1

THERMODYNAMIC ANALYSIS OF PHYSICAL AND CHEMICAL

PROCESSES IN THE HIGH-TEMPERATURE REACTION ZONE OF A
LIQUID STEELMAKING BATH
1 2 3
O. Kharchenko , O. Smirnov , O. Volkova
1
Kharchenko Olеksandr, PhD (Engin.), Doctorant of Dept. of Metallurgy,
Engineering Institute, Zaporizhzhya National University, Zhukovskogo St. 66,
Zaporizhzhya, Ukraine. ORСID: 0000-0003-3717-3872, Email: odds@i.ua.
2
Smirnov Oleksiy, Dr. Sci. (Engin.), Professor, Head of Department, Physics and
Technology Institute of Metals and Alloys of the National Academy of Sciences of
Ukraine, Academician Vernadsky Blvd. 36, Kyiv, Ukraine. ORCID: 0000-0001-
5247-3908, Email: stalevoz@i.ua.
3
Volkova Olena, Dr. Sci. (Engin.), Professor, Head of Iron and Steel Institute, TU
“Bergakademie Freiberg”, Akademiestraße 6, Freiberg, Germany. ORCID: 0000-
0001-8647-3885, Email: volkova@iest.tu-freiberg.de.

The work is devoted to the analysis of physical and chemical processes in the
high-temperature reaction zone (HTRZ) aka hot spot, which is formed in
steelmaking processes with oxygen blowing, such as BOF production. Detailed
thermodynamic analysis of HTRZ has been conducted. Parameters of HTRZ have
been determined, such as temperature, masses and chemical composition of
metal, slag and gas phases. It is concluded that the carbon contained in the metal
of HTRZ behaves as a catalyst for the transition of the iron into the gas phase and,
accordingly, the irrevocable loss of iron in the steelmaking process. The results of
the study allowed to build previously unknown fragments of equilibrium phase
diagrams of the high-temperature region of systems "iron-oxygen" and «iron-
oxygen-carbon». Another aspect of this study is removal of impurities from HTRZ.
It is important process in which chemical elements are irretrievably removed from
the space of the steelmaking unit. According to the temperature and the degree of
removal into the gas phase, studied impurities can be divided into three groups: a)
carbon, which is almost completely removed at a relatively low total oxygen content
in the HTRZ and temperatures up to 2000°C; b) silicon, calcium, magnesium and
phosphorus, which are almost completely removed into the gas phase in the
temperature range of 2100...2800°C; c) manganese, sulfur, iron and aluminum,
which are partially removed at temperatures above 2600°C. With an increase in the
total oxygen content in the HTRZ above 15%, temperature increase sharply slows
down, reaching limit of 2900°C at a total oxygen content of 20%. In this case, iron
intensively escapes into the gas phase along with impurities. Therefore, blowing
the steelmaking bath with oxygen at a very high rate is inappropriate, since it does
not lead to a significant increase in the productivity of steelmaking unit.
Keywords: hot spot, reaction zone, steelmaking bath, oxygen blowing,
oxygen converter, impurities, Gibbs energy, chemical potential.

Introduction
Studies of high-temperature reaction zones (HTRZ) in steelmaking processes
with oxygen blowing have a number of theoretical and practical aspects that
determine their exceptional importance in the context of creating new efficient
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technologies and design systems for converter melting. First, the concept of
reaction zone (RZ) based on the principle of quasi-local equilibrium has existed for
quite a long time as a means of describing non-equilibrium processes that
inevitably arise when materials are introduced into a liquid bath [1]. This concept is
an alternative to solving a system of dynamic differential equations with respect to
the numbers of moles of chemical elements in the metal, slag, and gas phase [2].
Second, the consideration of any reaction zone, including HTRZ, is always
associated with the need for a priori estimation of their boundaries and volumes [3].
In most cases, such estimates do not have sufficient justification due to the
continuous change in any parameters of the liquid steel bath along its cross
section. Therefore, it often becomes necessary to split the reaction zone into
smaller structural components, within which the constancy of certain individual
parameters is postulated. Thirdly, the known state diagrams “iron-oxygen” and
“iron-oxygen-impurity element” do not contain information on the phase equilibria at
temperatures above 1900 °C. In particular, for such temperatures there are no data
on the pressure and composition of the gas phase. Fourthly, any HTRZ calculation
assumes partial (as a rule) or complete mixing of two or more “metal-slag-gas”
systems with different temperatures. In this relation, a special role is played by the
accurate calculation of the material and enthalpy heat balances taking into account
the chemical interaction of the components.
An important criterion for the correctness of any calculations involving reaction
zones is the equality of the final results of bringing all reaction zones into complete
equilibrium with the basic system “metal-slag-gas” with an arbitrary choice of
technological process trajectory. In particular, in the complete absence of reaction
zones, the final calculation result should be the same. This is explained by the fact
that the thermodynamic equilibrium in the system is described by integral state
variables (Gibbs energy, enthalpy and entropy) that do not depend on the process
trajectory. Of course, a closed thermodynamic system is considered, and all its
parts without exception are brought to equilibrium. In real processes, the difference
from complete equilibrium can be due to the partial escape of the substance from
the system through the gas phase and the low rate of heat and mass transfer at
the interphase boundaries and in the volume of the phases themselves.
Regardless of how far the real system from the equilibrium state is, the result of
bringing it into equilibrium, taking into account losses to the gas phase, should be
the same for any technological process trajectory.

Part 1. Iron-oxygen, iron-oxygen-carbon systems

1.1. Problem statement
Objective of the work is to perform a thermodynamic analysis of physical and
chemical processes in the high-temperature reaction zone of a liquid steelmaking
bath when it is blown with oxygen. The model system includes the main elements:
iron, oxygen and carbon. The influence of the inevitable impurities of silicon,
manganese, sulfur and phosphorus, inherent to the real steelmaking processes,
and their removal from the gas phase will be considered in the next part.
1.2. Research methodology
The Gibbs method of chemical potentials [4] is a universal tool for studying
HTRZ. It is implemented in the “Excalibur” research software package [5-7]. This
program uses thermodynamic models of multicomponent condensed phases for
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liquid metal [8-10] and slag [11], as well as thermal model of the “metal-slag-gas”
thermodynamic system [12; 13]. It can simulate a high-temperature reaction zone
around an oxygen jet in a liquid steelmaking bath. It is assumed that the total
oxygen content in the HTRZ is a value proportional to the intensity of oxygen
3
blowing through the liquid steelmaking pool. At a blowing rate of 4-5 m /(t·min), iron
losses to the gas phase are 1-1.5 wt.% [14], which corresponds to the total oxygen
content in the HTRZ at a level of 15–16 wt.%. In the real conditions of steelmaking,
the correspondence between the intensity of blowing, iron losses and the total
oxygen content in the HTRZ is the subject of an adaptive calculation, taking into
account all factors, based on the data of balance heats.
For the modeling, the average initial temperature of the metal was taken equal
to 1500 °C, when the “metal-slag” system was already fully formed during the
blowing process. The initial carbon content in the HTRZ metal was varied from 0 to
4 wt.%. The total oxygen content in the system was varied from 0 to 18 wt.%. In
the calculations, the initial mass of the HTRZ was assumed to be 100 tons. The
processes occurring in the HTRZ are autothermal, that is, without external heat
sources and energy supply.
It is obvious that during the bottom blowing, one should take into account the
additional ferrostatic pressure of the metal in the range of 100-200 kPa, depending
on the depth of the liquid metal in a given melting period and the configuration of
the steelmaking unit.
1.3. Temperature and oxygen content in metal phase of the reaction zone
Figure 1, a shows results of calculations of the HTRZ temperature depending
on the oxygen content in it and the initial carbon content in the liquid metal.

a) b)
Figure 1 – Effect of the total oxygen content in HTRZ and initial carbon content
in the liquid metal (numbers at curves in wt.%) on the temperature of reaction zone (a) and oxygen
content in the metal phase (b)

Figure 1, a is a good illustration of the fact that by increasing the blowing

intensity it is impossible to achieve an arbitrary increase in the temperature of the
HTRZ, and, consequently, the temperature of the steelmaking bath. As can be
seen from the graph, the upper temperature limit of any HTRZ is the black curve for
the Fe-O system without carbon. With a total oxygen content in the system of 15-
20 wt.% and a temperature of 2928 °С in the reaction zone, a high-temperature
non-variant equilibrium is established, at which a further increase in the oxygen
content in the HTRZ does not lead to a change in the temperature and chemical
 4

composition of all phases. In fact, the horizontal section of the carbon-free (black)
curve in Fig. 1 is a previously unknown fragment of the “iron-oxygen” phase
diagram. With an increase in the total oxygen content in the carbon-free HTRZ
above 15 wt.%, the evolution of a gas phase begins, which is composed (in
descending order of partial pressure) of Fe, FeO, O, O2, FeO2, O3 molecules. At
the same time, there is a decrease in the mass of the metal phase and a further
increase in the mass of slag, consisting of iron oxide. On a horizontal section, an
increase in the initial temperature of the metal over 1500 °С has the same effect as
an increase in the oxygen content in the HTRZ, that is, it leads to a redistribution of
the masses of the phases with a constant chemical composition and temperature.
At total oxygen content of 20 wt.%, complete oxidation of the metal occurs,
and only slag and the gas phase remain in the system. A further increase in the
total oxygen content in the HTRZ leads to a slight increase in temperature above
2928 °C.
For the carbon containing HTRZ, the temperature increases in proportion to
the total oxygen content until the carbon burns out of the metal to trace
concentrations. It is obvious when Fig. 1, a is compared with the graph in Fig. 5, a.
Figure 1, b shows change in the oxygen content in the metal phase depending
on the total oxygen content in HTRZ and initial carbon content in metal. It
corresponds to the temperature changes shown in Fig. 1, a. Solubility limit of
oxygen in the metal at a temperature of 2928 °C was found to be 9.67 wt.%. At
such oxygen content, the graph of the carbon-free curve shows the same
horizontal area as for the temperature of the system in a state of non-variant
equilibrium. All curves for the carbon containing HTRZ lie below the non-carbon
curve, and correspond to the lower temperatures. The temperature range in Fig. 1,
a is consistent with experimental and modeling data of Lee and Kolbeinsen [ 15].
1.4. Solubility of oxygen in iron as function of temperature
If the data of the same graphs in Fig. 1 presented in the coordinates “X –
oxygen content in the metal” and “Y – temperature”, it becomes obvious that even
with an oxygen content in the metal of 1 wt.%, almost all carbon goes into the gas
phase, and all the curves merge into one curve – the curve of the solubility of
oxygen in iron up to the limiting point corresponding to the temperature of the
system 2928 °C. This dependence is shown in Figure 2. In the temperature range
up to 1800 °C, the curve corresponds to Fontana-Chipman experimental data [16].

a) b)
Figure 2 – Solubility of oxygen in iron depending on the temperature and initial carbon content in the
metal (numbers at curves in wt.%): scales of 10% (a) and 1% (b) of [O]
 5

1.5. Slag to metal and gas to metal phase ratios

Figure 3 shows the effect of the total oxygen content in HTRZ on the slag to
metal and gas to metal phase ratios in weight percent. Figure 3, a indicates that
the formation of oxide slag in the HTRZ occurs at a higher total oxygen content as
carbon content in metal increases. At the same time, the carbon-containing HTRZ
feature a noticeable deviation of the oxygen solubility curves from this value for the
HTRZ without carbon, as can be seen in Fig. 2, b. On this graph, the points of
contact of the curves for HTRZ with carbon with the carbon-free curve correspond
to the beginning of the formation of oxide slag during almost complete oxidation of
carbon and its escape into the gas phase.

a) b)
Figure 3 – Effect of the total oxygen content in HTRZ and initial carbon
content in the liquid metal (numbers at curves in wt.%) on the slag to metal (a)
and gas to metal (b) phase ratios of reaction zone

As can be seen in Fig. 3, b, in the carbon-free HTRZ, gas phase begins to

evolve at a total oxygen content of more than 15 wt.%, while for the HTRZ with
carbon, the formation of a gas phase is typical at any non-zero oxygen content in
the reaction zone. At low oxygen contents and relatively low temperatures, the gas
phase consists mainly of CO and CO2. An increase in the iron content in the gas
phase is observed only when the total oxygen content in the HTRZ exceeds 5
wt.%, as shown in Fig. 4, a.
For the carbon containing HTRZ, gas to metal phase ratio increases in
proportion to the total oxygen content in the range from 0 to 5 wt.%, i.e. until the
carbon burns out from the metal to trace concentrations – similar to how the
system temperature increases (Fig. 1). After that, the evolution of the gas phase
temporarily slows down, and then accelerates again when the total oxygen content
in the HTRZ exceeds 10 wt.%.
1.6. Content of iron in the gas phase
Figure 4 shows the effect of the total oxygen content in HTRZ on the
elementary content of iron in the gas phase. It is obvious that in carbon-containing
HTRZ, after the carbon is burnt out from the metal at a total oxygen content of
more than 5 wt.%, an intensive escape of iron into the gas phase starts. This
process is accompanied by a synchronous decrease in the carbon content and an
increase in the iron content in the gas phase. In addition, comparison of Figs. 4, b
and 5, a allows to conclude that when the carbon content in the metal is more than
0.1 wt.%, the content of this element in the gas phase remains at a high level (42.8
 6

wt.%), which corresponds to the predominant content of carbon monoxide CO in

the gas phase (99.8 wt.%) and a small amount of CO2 (0.2 wt.%). With a decrease
in the carbon content in the metal below 0.1%, the gas phase is gradually
saturated with atomic iron and iron compounds FeO and FeO2. At a temperature of
2928°C in the Fe-O system , the total iron content in the gas phase of the HTRZ is
93.75 wt.%, of which 82.7 wt.% is atomic iron. The latter, reacting with air or blown
oxygen, forms Fe2O3 oxide, which leaves the steelmaking bath in the form of brown
smoke.

a) b)
Figure 4 – Effect of the total oxygen content in HTRZ and initial carbon content in the liquid metal
(numbers at curves in wt.%) on the elementary content of iron in the gas phase of reaction zone:
in wt.% (a) and tons (b)

An increase in the oxygen content in the HTRZ over 20 wt.% leads to the total
oxidation of the metal. Also, the content of molecular oxygen sharply increases in
the exhaust gas, and therefore the efficiency of oxygen blowing decreases. With an
extremely high total oxygen content in the HTRZ of over 28 wt.%, most of the gas
phase consists of O2 molecules. With a total oxygen content of 36 wt.%, molecular
oxygen O2 in the exhaust gas phase accounts for 81 % of the total partial pressure;
atomic oxygen accounts for 8.4%, atomic iron 5.6%, FeO 4.5%, FeO2 – less than
0.5%.
Based on the data presented in fig. 3, b and 4, it can be concluded that the
carbon contained in the HTRZ metal has been a catalyst for the escape of iron into
exhaust gas phase and, accordingly, the loss of iron in the steelmaking process. It
is especially well illustrated in Fig. 4, b where the iron content in the gas phase is
presented in absolute weight units. This graph shows that the weight of iron in the
gas phase grows exponentially with an increase in the total oxygen content in the
carbon-containing HTRZ. However, the difference in the trajectories of curves with
different carbon contents is relatively small. Non-carbon (black) curve becomes
close to the curves with carbon only at high total oxygen content (above 17 wt.%).
In a wide range of the total oxygen content, and, consequently, the blowing
intensity, the presence of carbon in any concentration leads to an intensive escape
of iron into the gas phase. This effect is less significant at a bottom blowing, when
the ferrostatic pressure reduces evolution of the gas phase.
1.7. Content of carbon in the metal and gas phase
Figure 5 shows the dependence of the carbon content in the metal and gas
phase of the reaction zone on the total oxygen content in the HTRZ and initial
carbon content in metal. It is obvious that the degree of carbon burnout in the
 7

HTRZ linearly depends on the oxygen content in the HTRZ (Fig. 5, a) and,
consequently, on the blowing intensity. Only at small values of carbon content, an
exponential approach to the zero horizontal is observed. Graphs in Fig. 5, a are
consistent with those obtained in the recent work of Singha and Shukla [ 17] with
blowing time as an independent variable.
Carbon content in the gas phase expectedly decreases with an increase in the
iron content as shown in Fig. 5, b.

a) b)
Figure 5 – Effect of the total oxygen content in HTRZ and initial carbon content in liquid metal (numbers
at curves in wt.%) on the content of carbon in the metal (a) and gas (b) phase of reaction zone

1.8. High temperature phase diagrams for Fe-O and Fe-O-1%C systems
Analysis of all the data obtained in the work made it possible to build a
previously unknown fragment of the phase equilibrium diagram in the “iron-oxygen”
system in the high-temperature region, shown in Figure 6, a. The diagram has five
areas: “metal”, “gas”, “metal+gas”, “metal+slag” and “slag+gas”. The dotted line
separating the areas of gas and the coexistence of slag and gas is an estimate.
The diagram shows that with an increase in the oxygen content in iron, the
temperature interval for the coexistence of the metal and gas phases increases to
a limit value of 2928 °C. The coexistence of three phases simultaneously – metal,
slag and gas – is possible on a horizontal peritectic line at a temperature of 2928
°С in a wide range of oxygen concentrations in the system. This line is also called
the three-phase invariant equilibrium isotherm. Within this line, composition of the
phases remains constant. Only their relative amounts change. The curve
separating the regions of metal and the coexistence of metal and slag is a high-
temperature fragment of the oxygen solubility curve in liquid iron (Fontana-
Chipman curve) shown in Fig. 2. The maximum oxygen content in the metal on this
line is 9.67 wt.% at a temperature of 2928 °C.
 8

a) b)
Figure 6 – High-temperature region of the phase equilibrium diagrams for the systems
“iron-oxygen” (a) and “iron-oxygen-1% C” (b) at a pressure of 1 atm

The effect of carbon on the equilibrium diagram Fe-O is significant. Carbon,

even at low concentrations, radically changes the appearance of the diagram, as
can be seen in Figure 6, b. This is explained by the fact that at high temperatures
almost all carbon is oxidized to form gaseous oxides. Therefore, there are no
regions without a gas phase in the diagram, except for a very narrow region at
temperatures below 2873 °C. The quadruple point with coordinates 7.47 wt.% O
and 2916 °C is of particular interest. At this point, the system consists only of gas
phase, but, depending on the direction of change in temperature and oxygen
content, metal, slag, or metal with slag can be added to the gas phase.

Part 2. Removal of impurities

Removal of impurities from the gas phase of a liquid steelmaking bath is an
important process in which chemical elements are irretrievably removed from the
space of the steelmaking unit. There is a need to study this process in detail when
blowing a liquid iron-carbon melt with oxygen in order to effectively control the
technological parameters of melting. The work studies the behavior of iron and
impurities of carbon, oxygen, silicon, manganese, aluminum, sulfur, phosphorus,
calcium and magnesium in the gas phase of the high-temperature reaction zone
(HTRZ) of a liquid steelmaking bath when it is blown with oxygen, taking into
account the influence of all components of the thermodynamic system “metal-slag-
gas”.
In the first part of this study, the behavior of three elements – iron, oxygen,
and carbon – was studied in detail in the high-temperature reaction zone (HTRZ) of
a steelmaking bath when it is blown with oxygen [18; 19]. This process is typical for
the oxygen-converter method (BOF) for the production of liquid steel semi-product.
Due to the extreme complexity of organizing an accurate measurement of the
composition of the gas phase of HTRZ at temperatures above 2000 °C,
thermodynamic modeling appears to be the only way to obtain quantitative
characteristics of the processes of removal of impurities in the process of oxidative
refining of steel, necessary for the effective design and control of steel melting.
Unlike condensed phases, the calculation of the thermodynamic functions of
the gas phase of arbitrary composition is possible with high accuracy, in particular,
due to the vast array of tabular data in the Glushkov reference book [22] and the
Astra databases [23]. The high accuracy of complex thermodynamic calculations
 9

involving the gas phase made it possible to build phase equilibrium diagrams in the
high-temperature region in Fe-O and Fe-O-C systems [18].
There is an assumption, based on the analysis of the change in the Gibbs
energy in the standard state, that when the steelmaking bath is blown with oxygen,
any impurities present in the liquid melt, except for oxygen, are removed
synchronously (figurative expression: “they ride in the same tram”) [21]. However,
industrial practice shows that this principle is fulfilled only in the marginal case of
total oxidation. In the general case, it is necessary to take into account the
peculiarities of the behavior of each chemical element not only in the condensed
phases of HTRZ, but also in the gas phase, the composition of which changes
significantly at high temperatures.
Removal of impurities from the gas phase seems to be especially important
process in which the irretrievable escape of chemical elements from the space of
the steelmaking unit occurs. Removal of iron results in its losses, which reduce the
technical and economic indicators of melting. The desire to remove impurities as
much as possible in the process of blowing metal with oxygen is always associated
with the probability of unacceptable losses of iron. Thus, there is a need to study in
detail the process of removing impurities when blowing a liquid iron-carbon melt
with oxygen in order to effectively control this process at the technological level.
2.1. Formulation of the problem
The aim of this work is to perform a thermodynamic analysis of physical and
chemical processes in the high-temperature reaction zone of a liquid steelmaking
bath when it is blown with oxygen, taking into account the influence of all
components of the “metal-slag-gas” thermodynamic system. The model system
includes the main elements: iron, oxygen and carbon, as well as impurities of
silicon, manganese, aluminum, sulfur, phosphorus, magnesium, and calcium,
which are typical for real steelmaking processes.
2.2. Research methodology
The average initial temperature of the metal was taken equal to 1500 °C.
Table 1 shows the initial composition of the metal and slag of the HTRZ, based on
the observed average values. The initial slag to metal phase ratio was taken equal
to 0.01, which means that the initial composition of the HTRZ is formed mainly from
metal and partly from slag.

Fe/FeO C Si/SiO2 Mn/MnO S P/P2O5 Al/Al2O3 Ca/CaO Mg/MgO

Metal > 99 0.2 0.1 0.1 0.1 0.1 < 0.01 < 0.001 < 0.001
Slag 15 tr. 30 5 0.1 0.1 2.0 40 7.8
Table 1 – Chemical composition of initial metal and slag in wt. %

Gaseous oxygen is added to the original metal (100 t) and slag (1 t) in an

amount of 0 to 25 t, which corresponds to the total oxygen content in the reaction
zone (including oxides) from 0.36 to 20.1 wt.%. The last value for the selected
initial data can be related to the intensity of the liquid metal bath blowing with
oxygen by a simple empirical relation OHTRZ = 2.5÷3.5·i, where the blowing intensity
3
i has the dimension m /(t·min). That is, the total oxygen content in the reaction
zone is proportional to the intensity of the blowing (if the small values of OHTRZ,
which are not typical for the main blowing modes, are neglected) [19; 20].
 10

2.3. Composition of the gas phase and temperature of reaction zone

Figures 7, a-c show the change in the elementary composition of the gas
phase of the HTRZ in relative units depending on the total oxygen content. The
main inherent feature of this process is the gradual increase in the iron content in
the HTRZ gas up to 88 wt.%. This is also the reason for the decrease in the
relative content of all other elements at high total oxygen content. Most impurities
(Si, Ca, Mg, P, S, and Mn) are characterized by maxima on the curves “OHTRZ –
content of the element in the gas phase”. As it can be seen in Fig. 7, b, among
these impurities, silicon reaches the maximum concentration 12.8 wt.% in the gas
phase. The maximum concentration of phosphorus is about 2 wt.%.
Impurities of alkaline earth elements (calcium and magnesium) have a
negligible solubility in the liquid metal during oxidative refining and, accordingly, a
low concentration in the gas phase at ordinary steelmaking bath temperatures.
However, at high HTRZ temperatures (above 2000 °C), their concentration in these
phases increases significantly due to the redistribution of calcium and magnesium
from the oxide slag, into which these elements enter from the non-metallic part of
the charge materials and the lining of the unit. The calcium concentration in the
HTRZ gas phase reaches 9 wt.%, and magnesium 2.5 wt.%.

a) b)

c) d)
Figure 7 – Effect of the total oxygen content in HTRZ on the elementary composition
of the gas phase (a-c) and final temperature (d)

The change in the temperature of the HTRZ depending on the value of OHTRZ
is shown in Figure 7, d. At the maximum value of OHTRZ = 20 wt.% (i = 6.7
3
m /(t·min)) the local temperature of HTRZ reaches 2900°C. The monotonicity of the
 11

temperature dependence, in principle, allows all graphs to be plotted in the

coordinates “temperature – content of an element in a gas phase”. Then each
maximum content of the element in the gas will correspond to a specific
temperature.
Concentrations of impurities in the gas phase of the HTRZ at certain levels of
OHTRZ (or temperature) can be many times higher than the concentrations of these
elements in the original metal of the steelmaking bath, which creates preconditions
for their effective removal in the process of oxidative refining. However,
concentrations of elements in the gas phase of the HTRZ, shown in Fig. 7, a-c, do
not provide complete quantitative information about the redistribution of impurities
between the phases. Therefore, it is important to obtain additional information
about the absolute values of the masses of the elements in each of the phases.
2.4. Composition of the gas phase in absolute units
Figure 8 shows the change in the composition of the gas phase of the HTRZ
in absolute units (kilograms) depending on the total oxygen content. As it can be
seen, the content of all chemical elements without exception, including impurities,
increases monotonically with an increase in the total oxygen content, despite the
specific maxima of the contents in relative units (Fig. 7, b-c). The behavior of iron is
characterized by a sharp increase in its content with an increase in OHTRZ over 12
wt.%, which corresponds to an HTRZ temperature above 2600 °C and a blowing
3
intensity of more than 4 m /(t·min). Most impurities (except for manganese and
sulfur) are characterized by saturation areas, that is, reaching maximum content
level, at different values of OHTRZ. Coordinates of the maximum increase in the
mass of impurities in the gas coincide with the coordinates of the maxima of their
relative content shown in Fig. 7, b-c. It can be assumed that manganese and sulfur
behave in a similar way, but at higher temperatures (more than 2900 °C) which
cannot be achieved in the auto-thermal process by blowing iron-carbon melt with
oxygen.
Saturation of the gas phase with carbon occurs already at a total oxygen
content in the HTRZ of 5 wt.%, which corresponds to a temperature of 2080 °C and
3
a blowing intensity of 1.7 m /(t·min). This means that carbon can be removed from
the melt by blowing it with a low-intensity oxygen jet, which is used, in particular, in
electric steelmaking.

a) b)
Figure 8 – Dependence of elementary composition of the gas phase of HTRZ
from the total oxygen content: a) Fe, O (tons); b) C, Si, Ca, Mg, Mn, P, S (kg)
 12

2.5. Phase composition of reaction zone

It should be noted that composition of the HTRZ gas phase in absolute units,
shown in Figure 8, does not fully explain the saturation and the outgo of the curves
to the horizontal at large values of OHTRZ. In particular, there is no clarity about the
possibility of changing the course of the curves outside the studied range, that is,
OHTRZ > 20 wt.%. To clarify this issue, dependencies of the phase fraction of
elements in the gas phase and the phase composition of the HTRZ from the total
oxygen content are shown in Figure 9. The phase fraction of an element is defined
as the percentage ratio of the mass of an element in gas to the mass of this
element in the entire “metal-slag-gas” system.
The course of the curves in Figure 9, a explains the behavior of a number of
chemical elements in Figure 8, b by the fact that, regardless of their initial content
in the metal, they almost completely pass into the gas phase. In the range of OHTRZ
= 5…15 wt.%, an almost complete synchronous transition of a group of elements
(Si, Ca, Mg, P) from metal and slag into gas occurs. Another group of elements
(Mn, S, Fe, Al) begins the transition to the gas phase, starting from OHTRZ = 10
wt.%. However, even at the maximum studied total oxygen content in the HTRZ
(20 wt.%), only a partial transition of elements is observed in this group. The fact
that iron, which is present in this group, dominates in terms of relative and absolute
content in the gas phase at high values of OHTRZ, is explained by the overall high
content of this element in HTRZ. Carbon, which almost completely passes into the
gas phase of HTRZ at OHTRZ ≤ 5 wt.%, behaves separately and is not included in
any of the above groups.

a) b)
Figure 9 – Dependence of the phase fraction of elements in the gas phase (a)
and the phase composition of HTRZ (b) from the total oxygen content

As it can be seen in Figure 9, b, a significant increase in the mass of the gas

phase occurs when the total oxygen content in the HTRZ is above 10 wt.%, which
corresponds to a temperature above 2500 °C and a blowing intensity of more than
3
3.3 m /(t·min). At the maximum value of OHTRZ = 20 wt.%, the mass of the HTRZ
gas phase, in which the majority is iron, exceeds 20 tons. At the same time, almost
complete oxidation of the metal occurs. The main product of HTRZ is highly
oxidized slag, in which the proportion of iron oxides is more than 90% at OHTRZ > 4
wt.% and more than 99% at OHTRZ > 12 wt.%. In a real steelmaking process, the
FeO content in the slag rarely exceeds 50 wt.%, which allows us to conclude that
the HTRZ slag is assimilated by the steelmaking bath, so that some of the iron
oxides remain in the slag, and some are reduced. In this case, reduction occurs in
 13

two possible ways: 1) by interaction with the rest of the metal of the steelmaking
bath at the “metal-slag” interface and 2) by decomposition of FeO due to shift in the
equilibrium of the reaction [Fe] + [О] = (FeO) to the left side, based on
thermodynamic conditions in the steel bath outside the HTRZ.
2.6. Molecular composition of the gas phase
Figure 10 shows the molecular composition of the HTRZ gas phase in the
form of partial pressures of individual components. As it can be seen, the presence
of oxygen in the gas phase in a wide range is mainly due to the presence of carbon
oxides CO and CO2, which dominate at temperatures up to 2000 °C. However, with
an increase in the total oxygen content in HTRZ above 5 wt.%, and, accordingly,
temperatures above 2000 °C, the role of other gaseous compounds, such as SiO
and FeO, increases. At OHTRZ > 10 wt.%, there is a clear trend towards an increase
in the partial pressure of oxygen in the free state (O and O2) and a significant
increase in the content of atomic iron and FeO oxide.

a) b)
Figure 10 – Partial pressure of molecular and atomic gases in the gas
phase of HTRZ: a) CO, CO2, Fe, SiO; b) Ca, FeO, Mg, O, O2, PO, CaO

Transition of silicon into the gas phase occurs mainly due to the formation of
gaseous SiO oxide, the maximum concentration of which is reached at OHTRZ = 9
wt.%. Calcium and magnesium mostly pass into the gas phase in the atomic state.
Their maximum concentration is achieved at OHTRZ = 12.4 wt.% and 10 wt.%,
respectively. Phosphorus in the gas phase is present in the form of PO monoxide.
There are also two dozens gaseous compounds whose partial pressures vary
from 0.01 to 1 kPa (Mn, SiO2, MgO, PO2, SO, SO2, etc.), and hundreds of
compounds with vanishingly low concentrations that were not shown on charts.
However taken together, these compounds can make a significant contribution to
the total pressure of some individual elements.
Conclusions
1. The effect of the total oxygen content on the following high-temperature
reaction zone parameters was studied: temperature, slag to metal and gas to metal
phase ratios, chemical composition of the metal and gas phases. It has been
established that by increasing the blowing intensity it is impossible to achieve an
arbitrary increase in the temperature of the HTRZ, and, consequently, the
temperature of the steelmaking bath. The influence of the initial carbon content in
the metal on the parameters of the HTRZ has been studied. It was shown that the
carbon contained in the HTRZ metal has been a catalyst for the escape of iron into
 14

the gas phase and, accordingly, the loss of iron in the process of steelmaking.
Fragments of the phase equilibrium diagrams in the “iron-oxygen” and “iron-
oxygen-1% C” systems in the high-temperature region have been built.
2. The general trend in the behavior of impurities in HTRZ is manifested in the
fact that different impurities have a maximum concentration in the gas phase at a
certain temperature, which depends on the intensity of blowing. The impurity
concentration maxima are explained by the fact that the iron concentration
gradually increases in the gas phase up to the limiting value (almost 90%). These
maxima indicate the beginning of intensive removal of one or another impurity. In
absolute units, as the temperature increases, transition of given impurity into the
gas phase does not decrease, and in the general case no maxima are observed.
3. According to the temperature and the degree of removal into the gas phase,
studied impurities can be divided into three groups: a) carbon, which is almost
completely removed at a relatively low total oxygen content in the HTRZ and
temperatures up to 2000 °C; b) silicon, calcium, magnesium and phosphorus,
which are almost completely removed into the gas phase in the temperature range
of 2100...2800 °C; c) manganese, sulfur, iron and aluminum, which are partially
removed at temperatures above 2600 °C.
4. With an increase in the total oxygen content in the HTRZ above 15 wt.%,
the temperature increase sharply slows down, reaching the limit of 2900 °C at
OHTRZ = 20 wt.%. In this case, iron intensively passes into the gas phase along with
impurities. In addition, a significant amount of slag is formed, consisting mainly of
iron oxides. Therefore, blowing the steelmaking bath with oxygen at a rate of more
3
than 5 m /(t·min) is not justified, since it does not lead to a significant increase in
the productivity of the steelmaking unit. In addition, due to significant losses of iron,
the technical and economic indicators of heat are reduced.

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