metalloinvest LLC,
year, which
United is not currently
Metallurgical Company JSC,processed
and Pipe but almost completely
Metallurgical Company dumped.
PJSC [26]. Such dust cont
zincArcwithin 2–20%;
furnace in some
enterprises types
generate of dust,
about the zinc
650 thousand content
tons is up todust
of technogenic 30–35%. This tech
per year,
genic is
which raw
not material also contains
currently processed a significant
but almost completelyamount
dumped. of Such
iron dust
oxides (30–60%)
contains zinc and u
within
20% of2–20%;
oxidesinof some types
other of dust,(silicon,
elements the zinc content
calcium,is up to 30–35%. This technogenic
magnesium).
raw material
The study also contains
object wasa significant amount of iron oxides
the iron–zinc-containing (30–60%)
dust from andthe up
EAF to 20% of Magn
of PJSC
oxides of other elements (silicon, calcium, magnesium).
gorsk Iron and Steel Works (Magnitogorsk, Chelyabinsk region). It was studied usin
The study object was the iron–zinc-containing dust from the EAF of PJSC Magnito-
ser diffraction,
gorsk Iron and Steelelectron
Worksprobe microanalysis
(Magnitogorsk, (EPMA),
Chelyabinsk X-rayItphase
region). and fluorescence
was studied using (X
analysis
laser techniques,
diffraction, electronand scanning
probe electron
microanalysis microscopy
(EPMA), X-ray phase (SEM).
and fluorescence (XRF)
According
analysis techniques, toand
thescanning
study, EAFD
electronis a red-brown
microscopy (SEM). powder with a particle size of <
mm,According
determined to theonstudy, EAFD
a laser is a red-brown
particle powder
size analyzer with a particle
Analysette size of <0.06 mm,
22 NanoTecPlus (Fritsch, I
determined on a laser particle size
Oberstein, Germany); see Figure 1, Table 1. analyzer Analysette 22 NanoTecPlus (Fritsch, Idar-
Oberstein, Germany); see Figure 1, Table 1.

Figure1.1.Particle
Figure Particlesize distribution
size of an of
distribution EAFD samplesample
an EAFD [27]. [27].
Table 1. The EAFD sample particle size distribution.
Table 1. The EAFD sample particle size distribution.
Size, µm Output, %
Size,
1
μm 4.8
Output, %
2 1 4.8 4.8
5 2 4.8 4.8
8 4.8
10 5 5.3 4.8
15 8 15.1 4.8
20 37.9
30 10 80.1 5.3
38 15 95.3 15.1
45 99
20 37.9
71 100
30 80.1
38 95.3
13, x FOR PEER REVIEW 3 of 12
Appl. Sci. 2023, 13, x FOR PEER REVIEW 3 of 12

Appl. Sci. 2023, 13, 6204 45 99 3 of 12

45 99
71 71 100 100

Chemical analysis of the samples

Chemical
Chemical analysiswas
analysis of performed
of the
the samples
sampleswas onperformed
was an X-ray wavelength-dispersive
performed ononanan
X-ray wavelength-dispersive
X-ray wavelength-dispersive
spectrometer
spectrometer S8 spectrometer
TIGER S8 TIGER (Bruker, Billerica, MA, USA); the results areare
(Bruker,S8 TIGER
Billerica,(Bruker,
MA, Billerica,
USA); the MA,
resultsUSA);
are the
given results
in Table 2.given
given in in
Dust Table
Table 2.
2. Dust
samples were alsoDust samples
studied were
by also also
scanning studied
electron by scanning
microscopy electron microscopy (SEM) on an X-ray
samples were studied by scanning electron(SEM) on an X-ray
microscopy (SEM) diffrac-
on an X-ray diffrac-
diffractometer XRD-7000 (Shimadzu, Kyoto, Japan), Figure 2.
tometer XRD-7000 (Shimadzu, Kyoto, Japan), Figure 2.
tometer XRD-7000 (Shimadzu, Kyoto, Japan), Figure 2.
Table 2. Chemical composition of an EAFD sample.
Table 2. Chemical Table
composition of ancomposition
2. Chemical EAFD sample.
of an EAFD sample.
Components
Components Components
ZnO Fe2 O3 Na2 O K2 O CaO Cl P2 O5 SO3 SiO2 Al2 O3 MgO MnO PbO
ZnO Fe2O3 Na2ZnO
O K2O Fe2OCaO
3 Na2OClK2OP2O CaO
5 SO3ClSiOP 2 2OAl
5 SO
2O33 SiO
MgO2 Al2MnO
O3 MgO PbO MnO PbO
Content, wt%
Content, wt% Content, wt%
26.02 37.7 5.975 2.98 10.43 3.755 0.34 1.04 4.79 0.66 1.31 2.885 2.11
26.02
26.02 37.7 5.975 2.9837.710.43
5.975 2.980.34
3.755 10.43 3.755
1.04 4.790.34 0.66
1.04 4.79
1.31 0.66 2.885 1.312.11 2.885 2.11

(a) (b)
(a) (b)
Figure 2. Electronic image of an EAFD sample: (а) magnification ×500; (b) magnification ××2000.
Figure 2. ElectronicFigure
image2.ofElectronic
an EAFDimage
sample:
of an(а) magnification
EAFD sample: (a)×500; (b) magnification
magnification ××2000.
×500; (b) magnification ×2000.
The iron distribution throughout iron-containing phases in EAFD samples was stud-
ied byThe
The iron distribution iron
X-ray distribution
throughout
phase throughout
iron-containing
analysis iron-containing
on a DRON-3.0phases phasessamples
in EAFD
diffractometer in EAFD
(JSC samples
was stud-
ʺScientific was studieden-
production
ied by X-ray phase by X-ray phase
analysis
terprise analysis
on a DRON-3.0
ʺBurevestnikʺ, on a DRON-3.0 diffractometer
diffractometer
Saint Petersburg, (JSC Scientific
(JSCItʺScientific
Russia). production
productionthat
has been established enterprise
en-the dust con-
“Burevestnik”, Saint Petersburg, Russia). It has been established that the
tains valuable
terprise ʺBurevestnikʺ, components
Saint Petersburg, in the form
Russia). It hasofbeen
ZnFeestablished
2O4 and ZnO (Figure
that con- contains
dust
3) [27].
the dust
valuable components in the form of ZnFe2 O4 and ZnO (Figure 3) [27].
tains valuable components in the form of ZnFe2O4 and ZnO (Figure 3) [27].

Figure 3. X-ray diffraction diagram of the EAFD sample.

Appl. Sci. 2023, 13, 6204 4 of 12

3. Theoretical Background for the Pyrometallurgical Processing of EAFD

The pyrometallurgical processing of EAFD involves the reduction of iron and zinc in
a charge from their oxygen-containing forms with active reagents (C and CO) to obtain
granulated pig iron and a zinc-containing product [28].
The reduction of metal oxides with carbon monoxide is based on the reversible reaction:

MeO + CO  Me + CO2 . (1)

Reaction (1) proceeds to the right when the Gibbs energy decreases during the transi-
tion from the initial state to equilibrium.
The diagram of the temperature dependence of the equilibrium concentrations of CO
mixed with CO2 for the reduction of metal oxides with carbon monoxide shows that a gas
containing CO ≥ 50% at 600 ◦ C is a reducing agent for FeO and an oxidizing one for ZnO,
i.e., an excess of carbon is required to initiate reducing ZnO:

C + CO2 = 2CO. (2)

Increasing the temperature shifts the CO formation equilibrium towards an increase in

the CO content in the gas mixture, according to Le Chatelier’s principle, since this reaction
proceeds with heat absorption.
Zinc oxide is reduced by carbon monoxide according to the reaction:

ZnO + CO = Zn↑ + CO2 . (3)

Zinc starts reducing from its oxide at ~1000 ◦ C. The Zn reduction rate is a function of
carbon dioxide deoxidation where CO is continuously regenerated.
Based on Baikov’s principle of the sequence of transformations, iron reduces from
oxides gradually from higher oxides to lower ones according to the scheme: Fe2 O3 →Fe3 O4
→FeO→Fe.
CO acts as a reducing agent during metallization in a rotary hearth furnace:

3Fe2 O3 + CO = 2Fe3 O4 + CO2 , (4)

Fe3 O4 + CO = 3FeO + CO2 , (5)

FeO + CO = Fe + CO2 . (6)

Along with the aforementioned reactions, metallic iron is carburized in the system,
leading to the formation of iron carbide [29]:

3Fe + C = Fe3 C. (7)

Carburized iron has a lower melting point compared to pure iron. Thus, if pure iron
has a melting point of 1539 ◦ C, then with a carbon content of 2 and 4%, this temperature
decreases to 1380 and 1170 ◦ C, respectively. Melting transforms carburized iron into a
liquid state, and due to cohesive forces, small particles combine into larger ones, forming
drops of molten iron. The cohesion of reduced iron proceeds under conditions when the
slag-forming components of the charge are in a solid state due to their refractoriness.
The resulting slag melting temperature should be within 1300–1380 ◦ C. The slag
composition is defined based on the CaO-MgO-SiO2 system [30]; in this temperature range,
melting occurs in the pseudo-wollastonite region.
In the molten state, metal and slag are immiscible liquids that separate into indepen-
dent phases due to the difference in densities and have an interface with different surface
energies (interfacial tension). Upon cooling, the melt crystallizes while forming pig iron
and slag. In general, the granulated pig iron production stages are shown in Figure 4.
Appl. Sci. 2023, 13, x FOR PEER REVIEW 5 of 12
Appl. Sci. 2023, 13, 6204 5 of 12

Figure 4. Granulated pig iron production stages.

Figure 4. Granulated pig iron production stages.
EAFD contains 25.8% iron; however, to obtain granulated pig iron, the iron content
in the raw material
EAFD containsshould
25.8%be at least
iron; 50% (according
however, to obtaintogranulated
preliminarypig laboratory
iron, thestudies).
iron content
Therefore, a raw material with a high iron content should be added to EAFD to obtain an
in the raw material should be at least 50% (according to preliminary laboratory studies).
iron–zinc-containing feedstock meeting this requirement. Another technogenic material,
Therefore, a raw material with a high iron content should be added to EAFD to obtain an
an oily scale from Magnitogorsk Iron and Steel Works PJSC, was chosen as such raw
iron–zinc-containing
material for additionalfeedstock
charging. meeting
Oily scalethis
is anrequirement.
iron oxidationAnother
product,technogenic
mainly formed material,
aninoily scale
rolling andfrom Magnitogorsk
pipe-rolling Ironduring
industries and Steelthe Works PJSC, was
heat treatment chosenThe
of metal. as such raw ma-
scale’s
terial for additional charging. Oily scale is an iron oxidation product,
chemical composition mainly depends on the heat treatment conditions and the chemical mainly formed in
rolling and pipe-rolling
composition of the metal,industries during
and its amount thethickness)
(film heat treatment
dependsof metal. The scale’s
on the heat chemical
treatment
conditions [31].
composition The studied
mainly depends scale
on contains
the heatabout 13% of
treatment oil, which and
conditions should
thebechemical
removedcomposi-
to
use this scale as an iron-containing charge component. The scale is de-oiled by
tion of the metal, and its amount (film thickness) depends on the heat treatment conditions calcination,
and according to the results of structural and spectral analyzes, after removing the oil, the
[31]. The studied scale contains about 13% of oil, which should be removed to use this
scale contains 73.39% Fe2 O3 and 15.73% FeO (Table 3), which corresponds to a total iron
scale as an iron-containing charge component. The scale is de-oiled by calcination, and
content of 63.64%.
according to the results of structural and spectral analyzes, after removing the oil, the scale
Table 3. The
contains chemical
73.39% Fe2O composition of scale.
3 and 15.73% FeO (Table 3), which corresponds to a total iron content

of 63.64%.
Components
Fe2 O3 FeO SiO2 MgO MnO
Table 3. TheCu Ni
chemical S
compositionCr P 2 O5
of scale. K2 O TiO2 Zn C CaO Al2 O3
Content, wt%
73.39 15.73 4.55 0.26 0.94 0.44 0.39 0.2
Components
0.18 0.13
0.02 0.02 0.02 1.6 1.58 0.55
Fe2O3 FeO SiO2 MgO MnO Cu Ni S Cr P2O5 K2O TiO2 Zn С CaO Аl2О3
Content, wt%should be used as a carbonaceous
Raw material with the following specifications
73.39 15.73
reducing 4.55low0.26
agent: 0.94sulfur
ash and 0.44contents
0.39 0.2
and0.18
high0.13 0.02 ability.
reducing 0.02 0.02 1.6 a 1.58
As such raw 0.55
material, we chose hard coal of the long-flame little nut (DOM) brand; Table 4 shows the
chemical composition
Raw material withof the
this following
coal on a dry basis.
specifications should be used as a carbonaceous re-
The amount of carbonaceous reducing agent in the
ducing agent: low ash and sulfur contents and high reducing charge was calculated
ability. according
As such a raw mate-
to the reduction of iron and zinc from their oxides with an up to 10% excess from the
rial, we chose hard coal of the long-flame little nut (DOM) brand; Table 4 shows the chem-
stoichiometric point.
ical composition of this coal on a dry basis.

Table 4. The chemical composition of DOM coal.

Components
A ,%* C
d H O N S SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O TiO2
Content, wt% Content in ash, wt%
10.51 63.99 4.38 20.05 0.80 0.27 53.5 12.3 7.2 21.4 4.1 0.5 0.4 0.6
Appl. Sci. 2023, 13, 6204 6 of 12

Table 4. The chemical composition of DOM coal.

Components
Ad , % * C H O N S SiO2 Al2 O3 Fe2 O3 CaO MgO K2 O Na2 O TiO2
Content, wt% Content in ash, wt%
10.51 63.99 4.38 20.05 0.80 0.27 53.5 12.3 7.2 21.4 4.1 0.5 0.4 0.6
* Ad —ash content.

The required amount of hard coal with a C content of 63.99% will be:

12.85 × 100/63.99 = 20.08 g

The SiO2 and CaO sources used as slag-generating components are quartz sand [32]
and lime [33]; see Table 5.

Table 5. The chemical composition of fluxes.

Components
Material SiO2 CaO Al2 O3 Fe2 O3 MgO SO3 MnO TiO2 H2 O
Content, wt%
Quartz sand 97.60 0.36 0.10 0.12 0.15 - 0.07 0.05 1.55
Lime 0.4 90.80 1.42 1.50 5.68 0.20 - - -

Hard coal of the long-flame little nut brand is recommended for use as a carbonaceous
reducing agent. The number of fluxes (SiO2 , CaO) added to the charge was calculated
considering the presence of these components in iron–zinc-containing raw materials and
reducing agent to generate slag with a melting point of 1300–1380 ◦ C (based on the afore-
mentioned system CaO-MgO-SiO2 ).
Thus, calculations showed the content of components in the charge as follows, in %:
EAFD—17.44; scale—51.33; DOM coal—20.61; quartz sand—4.71; lime—5.91.

4. Experimental EAFD Processing

The pelletized charge was used for melting in laboratory experiments. The mill scale
was de-oiled in a muffle furnace in a nitrogen environment without access to oxygen,
thereby avoiding the ignition of the organic fraction. The test charge components were
carefully homogenized in a porcelain mortar; water was then added to the resulting
homogeneous mix to form a paste-like mass, and spherical granules 10–25 mm in diameter
were manually formed. Carboxyl methylcellulose was used as a binder.
Wet granules were dried for 30 min at 200 ◦ C in an EKPS 10 laboratory muffle electric
furnace (SKTB, Smolensk, Russia). The pelletized charge underwent reduction melting on
a laboratory unit based on a high-temperature LHT 08/17 furnace (Nabertherm, Lilienthal,
Germany) equipped with a water-cooled gas flue with the forced removal of gaseous
products; see Figure 5.
The sublimation products formed in the reduction melting were captured using a dust
collecting system. Gaseous melting products were discharged through a pipe from the
upper part of the furnace’s working chamber by induced draft. The sublimed products
entered the water-cooled gas flue, where the gas stream cooling, condensation, and partial
precipitation of sublimates took place. Dust residues were captured by passing the dust-gas
flow through a water filter (a flask with water).
 were manually formed. Carboxyl methylcellulose was used as a binder.
Wet granules were dried for 30 min at 200 °C in an EKPS 10 laboratory muffle electric
furnace (SKTB, Smolensk, Russia). The pelletized charge underwent reduction melting on
a laboratory unit based on a high-temperature LHT 08/17 furnace (Nabertherm, Lilienthal,
Appl. Sci. 2023, 13, 6204 Germany) equipped with a water-cooled gas flue with the forced removal7 of of12gaseous
products; see Figure 5.

Figure 5. Laboratory EAFD processing unit: 1—crucible with charge; 2—furnace; 3—flue; 4—water-
Figure 5. Laboratory EAFD processing unit: 1—crucible with charge; 2—furnace; 3—flue; 4—water-
cooled jacket; 5—water trap for dust; 6—vacuum pump.
cooled jacket; 5—water trap for dust; 6—vacuum pump.
To reproduce the reduction conditions in an industrial rotary hearth furnace, the
experiments were performed in the following sequence:
• 20–30 g of hard coal with a particle size of 3.0–4.0 mm was placed in a ~55 mL
corundum crucible;
• The prepared pelletized charge was placed on the bedding in the crucible;
• A water-cooled refrigeration chamber with the forced removal of gaseous reaction
products was mounted at the furnace’s off-gas outlet;
• The crucible with bedding and the pelletized charge was placed in a furnace heated to
1150 ◦ C;
• The charge was reduction melted for 30 min according to the temperature regime
defined in the theoretical study;
• The crucible with melting products was removed from the furnace and cooled to room
temperature; the melting products were then externally examined and weighed;
• The sublime trap was cleaned, and the trapped and condensed products were weighed.
Based on the data obtained on the separation nature, mass, and chemical composition
of the charge melting products (granulated pig iron and slag), it was concluded that the
charge composition and the chosen melting temperature regime are expedient.
In the laboratory furnace, the charge underwent reduction melting in a way, repro-
ducing a similar process in a rotary hearth furnace. A series of experiments allowed for
determining the optimal temperature regime for melting the charge in a laboratory furnace,
which ensured the sequential flow of all physicochemical interactions occurring in the gran-
ulated pig iron production: feeding the charge at 1150 ◦ C, raising the furnace temperature
to 1350 ◦ C at a rate of 15 ◦ C/min, increasing the furnace temperature to 1425 ◦ C at a rate of
11 ◦ C/min, and decreasing the furnace temperature to 1150 ◦ C at a rate of 30 ◦ C/min.
The captured gaseous reduction melting products was removed through a pipe from
the upper part of the furnace’s working chamber by induced draft. The sublimed products
entered the water-cooled gas flue, where the gas stream cooling, condensation, and partial
precipitation of sublimates took place. Dust residues were captured by passing the dust-gas
flow through a water filter in the form of a flask with water.
The reduction melting of the pelletized charge formed slag granulated pig iron. Shock
cooling of this product in water leads to the instantaneous crystallization of iron particles
and their separation from the slag. The granulated pig iron particles obtained (Figure 6)
were 10–15 mm in size and had magnetic properties. The extraction of iron into pig iron
was 92–96%.
Appl. Sci.Sci.
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2023,13,
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Appl. Sci. 2023, 13, x FOR PEER REVIEW 8 of 12

Figure6.6.The
Figure Thegranulated
granulated
pigpig
ironiron samples.
samples.
Figure 6. The granulated pig iron samples.
Three
Threesamples
sampleswere takentaken
were to define the chemical
to define composition
the chemical of the pig iron
composition produced.
of the
Three samples were taken to define the chemical composition of the pig ironpig
pro-iron pro
The chemical analysis of inclusions was performed by electron probe microanalysis (EPMA)
duced. The chemical analysis of inclusions was performed by electron
duced. The chemical analysis of inclusions was performed by electron probe microanaly- probe microanaly
using an X-ray wave spectrometer and a KEVEX energy-dispersive spectrometer. The study
sis(EPMA)
sis (EPMA)usingusing an
anTableX-ray
X-ray wave spectrometeraand a KEVEX energy-dispersive spectrom
results are given in 6.wave spectrometer
Figure 7 shows theand KEVEX
distribution ofenergy-dispersive spectrom-
the selected elements in the
eter.
eter. The
The study
study results
results
characteristic X-rays. areare given
given in in
TableTable
6. 6. Figure
Figure 7 7
shows shows
the the distribution
distribution of the of the
selected selected
elements in the characteristic X-rays.
elements in the characteristic X-rays.
Table 6. The chemical composition of pig iron samples.
Table
Table6.6.The
Thechemical composition
chemical of pig
composition ofiron
pig samples.
iron samples.
Elements Fe C Si S Ni Cu
Elements Fe C Si S Ni Cu
Elements
Value, wt% Fe
95.01–95.5 4.2–4.6C 0.1–0.13Si 0.05–0.09 S 0.06–0.07 Ni0.09–0.1 Cu
Value, wt% 95.01–95.5 4.2–4.6 0.1–0.13 0.05–0.09 0.06–0.07 0.09–0.1
Value,
Average wt%
value, wt% 95.01–95.5
95.27 4.2–4.6 0.11
4.4 0.1–0.13 0.07
0.05–0.090.06 0.06–0.07
0.09 0.09–0.1
Average value, wt% 95.27 4.4 0.11 0.07 0.06 0.09
Average value, wt% 95.27 4.4 0.11 0.07 0.06 0.09

(a) (b) (c)

Figure
Figure 7.
7. The
The EPMA
EPMA results:
results: (а)
(a) iron;
iron; (b) sulfur; (c) silicon.
(a) (b)(b) sulfur; (c) silicon. (c)
A
Figure metallographic
A metallographic studywas
study
7. The EPMA results: was
(а) performed
performed
iron; to to determine
determine
(b) sulfur; (c) the the
silicon. microstructure
microstructure ofobtained
of the the ob-
tained
pig ironpig iron samples.
samples. The studied
The studied thin sections
thin sections (after with
(after etching etching withnitric
a 3–5% a 3–5%
acidnitric acid
solution)
solution) were
were analyzed analyzed
using an using
Olympusan Olympus
GX-51 GX-51
electron electron
microscope microscope
(Olympus,
A metallographic study was performed to determine the microstructure of (Olympus,
Tokyo, Tokyo,
Japan). It the ob
Japan).
has beenIt established
has been established
obtaining obtaining the hyper
the hyper eutectic eutectic
white whitethe
pig iron, pig iron, theofstructure
structure which is
tained pig iron samples. The studied thin sections (after etching with a 3–5% nitric acid
of which is represented
represented by perliteand
by perlite ledeburite ledeburite
primaryand primary(Figure
cementite cementite
8). (Figure 8).
solution) were analyzed using an Olympus GX-51 electron microscope (Olympus, Tokyo
Japan). It has been established obtaining the hyper eutectic white pig iron, the structure
of which is represented by perlite ledeburite and primary cementite (Figure 8).
 Appl. Sci. 2023, 13, x FOR PEER REVIEW 9 of 1
Appl.Appl.
Sci. 2023, 13, x FOR PEER REVIEW
Sci. 2023, 13, 6204 9 of 12

Figure 8. The pig iron sample metallography results (L—ledeburite; C—cementite primary).

Zinc sublimates caught in different deposition areas of the dust collecting system
Figure
Figure 8. The
8. The pig pig
iron iron sample
sample metallography
metallography results (L—ledeburite;
results (L—ledeburite; C—cementite
C—cementite primary). primar
were mixed to obtain an average product sample, the chemical composition of which wa
defined
Zinc by XRF. According
sublimates caught in to the data
different obtained,
deposition theofmajor
areas compound
the dust collectinginsystem
the sample i
Zinc sublimates caught in different deposition areas of the dust collecting
ZnOmixed
were with atocontent
obtain anofaverage
68.8 wt%; the presence
product ofchemical
sample, the chlorinecomposition
and fluorine was also
of which wasrecorded
wereamixed
defined
with by XRF.to
content obtain
According
of, an average
to the
respectively, data
5.32 product
obtained,
and sample,
thewt%.
1.31 the chemical
majorCalcination
compound inatthe composition
sample
1000 is ZnO
°C for 90 min ofwa
wh
defined
with
proposed by
a content XRF.
of 68.8 According
to remove wt%; to the
the presence
halogens. The data obtained,
of chlorine
chemical and fluorine
composition thewas
of major
ZnO compound
alsoafter
recorded with ain(Figur
calcination the s
content of, respectively, 5.32 and 1.31 wt%. Calcination at 1000 ◦ C for 90 min was proposed
ZnO
9) with in
is given a content of 68.8allows
Table 7, which wt%; forthe concluding
presence ofthat chlorine and fluorine
the resulting productwas also r
is suitabl
to remove halogens. The chemical composition of ZnO after calcination (Figure 9) is given
with
for a content
further of, respectively,
use. The 5.32 and 1.31
obtained zinc-containing wt%.consists
powder Calcination
of 80%atof1000 °C for
particles 90
with
in Table 7, which allows for concluding that the resulting product is suitable for further use.
proposed
size of 20–30 to remove
µm. halogens. The chemical composition of ZnO
The obtained zinc-containing powder consists of 80% of particles with a size of 20–30 µm. after calcination
9) is given in Table 7, which allows for concluding that the resulting product is
for further use. The obtained zinc-containing powder consists of 80% of particle
size of 20–30 µm.

Figure9.9.Zinc
Figure Zinc oxide
oxide obtained
obtained from
from technogenic
technogenic raw materials
raw materials by melting
by melting the charge.
the charge.

Table7.7.The
Table Thechemical composition
chemical of ZnO
composition samples
of ZnO after calcination.
samples after calcination.

Components ZnO Fe2 O3 Components

K2 O CaOZnO Cl Fe2O3 KSO2O3 CaOSiO2 Cl Al SO2O3 3 SiOF2 Al2MgO
O3 F MgO
Content, wt% 90.21 Figure 9. Zinc
1.97 Content, oxide obtained from
0.46wt% 0.3890.21 0.03 technogenic
0.2 raw
4.82materials
1.76by melting
- the charge.
0.17
1.97 0.46 0.38 0.03 0.2 4.82 1.76 - 0.17
Table 7. The chemical
AAprocess flowsheetcomposition
for for
the the
EAFD ofprocessing
ZnO samples after
(Figure 10)calcination.
has10)
been
process flowsheet EAFD processing (Figure hasdeveloped and
been developed and
proposed based on the laboratory study results. The basic unit in this technology is a rotary
proposed based on the laboratory
ZnO Fe2O3 K2O CaO Cl SO3 SiO2 Al2O3 ro
study results. The basic unit in this technology is a
hearthComponents
furnace. F
taryThe
hearth furnace.
proposed technology of EAFD processing consists of the recovery of iron and
Content, wt% 90.21 1.97 0.46 0.38 0.03 0.2 4.82 1.76 -
zinc from their oxygen-containing forms by active carbon-containing materials in a rotary-
hearth furnace [27,28]. The briquettes charge includes oxide scale, EAFD, long-flame little
A process
nut (DOM) flowsheet
coal, lime, for the
and molding sand.EAFD processing
Reduction (Figure
smelting of 10) leads
the charge has been
to the develo
proposed based on the laboratory study results. The basic unit in this technolog
formation of zinc fumes, which are captured during the purification of the exhaust furnace
gases. The general
tary hearth scheme of EAFD processing includes the following stages: reception
furnace.
and preparation of raw materials; obtaining briquettes with minimum moisture content
(2%); obtaining granulated pig iron and zinc-containing fumes during reduction smelting;
purification of zinc oxide fumes for obtaining a commercial product.
Appl. Sci. 2023, 13, x FOR PEER REVIEW 10
Appl. Sci. 2023, 13, 6204 10 of 12

Figure 10. Process flowsheet for the EAFD processing.

Figure 10. Process flowsheet for the EAFD processing.
5. Conclusions
Technology
The proposed has been developed
technology offor the pyrometallurgical
EAFD processing consistsprocessing of recovery
of the electric arcof iron
furnace dust of Magnitogorsk Iron and Steel Works PJSC with the production of granulated
zinc from their oxygen-containing forms by active carbon-containing materials in a rot
pig iron and a zinc-containing product. The content of the melting charge components was
hearth
calculatedfurnace
in % as[27,28].
follows:The briquettesscale—51.33;
EAFD—17.44; charge includes oxide
long-flame scale,
little EAFD,quartz
nut—20.61; long-flame l
nut (DOM)lime—5.91.
sand—4.71; coal, lime, and molding sand. Reduction smelting of the charge leads to
formation of zinc fumes,
The experimental study which are captured
was performed on aduring
laboratorythe unit
purification
based on of the exhaust furn
a high-tem-
perature LHT 08/17 furnace. The experiments allowed for defining the
gases. The general scheme of EAFD processing◦ includes the following stages: recepoptimal temperature
regime for reduction melting (feeding the charge at 1150 C, raising the furnace temperature
and preparation of raw materials; obtaining briquettes with minimum moisture con
to 1350 ◦ C at a rate of 15 ◦ C/min, increasing the furnace temperature to 1425 ◦ C at a rate of
(2%); obtaining
11 ◦ C/min, granulated
and decreasing the pig irontemperature
furnace and zinc-containing
to 1150 ◦ C atfumes
a rate during reduction smelt
of 30 ◦ C/min).
purification
The total of zinc oxide
extraction fumes
of iron forinto
and zinc obtaining a commercial
marketable products wasproduct.
94 and 91%, respec-
tively. As a result of laboratory tests, pig iron samples with granule sizes of 10–15 mm
5. Conclusions
were obtained, containing in wt%: Fe—95.27; C—4.4; Si—0.11; S—0.07; Ni—0.06; Cu—009.
The obtained granulated pig iron is recommended for use instead of metal scrap for steel
Technology has been developed for the pyrometallurgical processing of electric
production in electric furnaces. After calcination of the zinc oxide for 90 min at 1000 ◦ C,
furnace
the targetdust of Magnitogorsk
compound Irontoand
content increased Steel
90.21 wt%,Works
and thePJSC with
chlorine the production
content decreased of gra
lated
to 0.03pig
wt%iron(no and a zinc-containing
fluorine was detected in the product.
calcinedThe contentThis
samples). of the
ZnOmelting
grade meetscharge com
nents
customer was calculatedfor
requirements in manufacturing
% as follows:metallic
EAFD—17.44;
zinc or paintscale—51.33; long-flame
and rubber products, etc. little n
20.61;The proposed
quartz technology
sand—4.71; will allow for using the obtained granulated pig iron as a
lime—5.91.
substitute for scrap metal in
The experimental the electric
study arc furnace on
was performed steel a production,
laboratory which is in line
unit based onwith
a high-tem
the Russian ferrous metallurgy development strategy for 2014–2022 and up to 2030.
ature LHT 08/17 furnace. The experiments allowed for defining the optimal tempera
regime for reduction melting (feeding the charge at 1150 °C, raising the furnace temp
ture to 1350 °C at a rate of 15 °C/min, increasing the furnace temperature to 1425 °C
rate of 11 °C/min, and decreasing the furnace temperature to 1150 °C at a rate o
°C/min).
The total extraction of iron and zinc into marketable products was 94 and 91%
spectively. As a result of laboratory tests, pig iron samples with granule sizes of 10–15
were obtained, containing in wt%: Fe—95.27; C—4.4; Si—0.11; S—0.07; Ni—0.06; C
009. The obtained granulated pig iron is recommended for use instead of metal scrap
Appl. Sci. 2023, 13, 6204 11 of 12

Author Contributions: Conceptualization, N.V.N. and A.E.P.; methodology, N.V.N.; software, A.A.T.;
validation, N.V.N. and A.A.T.; formal analysis, N.V.N.; investigation, A.A.T. and A.E.P.; resources,
N.V.N.; data curation, A.A.T.; writing—original draft preparation, A.E.P.; writing—review and
editing, N.V.N.; visualization, A.A.T.; supervision, N.V.N. All authors have read and agreed to the
published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data underlying this article will be shared upon reasonable request
to the corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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