metals
Article
Effect of Al Dross Addition on Temperature Improvements in
Molten Steel by Blowing Dry Air
Sun-Joong Kim
Citation: Kim, S.-J. Effect of Al Dross
Addition on Temperature
Improvements in Molten Steel by
Blowing Dry Air. Metals 2022, 12,
1170. https://doi.org/10.3390/
met12071170
Academic Editor: Felix A. Lopez
Received: 8 June 2022
Accepted: 7 July 2022
Published: 9 July 2022
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Metals 2022, 12, 1170. https://doi.org/10.3390/met12071170
Department of Materials Science and Engineering, Chosun University, Gwangju 61452, Korea;
ksjoong@chosun.ac.kr; Tel.: +82-62-230-7200
Abstract: The CO2 emissions of electric arc furnaces (EAFs) can be reduced by decreasing the electrical
energy consumed in the melting of iron scraps by utilizing chemical energy. In general, the chemical
energy efficiency of the EAF process can be improved using oxidation reaction heat and carbon
combustion. When carbon is added to molten steel, it is not completely dissolved because of its
high melting point, and it floats to the slag layer, owing to its low density. Al dross is a byproduct
of aluminum smelting, and it contains over 27 mass% metallic aluminum. As the exothermic heat
of aluminum oxidation is larger than that of carbon oxidation, the Al dross is a useful source of
exothermic heat in the EAF process. In this study, to utilize the mixtures of cokes and Al dross
as chemical energy sources in the EAF process, we investigated the dissolution concentrations,
dissolution ratios, and dissolution rate constants of carbon and aluminum in molten steel. The
improvement in the molten steel temperature was investigated by blowing dry air into the melt after
the dissolution of the mixtures of cokes and Al dross.
Keywords: Al dross; dissolution behavior; molten steel; oxidation heats
1. Introduction
It is important to reduce CO2 emissions in order to achieve a sustainable society. Nu-
merous studies have investigated eco-friendly energy resources to reduce the consumption
of fossil fuels [1,2]. Among domestic industries in Korea, the steel industry generated
approximately 23% of CO2 emissions in 2017 [3]. In the global steel industry, ~65% of steel
is produced using blast furnaces and converters, and blast furnaces account for ~70% of
CO2 emissions. A process that uses hydrogen resources and direct reduced iron (DRI) has
been proposed to reduce CO2 emissions in the steel industry. The electric arc furnace (EAF)
process is required to produce high-grade steel products using DRI [4].
The CO2 emissions of the EAF process can be decreased by reducing the use of electric
energy and improving the efficiency of chemical energy. In Korea, domestic EAF companies
produce steel products using ~63% electrical energy, ~30% chemical energy, and ~3%
burner combustion heat. Electrical energy is primarily consumed for melting the scrap in
the EAF process, and over 50% of it is produced using coal and oil in Korea, which causes
CO2 emissions [5]. Therefore, it is necessary to improve the efficiency of chemical energy
consumption by utilizing raw materials that contain high thermal energy and oxidation
reaction heat by blowing oxygen.
Generally, coke added to the EAF process contains more than ~80% carbon, which is
used as a slag-forming material through its reaction with oxygen. Carbon generates more
energy in the second combustion compared to the first combustion. However, most of the
carbon material floats in a slag layer, owing to its low density. In addition, carbon cannot
be dissolved over a relatively short operation time, owing to its high melting point.
Over the past several decades, the dissolution behaviors and thermodynamic data
of carbon-based materials have been extensively investigated to improve the steelmaking
technology using carbon materials. Matoba et al. investigated the equilibrium of carbon and
https://www.mdpi.com/journal/metals
Metals 2022, 12, 1170 2 of 15

oxygen in a liquid Fe-C alloy using a graphite crucible and CO gas at 1573–1873 K. Based on
the Boudouard equilibrium, they obtained an empirical formula for the activity coefficients
of C and O in molten steel [6]. Kim et al. investigated the carbon solubility in various liquid
iron alloys, including V, Mo, and Ni, under an Ar atmosphere at 1873 K. They determined
the effect of the interaction parameters of V, Mo, and Ni on the activity coefficient of
carbon in carbon-saturated iron alloys [7]. Furthermore, the effect of the sulfur content in
molten iron alloys on the solubility of graphite was investigated at 1473–1973 K [8,9]. As
temperature increased, the solubility of carbon in steel increased and the sulfur content
decreased. Cham et al. investigated the dissolution behaviors of two Australian cokes in
molten steel at 1723–1823 K. They found that temperature had a significant effect on the
dissolution rates of cokes. In addition, the difference between the dissolution rates of cokes
was attributed to the different compositions of mineral matter in the coke, which limited
the interfacial contact area between the carbon source and molten iron [10]. Jang et al.
found that an ash layer that accumulated on the surface of cokes considerably reduced the
contact area between cokes and molten steel, thereby decreasing the dissolution rates of
carbon [11]. Even though the use of the carbon technology in the steel industry provides
superior results, the considerable amounts of carbon materials used in the steelmaking
process cause CO2 emissions. Thus, it is necessary to find appropriate materials to partly
replace carbon and reduce CO2 emissions in the steel industry.
Al dross, which is a by-product of Al smelting, contains approximately 27 mass%
metallic aluminum, whose oxidation heat is approximately 3 times higher than that of car-
bon. Approximately 60,000 tons of Al dross is produced annually in Korea and 800,000 tons
in the United States [12–14]. Al dross is almost entirely landfilled because practical recy-
cling methods have not been established [15]. One of the recycling methods for Al dross is
the use of additives for reduction and heating resources in the steelmaking process because
of the metallic aluminum content in Al dross. Kim et al. investigated the effect of a mixture
of Al dross and graphite powder on iron reduction in EAF slag. When Al dross was added
at 5% of the slag weight, the reduction rate of iron in the slag was 2.5 times higher than
that obtained using only the graphite powder [16]. Even though the Al dross is useful for
the reduction of FeO from slag, the sources of oxidation heat in the dissolution of Al dross
in molten steel have not been investigated.
In this study, the dissolution of Al dross was investigated in order to improve the
molten steel temperature using the oxidation heat of metallic aluminum to utilize an Al
dross as a chemical energy source in the EAF process. The coke and the Al dross were
mixed, and the effect of the mixing ratio and molten steel temperature on the concentration,
dissolution ratio, and dissolution rate constants of carbon and aluminum in molten steel
were investigated. Furthermore, the temperature changes in molten steel due to blowing
dry air into the melt were examined after the dissolution of the mixture of coke and the
Al dross.

2. Experimental Method
2.1. Dissolution of Al Dross and Cokes in Molten Steel
The components of coke particles and Al dross were obtained using proximate and
ICP analyses. Tables 1 and 2 list the compositions of the cokes and Al dross, respectively.
The metallurgical cokes contained 86.06 mass% C and 10.91 mass% ash. The Al dross
contained approximately 27 mass% metallic Al, 7 mass% SiO2 , and 65 mass% Al2 O3 . As the
amount of the coke and Al dross mixture increases, the ash, SiO2 , and Al2 O3 can affect the
slag composition. This effect was reduced by setting the amount of the mixture as 5 mass%
of the total iron mass. The particle sizes of the coke and Al dross were less than 150 µm,
and the total weight of iron was approximately 90 g.
 Metals 2022, 12, 1170 3 of 15
Metals 2022, 12, x FOR PEER REVIEW 3 of 16

Table 1. Coke components obtained using proximate analysis (mass%).

Table 1. Coke components obtained using proximate analysis (mass%).
Fixed Carbon Volatile Moisture Ash
Fixed 86.06
Carbon Volatile
2.1 Moisture
0.93 Ash
10.91
86.06 2.1 0.93 10.91
Table 2. Composition of Al dross obtained using ICP analysis (mass%).
Table 2. Composition of Al dross obtained using ICP analysis (mass%).
Al Fe Sn Zn SiO2 Al2 O3
Al Fe Sn Zn SiO2 Al2O3
27.02 0.16 0.01 0.03 7.00 65.78
27.02 0.16 0.01 0.03 7.00 65.78

Figure11shows
Figure showsaaschematic
schematicofofthe theinduction
inductionfurnace
furnaceusedusedfor
forthe
thedissolution
dissolutionofofAlAl
dross and
dross and cokes in molten steel. First, flake-type electrolytic iron was charged into
in molten steel. First, flake-type electrolytic iron was charged into 2an 3 an Al O
crucible
Al with awith
2O3 crucible diameter of 35 mm.
a diameter Themm.
of 35 mixture
The of the coke
mixture ofand
the Al dross
coke was
and Alcharged
dross wasinto
an iron into
charged crucible withcrucible
an iron a diameter
withofa 20 mm, and
diameter then,
of 20 mm,electrolytic
and then,iron was placed
electrolytic ironin
wasthe
prepared
placed iron
in the crucible.
prepared Table
iron 3 shows
crucible. Tablethe3 shows
mass ratio of the
the mass coke
ratio ofand Al dross
the coke and Almixtures.
dross
C/Al represents
mixtures. the ratiothe
C/Al represents of ratio
carbon to aluminum
of carbon in the mixture.
to aluminum The prepared
in the mixture. Al2 O3
The prepared
crucible with the samples was covered with a graphite crucible and protection
Al2O3 crucible with the samples was covered with a graphite crucible and protection cru- crucible. The
oxidation of iron, carbon, and aluminum during the dissolution experiments
cible. The oxidation of iron, carbon, and aluminum during the dissolution experiments was prevented
through
was deoxidized
prevented through Ardeoxidized
gas flow atAr 500 mL/min.
gas flow at 500ThemL/min.
deoxidation treatment with
The deoxidation Ar gas
treatment
was Ar
with carried
gas wasout carried
at 773 Kout
using MgKchips.
at 773 using Mg chips.

Figure
Figure1.1.Schematic
Schematicofofinduction
inductionfurnace.
furnace.

Massratio
Table3.3.Mass
Table ratioofofcoke
cokeand
andAl
Aldross
drossmixtures.
mixtures.

Mixture
Mixture Coke:Al
Coke: AlDross
Dross
Ratio
Ratio(%)
(%) 80:20
80:20 60:40
60:40 40:60
40:60
C/Al
C/Al 0.4
0.4 0.2
0.2 0.1
0.1

The
Thetemperature
temperatureofofthe themolten
moltensteel
steelwas
wasmeasured
measuredusing
usingaaB-type
B-typethermocouple,
thermocouple,and and
the
the reaction temperatures were 1823 K, 1873 K, and 1973 K. The time requiredtotoachieve
reaction temperatures were 1823 K, 1873 K, and 1973 K. The time required achieve
the
thetarget
targettemperature
temperaturewas wasmaintained
maintainedasasconstant
constantatat11h.h.The
Theinitial
initialtime
timeimmediately
immediately
after
afterachieving
achievingthethetarget
targettemperature
temperature was
was set as “0.”
“0”. The reaction
reaction times
times were
were600
600s,s,1800
1800s,
s,3600
3600s,s,and
and7200
7200s,s,and
andthe
thecrucible
cruciblewith
withthe
thesample
samplewaswasremoved
removedand andwater
waterquenched
quenchedat
ateach
eachtime
time stamp.
stamp. The The concentrations
concentrations of carbon
of carbon andand aluminum
aluminum in obtained
in the the obtained
metalmetal
were
were measured
measured usingusing C/S analysis
C/S analysis (CS-2000,
(CS-2000, ELTRA,ELTRA,
Haan, Haan,
Germany)Germany) and ICP-OES
and ICP-OES (In-
(Inductively
ductively
Coupled Coupled Plasma Emission
Plasma Optical Optical Emission Spectroscopy,
Spectroscopy, since here,since here, regarding
regarding as ICP) as ICP)
analysis
analysis
(Optima(Optima
5300 DV, 5300 DV,Elmer
Perkin PerkinLtd.,
Elmer Ltd., Waltham,
Waltham, MA, USA),MA,respectively.
USA), respectively. The pre-
The pretreatment
treatment for ICP analysis was as follows: First, 2 g of metal specimens were obtained
Metals 2022,12,
Metals2022, 12,1170
x FOR PEER REVIEW 44 of
of 15
16

for ICPthe
from analysis
upper,was as follows:
middle, First,portions
and lower 2 g of metal specimens
of the were obtained
metal sample. from the
Subsequently, theupper,
metal
middle, and lower portions of the metal sample. Subsequently, the metal specimens were
specimens were dissolved using nitric acid, hydrochloric acid, and perchloric acid. Iron
dissolved using nitric acid, hydrochloric acid, and perchloric acid. Iron was separated from
was separated from the sample solution using MIBK (Methyl isobutyl ketone). The sepa-
the sample solution using MIBK (Methyl isobutyl ketone). The separation process was
ration process was performed five times because the concentration of aluminum in the
performed five times because the concentration of aluminum in the metal was significantly
metal was significantly lower than that of Fe. The concentrations of carbon and aluminum
lower than that of Fe. The concentrations of carbon and aluminum obtained in each analysis
obtained in each analysis were used to calculate the dissolution ratio.
were used to calculate the dissolution ratio.
2.2. Measurement
2.2. Measurement of ofMolten
MoltenSteel
SteelTemperature
Temperatureby byBlowing
BlowingDryDryAir
Air
After the
After the complete
complete dissolution
dissolution of of the
the Al
Al dross
dross and
andcoke
cokemixtures,
mixtures, the
thetemperature
temperature
change in the molten steel was measured by blowing dry air. The
change in the molten steel was measured by blowing dry air. The mixture ratio of mixture ratio ofthe
theAl
Al
dross and coke mixtures was 0.2, according to the dissolution experiments.
dross and coke mixtures was 0.2, according to the dissolution experiments. Figure 2 and Figure 2 and
Table44show
Table showthetheschematic
schematicof ofthe
theexperimental
experimentalmethod method and
and the
the experimental
experimental conditions,
conditions,
respectively. The temperature of the melt and the atmosphere in the furnace
respectively. The temperature of the melt and the atmosphere in the furnace was maintained was main-
tained at 1873 K under N gas (500 mL/min). Subsequently, the
at 1873 K under N2 gas (500 mL/min). Subsequently, the Al dross and coke mixture
2 Al dross and coke mixture
was
was dissolved for 1 h. Thereafter, dry air was blown into the melt.
dissolved for 1 h. Thereafter, dry air was blown into the melt. The concentrations ofThe concentrations of
aluminumand
aluminum andcarbon
carbonininthethemetal
metal sample
sample before
before andand after
after blowing
blowing dry dry air were
air were meas-
measured
ured using
using the methods
the methods described
described in Section
in Section 2.1. 2.1.

Figure2.2.Schematic
Figure Schematicof
ofexperimental
experimentalmethod.
method.

Table4.4.Experimental
Table Experimentalconditions.
conditions.

Temperature
Temperature (K)(K) 1873
1873
Atmosphere (mL/min)
Atmosphere (mL/min)
Ar (500)
Ar (500)
Blowing gas (mL/min) Dry Air (100)
Blowing gas (mL/min) Dry Air (100)
Dissolution time (s) 3600
Dissolution time (s) 3600
Blowing time (s) 3600
Blowing time (s) 3600
3. Results and Discussion
3. Results
3.1. and Discussion
Dissolution of Al Dross and Coke in Molten Steel
3.1. Dissolution of Al Dross and Coke in Molten Steel
Figures 3–5 show the change in the dissolution concentrations of carbon and alumi-
Figures
num in molten 3–5steel
showaccording
the changetoin themixing
the dissolution concentrations
ratio (C/Al) of carbon
and reaction time and aluminum
at 1823 K, 1873
in molten steel according to the mixing ratio (C/Al) and reaction time at
K, and 1973 K. At 1823 K and 1873 K, the dissolution concentrations of C and Al 1823 K, 1873 K,were
and
1973 K. At 1823 K and 1873 K, the dissolution concentrations of C and Al were constant
constant at 3600 s and 1800 s or more, respectively. At 1973 K, the dissolution concentra- at
3600 s and 1800 s or more, respectively. At 1973 K, the dissolution concentrations
tions of carbon and aluminum were constant over 1800 s. At a constant molten steel tem- of carbon
and aluminum
perature, were of
the effect constant over ratio
the mixing 1800 s.
onAt a constant
the molten
time required tosteel temperature,
reach the maximum the disso-
effect
of the mixing ratio on the time required to reach the maximum dissolution concentrations
Metals 2022, 12, x FOR PEER REVIEW 5 of 16
Metals 2022, 12, 1170 5 of 15

lution
was notconcentrations
significant. Thewas not significant.
maximum dissolutionThe maximum dissolution
concentrations concentrations
increased with the molten in-
creased with the molten steel temperature. In addition, as the mixing ratio increased, the
steel temperature. In addition, as the mixing ratio increased, the maximum dissolution
maximum dissolution
concentration of carbon concentration of carbon
increased and that increased
of aluminum and that of aluminum decreased.
decreased.

Figure3.3.Change
Figure Changeininconcentrations
concentrationsofof C and
C and Al Al at 1823
at 1823 K. K.

Figure4.4.Change
Figure Changeininconcentrations
concentrationsofof C and
C and Al Al at 1873
at 1873 K. K.

Figure 6 shows the theoretical oxidation reaction heat, as calculated using the maxi-
mum dissolution concentrations of carbon and aluminum at each molten steel temperature
and the concentration of impurities generated in molten steel by changing the mixing ratio.
The impurities were ash, SiO2 , and Al2 O3 . The oxidation heat of aluminum was assumed
to be ~30,868 J/g, which is the heat of combustion of aluminum [17], and the oxidation heat
of carbon was assumed to be ~9211 J/g, which is the enthalpy of formation of CO gas [18].
Metals 2022,12,
Metals2022, 12,1170
x FOR PEER REVIEW 66 of
of 15
16

Figure 5. Change in concentrations of C and Al at 1973 K.

Figure 6 shows the theoretical oxidation reaction heat, as calculated using the maxi-
mum dissolution concentrations of carbon and aluminum at each molten steel tempera-
ture and the concentration of impurities generated in molten steel by changing the mixing
ratio. The impurities were ash, SiO2, and Al2O3. The oxidation heat of aluminum was as-
sumed to be ~30,868 J/g, which is the heat of combustion of aluminum [17], and the oxi-
dation heat of carbon was assumed to be ~9211 J/g, which is the enthalpy of formation of
Figure
gas5.5.[18].
Figure
CO Change in
Change in concentrations
concentrations of
of C
C and
and Al
Al at
at 1973
1973K.
K.

Figure 6 shows the theoretical oxidation reaction heat, as calculated using the maxi-
mum dissolution concentrations of carbon and aluminum at each molten steel tempera-
ture and the concentration of impurities generated in molten steel by changing the mixing
ratio. The impurities were ash, SiO2, and Al2O3. The oxidation heat of aluminum was as-
sumed to be ~30,868 J/g, which is the heat of combustion of aluminum [17], and the oxi-
dation heat of carbon was assumed to be ~9211 J/g, which is the enthalpy of formation of
CO gas [18].

Figure 6. Theorical oxidation reaction heats and concentrations

concentrations of impurities,
impurities, C, and Al in molten
steel as function of mass ratio of C/Al.
steel as function of mass ratio of C/Al.

At aa constant
constantmolten
moltensteel
steeltemperature,
temperature,thethe
theoretical oxidation
theoretical reaction
oxidation heatheat
reaction and and
con-
centration of impurities decreased as the mixing ratio increased. The theoretical oxidation
concentration of impurities decreased as the mixing ratio increased. The theoretical oxi-
reactionreaction
dation heat was calculated
heat using the
was calculated following
using equation:
the following equation:
heats (𝐽⁄𝑔oxidation
Theorical oxidation Theorical ) heats ( J/g)
(𝑤𝑡. %𝐶 ×(wt.%C
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐹𝑒
×weight × ×9211)
of Fe (𝑤𝑡. ×
9211)+(+wt.%Al %𝐴𝑙 × 𝑤𝑒𝑖𝑔ℎ𝑡
weight 𝑜𝑓)𝐹𝑒 × 30868)
of Fe×30868 (1)
=
Figure 6. Theorical =
oxidation reaction heats weight
and concentrations
of Fe . C, and Al in. molten
of impurities,
steel as function of mass ratio of C/Al. 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐹𝑒
In Equation (1), wt.% C and wt.% Al denote the maximum dissolution concentrations
At a and
of carbon constant molteninsteel
aluminum temperature,
molten the theoretical
steel, respectively, oxidation
as shown reaction
in Figures heatmass
4–6. The and
concentration
of of impurities
iron is assumed to be thedecreased as the
initial mass mixing
of Fe. As ratio
shown increased.
in FigureThe
6, theoretical oxi-
the theoretical
dation reaction
oxidation heat
heats of thewas calculated
Al dross using
and coke the following
mixture equation:
decreased with the mixing ratio because
the maximum concentration of aluminum in molten steel decreased. At 1823 K and
Theorical oxidation heats (𝐽⁄𝑔)
1873 K, the oxidation reaction heats at mixing ratios of 0.1 and 0.2 were not significantly
(𝑤𝑡. %𝐶 × 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐹𝑒 × 9211) + (𝑤𝑡. %𝐴𝑙 × 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐹𝑒 × 30868) (1)
different. =
However, the concentration of impurities in molten steel increased as the . mass
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐹𝑒
Metals 2022, 12, x FOR PEER REVIEW 7 of 16

In Equation (1), wt.% C and wt.% Al denote the maximum dissolution concentrations
Metals 2022, 12, 1170 7 of 15
of carbon and aluminum in molten steel, respectively, as shown in Figures 4–6. The mass
of iron is assumed to be the initial mass of Fe. As shown in Figure 6, the theoretical oxida-
tion heats of the Al dross and coke mixture decreased with the mixing ratio because the
ratio decreased.
maximum High concentrations
concentration of aluminumofinimpurities,
molten steelincluding
decreased.Al2 O and SiO
At3 1823 2 , decrease
K and 1873 K,
slag basicity. Therefore,
the oxidation on the
reaction heats basis of
at mixing the of
ratios theoretical oxidation
0.1 and 0.2 were notreaction heatsdifferent.
significantly and the
concentration
However, theof impurities inof
concentration the Al dross and
impurities coke mixture,
in molten the appropriate
steel increased mixing
as the mass ratio
ratio de-
was assumed to be 0.2.
creased. High concentrations of impurities, including Al2O3 and SiO2, decrease slag basic-
Figures 7 on
ity. Therefore, andthe
8 basis
showofthetheeffect of theoxidation
theoretical molten steel temperature
reaction heats andonthethe maximum
concentration
dissolution ratios of carbon and aluminum in molten steel. The maximum
of impurities in the Al dross and coke mixture, the appropriate mixing ratio was assumed dissolution
ratios were calculated using Equation (2). wt.% M is the dissolution concentration of carbon
to be 0.2.
or aluminum
Figures 7inand
molten steel.the
8 show Theeffect
weight of iron
of the and the
molten steelinitial weight ofon
temperature Mthe
are maximum
the initial
mass of iron and the weight of carbon or aluminum, as calculated before
dissolution ratios of carbon and aluminum in molten steel. The maximum dissolution ra- the dissolution
experiments, respectively.
tios were calculated using Equation (2). wt.% M is the dissolution concentration of carbon
or aluminum in molten steel. The weight of(wt.%
iron and
M ×the initialofweight
weight Fe) of M are the initial
Dissolution
mass of iron and ratio
the weight ofof M(%)or
carbon =aluminum, as calculated before× 100.the dissolution
(2)
Initial weight of M
experiments, respectively.

Metals 2022, 12, x FOR PEER REVIEW 8 of 16

Figure7.7.Effect
Figure Effectofofthe
themolten
molten steel
steel temperature
temperature on the
on the maximum
maximum dissolution
dissolution ratioratio ofmolten
of C in C in molten
steel.
steel.

Figure 8. Effect
Figure Effectofof
thethe
molten steel
molten temperature
steel on the
temperature on maximum dissolution
the maximum ratio of
dissolution Al in
ratio ofmolten
Al in
steel.
molten steel.

(wt. % M × weight of Fe)

Dissolution ratio of M(%) = × 100. (2)
Initial weight of M
At a constant mixing ratio, the maximum dissolution ratios increased with the molten
steel temperature. This indicates that the dissolution of aluminum and carbon in the mix-
 Metals 2022, 12, 1170 8 of 15

At a constant mixing ratio, the maximum dissolution ratios increased with the molten
steel temperature. This indicates that the dissolution of aluminum and carbon in the
mixture can be improved when the molten steel temperature is increased because of the
oxidation heat of the dissolved aluminum and carbon by blowing oxygen. However, the
influence of the mixing ratio on the maximum dissolution ratios was not significant, as
shown in Figures 7 and 8. The relationship between the molten steel temperature and the
maximum dissolution ratios is expressed as follows:

Dis.rat.of [C] = −536.38 + 0.2839 × T(K). (3)

Dis.rat.of [Al] = −227.63 + 0.1363 × T(K). (4)

Figures 9 and 10 show the influence of the mixing ratio on the maximum dissolution
ratios at a constant molten steel temperature. The average values of the maximum dissolu-
tion ratios at a constant molten steel temperature are represented by each line in Figures 9
and 10. At a molten steel temperature of 1973 K, the maximum dissolution ratios were
~90% and ~40%, respectively. However, at a given temperature, the maximum dissolution
ratios were similar at mixing ratios of 0.1–0.4. Therefore, the molten steel temperature had
Metals 2022, 12, x FOR PEER REVIEW 9 of 1
a stronger effect on the dissolution behaviors of carbon and aluminum compared to the
mixing ratio.

Figure9.9.Changes
Figure Changes in the maximum
in the dissolution
maximum ratio of ratio
dissolution C in molten steel
of C in as a function
molten steel asofamixing ratioof mixing
function
of C/Al in the Al dross and coke mixtures.
ratio of C/Al in the Al dross and coke mixtures.
3.2. Kinetics for Dissolution of Al and C from Al Dross and Coke Mixture in Molten Steel
Based on the data shown in Figures 4–6, the dissolution rate constants of carbon and
aluminum were obtained using the following equations:

d[%M] Ak
= × ([%M]Sat. − [%M]). (5)
dt V
([%M]Sat. − [%M] Init. )
α = ln = −Kt. (6)
([%M]Sat. − [%M]time )
Metals 2022, 12, 1170 9 of 15
Figure 9. Changes in the maximum dissolution ratio of C in molten steel as a function of mixing
ratio of C/Al in the Al dross and coke mixtures.

10. Changes
Figure 10.
Figure inthe
Changes in themaximum
maximumdissolution
dissolution ratio
ratio of of
AlAl
in in molten
molten steel
steel as aasfunction
a function of mixing
of mixing
ratio of
ratio of C/Al
C/Al in
inthe
theAl
Aldross
drossand
andcoke mixtures.
coke mixtures.

3.2. Kinetics for Dissolution

In Equation (5), ‘A’ is of Alinterface
the and C from Al (m
area 2 ) between
Dross and Cokethe Mixture
moltenin Molten
steel andSteel
the Al dross
Metals 2022, 12, x FOR PEER REVIEW
and coke mixture charged in the iron crucible. ‘k’ is the dissolution
Based on the data shown in Figures 4–6, the dissolution rate constants of carbon rate constant (m/s),
10 ofand16
and
‘V’ is the volume of molten steel (m 3 ). Equation (6) can be obtained from Equation (5), and
aluminum were obtained using the following equations:
‘K’ denotes the apparent dissolution rate constant (K = Ak/V). In Equation (6), ‘[%M]sat. ’ and
𝑑 %𝑀 𝐴𝑘
‘[%M]Init. ’ are the maximum and initial × ( %𝑀 concentrations
= dissolution . − %𝑀 ). of carbon or aluminum (5)
(6), ‘[%M]sat.’ and ‘[%M]Init.’ are the 𝑑𝑡 maximum 𝑉 and initial dissolution concentrations of car-
in molten steel, respectively. ‘[%M]time ’ is the dissolution concentration of carbon or
bon or aluminum in molten steel, respectively. ( %𝑀 %𝑀 time. )’ is the dissolution concentration
− ‘[%M]
aluminum in molten steel at 𝛼= each reaction. time.
𝑙𝑛steel = −𝐾𝑡. (6)
of carbon or aluminum in molten at each reaction time.
Figures 11 and 12 show the( change %𝑀 − ‘α
. in %𝑀‘ and
C
) ‘α ‘ obtained using Equation (6)
Al
Figures 11 and 12 show the change in ‘αC‘ and ‘αAl‘ obtained using Equation (6) and
and the present experimental
In Equation is the results
(5), ‘A’ results interface asarea
a function
(mreaction of reaction
2) between the time. steel
molten The slope
and the between
the Al
the present experimental as a function of time. The slope between ‘α’
the
dross‘α’and
andcokethe reaction
mixture time is ‘K’.
charged in As iron
the shown in Figure
crucible. ‘k’ 11,
is thethe apparent rate
dissolution dissolution
constant rate
and the reaction time is ‘K’. As shown in Figure 11, the apparent dissolution rate constant
constant
(m/s),
of carbon
of
and(α ‘V’carbon (α
is the volume
C ) increased
of molten steel (m ). Equation (6) can be obtained from Equa- the
with the 3molten steel
C) increased with the molten steel temperature, even though the maximum
temperature, even though
maximum
tion (5), and
dissolution dissolution
‘K’ denotes
concentration concentration
thecarbon
of apparent at of carbon
dissolution
1973 K was atsaturated
1973
rate K was
for saturated
constant (K s,
1800 for 1800
= Ak/V).
as shownIn in s,Figure
as shown
Equation
in Figure 5. In contrast, the apparent dissolution rate constant
5. In contrast, the apparent dissolution rate constant of aluminum (αAl) was weakly influ- of aluminum (α Al ) was
weakly
enced by the molten steel temperature, as shown in Figure 12. Therefore, the influence of the
influenced by the molten steel temperature, as shown in Figure 12. Therefore,
influence
the moltenof thetemperature
steel molten steelontemperature
the dissolution on rate
the dissolution
constant of carbonrate constant of carbon
was stronger than was
stronger than that on the dissolution
that on the dissolution rate constant of aluminum. rate constant of aluminum.

Figure 11.
Figure 11. Changes
Changesininαα
Coke obtained using Equation (6) as a function of reaction time.
Coke obtained using Equation (6) as a function of reaction time.
Metals 2022, 12, 1170 10 of 15

Figure 11. Changes in αCoke obtained using Equation (6) as a function of reaction time.

Figure
Figure 12. Changes
Changes in
in α Alobtained
αAl obtainedusing
usingEquation
Equation(6)
(6)as
asaafunction
functionof
ofreaction
reactiontime.
time.

Figure 13
Figure 13 shows
shows the
the influence
influence ofof the
the molten
molten steel
steeltemperature
temperatureon onthe
theapparent
apparentdisso-
disso-
lution rate
lution rate constant
constant ofof the
the AlAl dross
dross and
and coke
coke mixtures,
mixtures, obtained
obtained inin the
the present
present study,
study, and
and
Metals 2022, 12, x FOR PEER REVIEW 11 of 16
the dissolution
the dissolution rate constant of carbon, obtained in a previous study [11]. The dissolution
The dissolution
rate constant
rate constantof ofcarbon
carbonobtained
obtainedininthe the present
present study
study waswas lower
lower thanthan
thatthat obtained
obtained in
in the
the previous
previous study.
study. The previous
The previous studystudy used carbon-saturated
used carbon-saturated conditions
conditions with a com-
with a compressed
pressed
board ofboard
coke onof the
coke on the
surface ofsurface
molten of molten
steel. steel. Conversely,
Conversely, in the present in study,
the present study,
the mixture
the
wasmixture
prepared was
byprepared
charging by Al charging Al dross
dross powder andpowder
coke in and coke
an iron in an iron
crucible. As crucible. As
the reaction
the
areareaction area
could not becould not bedetermined
accurately accurately determined
in the present in the present
study, study, the
the apparent apparent
dissolution
dissolution
rate constantrate
of constant
carbon wasof carbon
assumed was to assumed to be
be different different
from that offrom that of the
the previous previous
study. Fur-
study. Furthermore, it was assumed that the shape of the carbon source
thermore, it was assumed that the shape of the carbon source was related to the dissolu- was related to
the dissolution behavior of carbon. As shown in Figure 13, the apparent
tion behavior of carbon. As shown in Figure 13, the apparent dissolution rate constant of dissolution rate
constant
aluminum of in
aluminum
the mixturein the mixtureslightly
increased increased slightly
with with the
the molten molten
steel steel temperature,
temperature, compared
compared
to carbon. to carbon.

Figure 13.
Figure 13. Influence
Influence of
of molten
molten steel
steel temperature
temperature onon the
the apparent
apparent dissolution
dissolution rate
rate constant
constant of
of the
the Al
Al
dross and
dross and coke
coke mixtures
mixtures obtained
obtained in
in the
the present
present study,
study, and
and the
the dissolution
dissolution rate
rate constant
constant of
of carbon
carbon
obtained in a previous study [11].
obtained in a previous study [11].

Figures 14–16 show the experimental and calculated values of the changes in the dis-
solution concentrations of carbon and aluminum in molten steel. The dissolution rate con-
stants of carbon and aluminum shown in Figure 13 were used to calculate the dissolution
concentrations at different molten steel temperatures and mixing ratios. At 1823 K, 1873
K, and 1973 K, the calculated dissolution concentrations showed good agreement with the
experimental data. The dissolution concentration and dissolution efficiency of the Al
Metals 2022, 12, 1170 Figure 13. Influence of molten steel temperature on the apparent dissolution rate constant of11the Al
of 15
dross and coke mixtures obtained in the present study, and the dissolution rate constant of carbon
obtained in a previous study [11].

Figures
Figures 14–16 show the
14–16 show theexperimental
experimentalandandcalculated
calculated values
values of of
thethe changes
changes in dis-
in the the
dissolution concentrations
solution concentrations of carbon
of carbon andand aluminum
aluminum in molten
in molten steel.
steel. The The dissolution
dissolution rate rate
con-
constants of carbon
stants of carbon andand aluminum
aluminum shownininFigure
shown Figure1313were
wereused
usedto
to calculate
calculate the
the dissolution
dissolution
concentrations at different molten steel temperatures and mixing ratios.
concentrations at different molten steel temperatures and mixing ratios. At 1823 At 1823 K, K,
1873 K,
1873
and 1973 K, the calculated dissolution concentrations showed good agreement
K, and 1973 K, the calculated dissolution concentrations showed good agreement with the with the
experimental
experimentaldata.
data.TheThedissolution
dissolutionconcentration andand
concentration dissolution efficiency
dissolution of theofAlthe
efficiency dross
Al
and coke
dross andmixtures could be
coke mixtures predicted
could using the
be predicted equations
using proposed
the equations this study.
proposed this study.

Metals 2022, 12, x FOR PEER REVIEWFigure 14.

Figure 14. Comparison of experimental
experimental values
valueswith
withvalues
valuescalculated
calculatedusing
usingkapkapatat1823 KK
1823 shown
shown
12 in
of 16
Figure
in 13.13.
Figure

Figure 15.
Figure 15. Comparison
Comparison of
of experimental
experimental values
values with
with values
values calculated
calculated using
using kkapap at 1873 K
K shown
shown in
in
Figure 13.
Figure 13.

3.3. Changes in Molten Steel Temperature by Blowing Dry Air after Dissolution of Al Dross and
Coke Mixture
The improvement in the molten steel temperature due to the Al dross and coke mixture
was verified by measuring the molten steel temperature by blowing dry air gas after the
dissolution of the mixture. The mixing ratio was 0.2 and the mixture was completely
dissolved at 1873 K for 1 h. Then, dry air was blown for 1 h at a starting temperature of
1873 K. Furthermore, the coupled reaction model of the BOF process was used to simulate
the changes in molten steel temperature. The details of this model have been reported
elsewhere [19]. The model can simulate the changes in the temperature and composition
of molten steel and slag during top and bottom blowing. The mass transfer coefficient of
Metals 2022, 12, 1170 12 of 15

Metals 2022, 12, x FOR PEER REVIEW 12 of 16

the components in the metal phase was calculated using the stirring energies of top and
bottom blowing. In the present study, the stirring energy of bottom blowing was fixed
at unity, and the mass transfer coefficient of the components in the metal phase (km ) was
calculated using the stirring energies of top blowing, as follows:

0.632 × 10−6 Q3 M
ε∗Top = cosϑ 2T 3 . (7)
W n L de h
!!
h2 125000
log k m = 1.98 + 0.5log (ε∗ × 1000) V − . (8)
dv 2.3RT

In Equation (7), ‘ε∗Top ’ is the stirring energy of top blowing (Watt/ton) and ‘Q T ’ is the
flow rate of the top blowing gas (Nm3 /min). ‘n L ’ and ‘de ’ are the number and diameter (m)
of nozzles, respectively. ‘h’ is the height of the nozzle tip from the surface of the molten
steel (m). ‘M’ and ‘W’ are the molecular weight of the top blowing gas and the total weight
of the metal, respectively. In Equation (8), ‘hV ’ and ‘dV ’ are the height and diameter of
the vessel (m), respectively. The mass transfer coefficients of the components in the slag
phase
Figurewere 10 times lower
15. Comparison than those
of experimental in thewith
values metal phase.
values Table using
calculated 5 presents the input
kap at 1873 data
K shown in
for the 13.
Figure simulations.

Figure 16.
Figure 16. Comparison
Comparison of
of experimental
experimentalvalues
valueswith
withand
andvalues
valuescalculated
calculatedusing
usingkkapap at
at 1973
1973 K
K shown
shown
in Figure
in Figure 13.
13.

3.3. Changes
Table 5. Inputin Molten
data Steel Temperature by Blowing Dry Air after Dissolution of Al Dross and
for simulations.
Coke Mixture
Starting Temperature (K) 1873
The improvement in the molten steel temperature due to the Al dross and coke mix-
ture was verified
Gas flowby measuring
rate (Nm3 /min) the molten steel temperature by0.0001
blowing dry air gas after
(dried air, M = 29 g/mol)
the dissolution of the mixture. The mixing ratio was 0.2 and the mixture was completely
Weight
dissolved at 1873 K offormetal
1 h. (g)
Then, dry air was blown for 1 h at a 90 starting temperature of
1873 K. Furthermore, the coupled reaction model of the BOF process 0.008was used to simulate
Inner diameter of nozzle (m)
the changes in molten steel temperature. The details of this (single
modelnozzle)
have been reported
elsewhereHeight
[19]. The model can simulate
of the nozzle tip (m) the changes in the temperature
0.01 and composition
of molten steeldiameter
Inner and slag of during
crucible top
(m) and bottom blowing. The mass 0.035transfer coefficient of
the components in the metal phase was calculated using the stirring energies of top and
Blowing time (s) 2400
bottom blowing. In the present study, the stirring energy of bottom blowing was fixed at
unity, and the mass transfer coefficient of the components in the metal phase (km) was
Figureusing
calculated 17 shows the images
the stirring of molten
energies steel with
of top blowing, asthe dissolved Al dross and coke
follows:
mixtures and after blowing dried air. In Figure 17a, residue particles from the dissolved
∗
0.632 × 10 𝑄 𝑀
mixtures were observed on the𝜀surface = of the molten steel. As .shown in Figure 17b, a slag
𝑐𝑜𝑠𝜗 (7)
film was formed on the surface of the molten 𝑊 steel after𝑛approximately
𝑑 ℎ 1600 s blowing of
 Height of the nozzle tip (m) 0.01
Inner diameter of crucible (m) 0.035
Blowing time (s) 2400

Figure 17 shows the images of molten steel with the dissolved Al dross and coke
Metals 2022, 12, 1170 13 of 15
mixtures and after blowing dried air. In Figure 17a, residue particles from the dissolved
mixtures were observed on the surface of the molten steel. As shown in Figure 17b, a slag
film was formed on the surface of the molten steel after approximately 1600 s blowing of
dried air.
air. The slag film became thicker during blowing and the temperature decreased, as
shown in Figure 17c.

17. Images
Figure 17. Images ofof molten
moltensteel
steelwith
withdissolution
dissolutionofofthe
theAlAldross
drossand coke
and mixtures
coke and
mixtures blowing
and of
blowing
of dry
dry air:air:
(a)(a) Before
Before blowing;
blowing; (b)(b) Blowing
Blowing at 1600
at 1600 s; (c)
s; (c) After
After blowing.
blowing.

Figure 18 shows the changes changes in the the composition

composition and temperature of molten steel
caused
caused by by blowing
blowingdry dryair airand
andthe thesimulation
simulation results.
results.TheTheblack andand
black redred
lines represent
lines representthe
measured
the measured and and
simulated
simulated temperatures
temperaturesof molten
of moltensteel,steel,
respectively.
respectively.The blue symbols
The blue and
symbols
line
and indicate the measured
line indicate the measured and andsimulated compositions
simulated compositions of carbon in molten
of carbon in moltensteel,steel,
respec-
re-
tively. The green symbols and line denote the measured and
spectively. The green symbols and line denote the measured and simulated compositions simulated compositions of
aluminum in molten steel, respectively. The measured temperature
Metals 2022, 12, x FOR PEER REVIEWof aluminum in molten steel, respectively. The measured temperature increased14 increased significantly
signifi-
of 16
for approximately
cantly 700 s when
for approximately 700 the aluminum
s when in molteninsteel
the aluminum was steel
molten primarily oxidized, and
was primarily oxi-
the aluminum
dized, and thecontent
aluminum decreased.
contentThe molten steel
decreased. temperature
The molten gradually increased
steel temperature gradually as the
in-
carbon content
creased Finally, in
as the carbonthe molten steel gradually decreased. At approximately 1600 s, the mea-
formed.
sured temperature the content
as decreased
slag phase in the
slightly
molten
became
because
steel gradually
thicker
a thinwith
filmthe
of
decreased.
blowing
slag was
At approximately
of dry
formed. air, the meas-
Finally, aswas
the
1600
ured s, the
temperaturemeasured
decreasedtemperature
after 2200decreased
s. Figure slightly
19 shows because
the a
results thin
of film
the of slag
X-ray diffrac-
slag phase became thicker with the blowing of dry air, the measured temperature decreased
tion
after(XRD)
2200 s.analysis
Figure 19 of shows
the slag. theThe slag of
results phase was composed
the X-ray diffractionof Fe3O4analysis
(XRD) and Al2of O3the
, and it
slag.
was generated by the oxidation of aluminum and iron caused
The slag phase was composed of Fe3 O4 and Al2 O3 , and it was generated by the oxidationby blowing air. The simu-
lated and measured
of aluminum and iron results
causedof the
by changes
blowing in air.the
Themolten steel temperature
simulated and measured and the alumi-
results of the
num and carbon contents of molten steel were in good agreement.
changes in the molten steel temperature and the aluminum and carbon contents of molten In conclusion, the mol-
ten steel temperature can be improved by the oxidation of the aluminum
steel were in good agreement. In conclusion, the molten steel temperature can be improved dissolved from
the Al dross.
by the oxidation In the
of thefuture, the electrical
aluminum dissolvedenergy
from consumed
the Al dross. in In
thetheEAF process
future, may be
the electrical
reduced using Al dross and coke mixtures.
energy consumed in the EAF process may be reduced using Al dross and coke mixtures.

Figure18.
Figure Comparison
18.Comparison of of experimental
experimental andand simulation
simulation results
results of changes
of changes in composition
in composition and
and tem-
perature of the
temperature ofmolten steelsteel
the molten by blowing dry air.
by blowing dry air.
Metals 2022, 12, 1170 Figure 18. Comparison of experimental and simulation results of changes in composition and 14
tem-
of 15
perature of the molten steel by blowing dry air.

Figure
Figure 19.19. X-ray
X-ray diffraction
diffraction analysis
analysis forfor slag.
slag.
4. Conclusions
4. Conclusions
We investigated the dissolution concentrations, dissolution ratios, and dissolution rate
We investigated
constants the aluminum
of carbon and dissolutioninconcentrations,
molten steel to dissolution ratios,
utilize coke and Al and
drossdissolution
mixed fuels
rate constants of carbon and aluminum in molten steel to utilize
as chemical energy sources in the EAF process. Furthermore, the changes coke and Al dross
in themixed
molten
fuels
steelastemperature
chemical energy
weresources in theby
investigated EAF process.
blowing dryFurthermore, the changes
air into the melt after theindissolution
the mol-
ten
ofsteel temperature
the coke weremixtures.
and Al dross investigated
Theby blowingresults
following dry airwere
into the melt after the dissolu-
obtained:
tion of the coke and Al dross mixtures. The following results were obtained:
(1) The dissolution experiments of the coke and Al dross mixtures were conducted at
(1) The dissolution
1823–1973 experiments
K. The of the
dissolution coke and Al of
concentrations dross mixtures
carbon were conducted
and aluminum at
in molten
1823–1973 K. The dissolution concentrations of carbon and aluminum in molten
steel increased with the reaction time and molten steel temperature. The dissolution steel
concentration of aluminum in molten steel was constant after 1800 s. At 1823 K
and 1873 K, the dissolution concentration of carbon in molten steel was constant
after 3600 s. At 1973 K, and the dissolution concentration of carbon in molten steel
remained constant after 1800 s. The theoretical oxidation heat was calculated using
the maximum dissolution concentrations of carbon and aluminum in molten steel.
(2) At a constant mixing ratio of coke and Al dross, the maximum dissolution ratio of
carbon and aluminum in molten steel increased with the molten steel temperature. At
a constant molten steel temperature, the effect of the mixing ratio on the maximum
dissolution ratio of carbon and aluminum was not significant. The relationship
between the maximum dissolution ratio of carbon and aluminum in molten steel and
the molten steel temperature was obtained.
(3) The dissolution rate constants of carbon and aluminum increased with the molten
steel temperature. The dissolution concentrations of the coke and Al dross were
calculated using the dissolution rate constants of carbon and aluminum, and the
calculated values were in good agreement with the experimental data.
(4) After the dissolution of the coke and Al dross mixtures, the molten steel temperature
was measured and simulated by blowing dry air into the melt at a starting temperature
of 1873 K. The molten steel temperature increased significantly immediately after
the blowing of dry air started, owing to the oxidation of aluminum. Subsequently,
the molten steel temperature increased gradually, due to the combustion of carbon.
A slag phase was formed at approximately 1600 s after the start of the blowing of
dry air, and it became thicker with the continued blowing of dry air. The slag phase
was composed of Fe3 O4 and Al2 O3 , as determined using XRD. The simulation results
for the changes in the temperature and composition of molten steel showed good
agreement with the measured results.
Metals 2022, 12, 1170 15 of 15

Funding: This research was funded by the Korea Institute of Energy Technology Evaluation and
Planning and the Ministry of Trade, Industry, and Energy of the Republic of Korea, grant number
20212010100060. This research was funded by a research fund from Chosun University, 2017.
Conflicts of Interest: The authors declare no conflict of interest.

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