Revisiting the Rist Diagram for Predicting Operating Conditions in Blast Furnaces With Multiple Injections

Open Research Europe Open Research Europe 2021, 1:141 Last updated: 02 MAR 2023
RESEARCH ARTICLE
Revisiting the Rist diagram for predicting operating

conditions in blast furnaces with multiple injections [version
1; peer review: 2 approved]
Manuel Bailera 1,2, Takao Nakagaki3, Ryoma Kataoka4
1Graduate School of Creative Science and Engineering, Waseda University, Tokyo, 1698555, Japan
2Escuela de Ingeniería y Arquitectura, University of Zaragoza, Zaragoza, 50018, Spain
3Department of Modern Mechanical Engineering, Waseda University, Tokyo, 1698555, Japan
4Exergy Engineering Research, Nakagaki Lab, Waseda University, Tokyo, 1698555, Japan
v1 First published: 29 Nov 2021, 1:141 Open Peer Review

https://doi.org/10.12688/openreseurope.14275.1
Latest published: 29 Nov 2021, 1:141
https://doi.org/10.12688/openreseurope.14275.1 Approval Status
1 2
Abstract
Background: The Rist diagram is useful for predicting changes in version 1
blast furnaces when the operating conditions are modified. In this 29 Nov 2021 view view
paper, we revisit this methodology to provide a general model with
additions and corrections. The reason for this is to study a new
1. Johannes Schenk , Montanuniversität
concept proposal that combines oxygen blast furnaces with Power to
Gas technology. The latter produces synthetic methane by using Leoben, Leoben, Austria
renewable electricity and CO2 to partly replace the fossil input in the
2. Eleonora Bargiacchi, IMDEA Energy
blast furnace. Carbon is thus continuously recycled in a closed loop
and geological storage is avoided. Institute, Madrid, Spain
Methods: The new model is validated with three data sets
corresponding to (1) an air-blown blast furnace without auxiliary Any reports and responses or comments on the
injections, (2) an air-blown blast furnace with pulverized coal injection article can be found at the end of the article.
and (3) an oxygen blast furnace with top gas recycling and pulverized
coal injection. The error is below 8% in all cases.
Results: Assuming a 280 tHM/h oxygen blast furnace that produces
1154 kgCO2/tHM, we can reduce the CO2 emissions between 6.1% and
7.4% by coupling a 150 MW Power to Gas plant. This produces 21.8
kg/tHM of synthetic methane that replaces 22.8 kg/tHM of coke or 30.2
kg/tHM of coal. The gross energy penalization of the CO2 avoidance is
27.1 MJ/kgCO2 when coke is replaced and 22.4 MJ/kgCO2 when coal is
replaced. Considering the energy content of the saved fossil fuel, and
the electricity no longer consumed in the air separation unit thanks to
the O2 coming from the electrolyzer, the net energy penalizations are
23.1 MJ/kgCO2 and 17.9 MJ/kgCO2, respectively.
Discussion: The proposed integration has energy penalizations
greater than conventional amine carbon capture (typically 3.7 – 4.8
MJ/kgCO2), but in return it could reduce the economic costs thanks to
diminishing the coke/coal consumption, reducing the electricity
consumption in the air separation unit, and eliminating the
Page 1 of 30
requirement of geological storage.
Keywords
Blast furnace, Rist diagram, ironmaking, operating diagram, Carbon
capture, Power to Gas, Oxyfuel combustion, CO2
This article is included in the Marie-Sklodowska-

Curie Actions (MSCA) gateway.
This article is included in the Chemical

Engineering gateway.
Corresponding author: Manuel Bailera ([email protected])

Author roles: Bailera M: Conceptualization, Data Curation, Formal Analysis, Funding Acquisition, Methodology, Project Administration,
Software, Validation, Visualization, Writing – Original Draft Preparation; Nakagaki T: Conceptualization, Funding Acquisition, Project
Administration, Resources, Supervision, Writing – Review & Editing; Kataoka R: Formal Analysis, Validation
Competing interests: No competing interests were disclosed.
Grant information: This project has received funding from the European Union’s Horizon 2020 research and innovation programme
under the Marie Skłodowska-Curie grant agreement No 887077.
The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.
Copyright: © 2021 Bailera M et al. This is an open access article distributed under the terms of the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
How to cite this article: Bailera M, Nakagaki T and Kataoka R. Revisiting the Rist diagram for predicting operating conditions in
blast furnaces with multiple injections [version 1; peer review: 2 approved] Open Research Europe 2021, 1:141
https://doi.org/10.12688/openreseurope.14275.1
First published: 29 Nov 2021, 1:141 https://doi.org/10.12688/openreseurope.14275.1
Page 2 of 30
Open Research Europe 2021, 1:141 Last updated: 02 MAR 2023
Plain language summary moderate reductions, water electrolysis power capacities of

The steel industry is one of the most CO2 emitting industries about 880 MW would be required. Additionally, Bailera et al.4
worldwide. In this article we study the possibility of recycling proposed a novel concept that combines power to methane
the CO2 that is emitted in order to produce natural gas. Thus, with oxygen blast furnaces (OBF). In the OBF, pure oxygen
the CO2 emissions are converted to a useful fuel instead of is used for combustion instead of air, thus obtaining a top gas
released to the atmosphere. For this process, renewable elec- with very little nitrogen. In this type of blast furnace, it is usual
tricity is used, so the natural gas produced can be considered to separate the CO2 from the top gas and to recycle the H2 and
environmentally friendly. With this natural gas we want to replace CO content again to the blast furnace to act as reducing agents
the fossil fuel that is conventionally used in the steel industry. and as a heat sink (because N2 is no longer present)7. Since
To make this study we have used a mathematical model that water electrolysis of the PtG process by-produces O2, it allows
was developed by a researcher named Rist between 1963 diminishing the electricity consumption of the air separa-
and 1967. We made some corrections and additions to this tion unit that feeds the OBF. A first approach to this OBF–PtG
mathematical model to make it more accurate. The results of system was studied by Perpiñán et al.8 by using overall energy
this study show that the CO2 emissions can be reduced between and mass balances. Assuming 430 MW electrolysis power capac-
6.1% and 7.4% by using commercially available technology. ity, they found a CO2 emission reduction of 8% and specific
electricity consumptions of 34 MJ/kgCO2.
1. Introduction
The potential contribution of carbon capture and utilization to the In order to deep in the concept of OBF–PtG integration, a
global warming mitigation challenge has shown to be very lim- more detailed analysis of the behavior of the blast furnace is
ited when compared with geological storage or electrification1,2. required. To do so, the Rist diagram (also known as the operat-
If we talk in particular about e-fuels (e.g., hydrogen from renew- ing diagram) is a convenient methodology for predicting changes
ables and synthetic methane), the electricity-to-useful-energy in blast furnaces when the operating conditions are modified.
efficiencies range from roughly 10% to 35%, meaning that This methodology is based on the graphical representation of
energy requirements are 2–14-times higher than for direct carbon, oxygen, and hydrogen balances through an operation
electrification2. However, some of the most energy- and line, restricted by the energy balance, which depicts the par-
carbon-intensive sectors worldwide face limitations when apply- ticipation of these elements in the formation of the reducing gas
ing electrification. In some cases, this is because the require- and its later utilization inside the furnace9. The original model
ment of high-temperature heat above 400°C (e.g., glass, cement) is thoroughly explained in a series of papers that progressively
and others because the nature of the process itself (e.g., iron- deeps into the topic9–13. However, some of the most impor-
making, long-distance aviation and shipping)2. Renewable tant parts were not written in English, and a paper summariz-
hydrogen and synthetic fuels can overcome this barriers, ing the general model is not available. As a result, relevant
delivering the same service at lower costs than the other CO2 aspects of his work are sometimes not widely known. Such is
abatement alternatives, so they should be targeted on these indus- the case that some authors claim to modify the Rist diagram to
tries from an economic and carbon-neutrality perspective1,2. include the H2 contribution14,15, when in fact this was already
Furthermore, given the substantial size of the mentioned sectors, taken into account by Rist. For these reasons, we decided to
the application of e-fuels within them should be prioritized2. revisit his original work, during which we made a number
of additions and corrections.
Within this framework, several authors have studied the appli-
cation of power to gas (PtG) to ironmaking processes based Thus, the first major novelty of this paper is presenting a gen-
on the reduction of iron ores with coke in a blast furnace (BF). eral operating diagram methodology that considers multiple
The PtG concept includes all those processes that converts injectants treated separately, with all calculations given as a
renewable electricity into gaseous fuel by using an electroly- function of the temperature of the thermal reserve zone that
sis stage (among other steps)3. In this case, the renewable fuel exists inside the furnace. Besides, the new model calculates
is used for the replacement of coke or coal in the blast furnace. the sensible heat of the hot metal and slag as a function of their
According to the literature4, the integrations involving power composition, and the heat of carburization as a function of
to syngas may lead to CO2 emission reductions between the austenite and cementite content in iron. Furthermore, it is
11% and 22%, with respect to conventional blast furnaces. added a supplementary model to compute the heat of decom-
The required electricity consumption of the overall sys- position of coal, an additional energy balance in the upper zone
tem, per kilogram of CO2 recycled, lies in the range 4.8–10.8 of the blast furnace to compute the final composition of the
MJ/kgCO2. Moreover, the thermal energy necessities vary from blast furnace gas (BFG), as well as other energy balance for the
1 to 2.5 MJ/kgCO2, increasing to 7.8 MJ/kgCO2 if carbon cap- calculation of the flame temperature. Regarding corrections
ture is used. The electrolysis power capacity required in this with respect to the Rist’s original model, the heat associated
integrations range between 100 MW and 900 MW. with the direct reduction of FeO now accounts for the moisture
of the hot blast, the heat associated with the lack of chemical
Regarding the integration of ironmaking with power to meth- ideality now includes the influence of the hydrogen coming
ane, the available studies in literature are very scarce. In these from auxiliary fuels and of the moisture of the hot blast, and
studies5,6, the CO2 emissions’ reduction compared with con- lastly, the sensible heat of hot metal and slag are now correctly
ventional ironmaking is in the range 13%–19%. Even for these computed and accounted.
Page 3 of 30
The second major novelty of the paper is analyzing for the first
time the OBF–PtG integration under the operating diagram
methodology and, therefore, by using consistent operation data
sets. Besides, the operating lines of these blast furnaces are
obtained, which cannot be found elsewhere in literature. The
third major novelty is to provide full operation data sets for dif-
ferent blast furnace, with detailed composition of all streams and
their most relevant operating parameters (e.g., temperature of
the thermal reserve zone, heat evacuated by the staves, and the
temperature of the flame). The availability of this information
in literature is very scarce, especially for OBFs.
The paper is divided in the following sections. First, a brief

description of a blast furnace is presented to summarize the proc-
esses that will be taken into account during the elaboration of
the operating diagram and in the calculation of the operating line
(Section 2). Then, the construction of the operating diagram
(Section 3) and the calculation methodology of the operat-
ing line (Section 4) are thoroughly described, highlighting the Figure 1. Schematic diagram of a blast furnace and its typical
temperature profile.
new contributions with respect to the original work of Rist. The
model is validated with different data sets elaborated from lit-
erature data (Section 5), and then used to obtain new oper-
exothermic), and then to wüstite (Eq.(3) and Eq.(4), endo-
ating lines of oxygen blast furnaces with synthetic natural
thermic)16. To ensure the reduction, the ratios of CO/CO2 and
gas injection (Section 6). The paper also includes an exhaustive
H2/H2O have to exceed their stoichiometric value. Otherwise,
section of appendixes to make the proposed methodology
the reactions would not achieve equilibrium because of
and the obtained results fully reproducible by the reader.
the short residence time of the gases in the furnace.
Moreover, the same notation as Rist has been used in order to
make easier the comparison between both methodologies.
3 Fe 2 O3 + CO → 2 Fe 3O4 + CO2 ∆ H = −52.85 kJ / mol (1)
2. Blast furnace
3Fe 2 O3 + H 2 → 2 Fe 3O4 + H 2 O ∆ H = − 4.86 kJ / mol (2)
The largest blast furnaces at present can produce 10–13 kt of hot
metal a day. They are about 34 m in inner height (distance from
the raw material entrance to the hot metal exit) and 16 m in diam- Fe 3O4 + CO → 3FeO + CO2 ∆ H = + 36.46 kJ / mol (3)
eter, with an internal volume in the range 5000–5500 m3 16,17.
The blast furnace has a vertical cylindrical structure, externally Fe 3 O4 + H 2 → 3FeO + H 2 O ∆ H = + 84.45 kJ / mol (4)
covered with a shell of steel and internally with refractories.
Between the shell and the refractories, the structure is cooled The middle zone of the blast furnace extends about 25 m down-
by staves16. Staves are cooling gadgets having one or more ward from the end of the upper zone. It takes 2.5–3 hours
inside channels through which water flows. The heat removed by for the burden to traverse the zone, during which the wüstite
cooling may be about 400–1800 MJ/thm10,17–20. is partially reduced following Eq.(5) and Eq.(6) (indirect
reduction)16. This process is exothermic for CO and endother-
Iron ore and coke, which are introduced at the top, take mic for H2. In addition, the water–gas shift reaction reaches
5–7 hours to descend to the bottom by gravity21. To reduce this equilibrium in this zone, Eq.(7)20.
burden, a reducing gas (mainly CO, but also H2) ascends through-
out the furnace in 5–10 seconds and reduces iron ores after FeO + CO → Fe + CO 2 ∆ H = − 17.13 kJ / mol (5)
going through numerous chemical reactions (Figure 1). The gas
is produced at the lower part of the furnace by burning the coke FeO + H 2 → Fe + H 2 O ∆ H = + 30.86 kJ / mol (6)
with O2-enriched pressurized air injected through the tuy-
eres (coke is the only charged material which descends to the CO + H 2 O ↔ CO 2 + H 2 ∆ H = −40.45 kJ / mol (7)
tuyere level in the solid state). The gases move upward due to
the pressure of this hot blast and exit the furnace at the top at In the lower zone (3–5 m above the tuyeres to the bottom),
2.0–2.5 bar. Auxiliary fuels, such as pulverized coal or natu- the rest of the wüstite is reduced by coke carbon through the
ral gas, can also be injected through the tuyeres to diminish the direct reduction process (Eq.(8), endothermic)16. Actually,
amount of coke introduced with the burden. At the bottom, the the interaction between iron and coke is limited, but at tem-
molten metal is collected16. peratures above 1000°C the CO2 and H2O reacts with coke and
forms CO and H2 (Eq.(9) and Eq.(10)), which subsequently
2.1 Chemical reactions reduce the iron oxide by Eq.(5) and Eq.(6). This way, coke is
Inside the blast furnace, the process is as follows (Figure 1). In consumed16.
the upper part (4–6 m from the top), hematite is reduced to
magnetite through irreversible reactions (Eq.(1) and Eq.(2), FeO + C → Fe + CO ∆ H = + 155.34 kJ /mol (8)
Page 4 of 30
CO 2 + C → 2CO ∆ H = + 172.47 kJ /mol (9) can be considered that sulfur dissolves into the hot metal
by Eq.(18), and then transfers to the slag by Eq.(19)20.
H 2 O + C → H 2 + CO ∆ H = + 124.48 kJ /mol (10)
Fe + 0.5S2 → FeS (18)
Apart from the direct reduction, other relevant processes
occur in the lower zone. The burden contains various impuri- FeS + CaO + C → Fe + CaS + CO (19)
ties that will either dissolve in iron or will form part of the slag.
For example, the Al2O3, CaO and MgO oxides are not reduced Per mole of S that ends in the slag, 1 mole of CO is added to
under the blast furnace conditions and therefore they trans- the reducing gas.
fer fully into the slag. In the case of SiO2, MnO and P2O5,
they are partially reduced and dissolved in the hot metal. It 2.2 Temperature profile
can be considered that these impurities are directly reduced The blast furnace process can be divided in three different tem-
by solid carbon following Eq.(11), Eq.(12) and Eq.(13). The peratures zones (Figure 1). At the lower part, the flame tem-
final silicon, manganese and phosphorous contents in the hot perature is normally between 2000 and 2300°C (defined as
metal are much less than the equilibrium values. the temperature reached by the raceway gas when all C and
H2O have been converted to CO and H2)22. This raceway gas
SiO 2 + 2C + 3Fe → Fe 3Si + 2CO ∆ H = + 622.5 kJ /mol (11) provides heat for the direct reduction process and for the
melting of the hot metal and slag20. The hot metal exits at
MnO + C → Mn + CO ∆ H = + 286.92 kJ / mol (12) 1350–1450°C and the slag at 1500–1550°C16. The gas, which
has been cooled to about 1000°C, ascends to the middle zone.
P2 O5 ⋅ 3CaO + 5C + 6 Fe →
∆ H = + 1184 kJ / mol (13) The middle zone is a region of thermal equilibrium. In prac-
2 Fe 3 P + 3CaO + 5CO tice, a non-zero temperature difference remains between
Another component that will end up dissolved in the hot metal gas and solids, but it passes through a minimum value in a
is carbon. As in the previous case, carbon never reaches satu- region of slow heat exchange. The temperature is kept almost
ration in pig iron20. At tapping temperatures (1350–1450°C) constant around 800–1000°C10.
the carbon content may vary from 2.5 to 4.5%16. As simplifica-
Lastly, in the upper zone, the gas and the burden exchanges
tion, it is assumed that the dissolved carbon forms, austenite and
heat rapidly. The gas is cooled down from 800–900°C to
cementite, in the hot metal, according to Eq.(14) and Eq.(15),
100–200°C as it leaves the furnace top, and the burden is heated
respectively11.
from ambient temperature to 800°C while descending16,20.
C(coke) → C(austenite) ∆ H = + 34.7 kJ / mol (14) The temperature profile and the reduction zones (pre-reduction,
indirect reduction, and direct reduction) more or less coincide,
3 Fe + C(coke) → Fe 3 C ∆ H = + 6.69 kJ / mol (15) so these three zones can be used to study the blast furnace.
Also, in the lower zone, in front of the tuyeres (i.e., the race- 3. Generalized Rist diagram with multiple
way), coke burns with the oxygen of the hot blast, thus pro- injectants
viding the process with heat and CO-reducing gas. The total The Rist diagram is named so in reference to its author, who
reaction of coke in the raceway can be considered as an incom- elaborated a model for predicting changes in blast furnaces
plete combustion due to the shortage of oxygen ((Eq.(16))16. when the operating conditions are modified9–13. The model is
Actually, in the inner part of the flame, complete combustion based on the graphical representation of carbon, oxygen, and
also occurs but the CO2 ends up dissociating by Eq.(9). hydrogen balances through an operation line that depicts the
participation of these elements in the formation and utiliza-
1 (16) tion of the reducing gas9. Additionally, the diagram includes
C+ O → CO ∆ H = − 113.68 kJ / mol
2 2 an equilibrium line to delimit the maximum oxidation state of
the gas according to the Chaudron diagrams for the Fe-O-H and
In case of injecting auxiliary fuels to diminish coke consump-
Fe-O-C systems23.
tion, incomplete combustion is assumed to follow Eq.(17),
where Z denotes the ashes in the case of pulverized coal. No
water is present since it rapidly dissociates by Eq.(10) as it The construction of the Rist diagram is introduced here with
occurred for CO216. additions and corrections with respect to the original work of
Rist. The model methodology is now described for the gen-
1 eral case of multiple injectants treated separately (instead of
CH 2 aO 2 b N 2 c S 2 d Zz + O → CO + aH 2 + bO 2 + cN 2 + dS2 + zZ (17) for an overall single injection). This is especially important
2 2
because it will allow to properly calculate the heat of decom-
When the injected fuel contains sulfur (e.g., pulverized coal), position of each auxiliary fuel, as well as to specify different
this will end forming part of the slag. As simplification, it inlet temperatures for each injectant. Additionally, a detailed
Page 5 of 30
description on how to find the equilibrium line for the diagram

is included.
3.1 Formation of the reducing gas (Rist diagram in the

range 0<X<1)
The mass balance of the formation of 1 mol of reducing gas
mixture (i.e., the gas exiting the lower zone) can be written
according to Eq.(20)9.
x v + 2 xe + ∑ ( a j + 2b j ) x j + xS i + xM n + xP + xS + xk + xd
(20)
= 1 mol of reducing gas
In this equation, each addend denotes the number of moles of

CO and/or H2 (per mole of the total reducing gas mixture) that
are either introduced in the blast furnace or produced through
a reaction. In other words, these addends are the individual
contributions (in mole fractions) to the formation of the reduc-
ing gas mixture. They are given according to the sources
of hydrogen (H2), oxygen (0.5 mole of O2 will give 1 mole
of CO) or water (1 mole of H2O will give 1 mole of CO
and 1 mole of H2).
The term xv denotes the CO produced when the O2 of the hot

blast react with C through Eq.(16) or Eq.(17). The term 2xe
accounts for the H2 and CO produced by the moisture of the
hot blast when dissociated through Eq.(10). The term ajxj
denotes the H2 from the incomplete combustion of an auxiliary
injection j (Eq.(17)), while 2bjxj is the CO produced when
the oxygen of that auxiliary injection react with C according
to Eq.(16). The terms xSi, xMn and xp stand for the CO pro-
duced when reducing the impurities SiO2, MnO and P2O5
((Eq.(11), Eq.(12) and Eq.(13)). The addend xS represents the
CO released when transferring the dissolved sulfur in the iron Figure 2. Rist diagram.
to the slag (Eq.(19)). The term xk is the H2 directly coming
from the hydrogen content of the coke. Lastly, xd denotes the
CO released during the direct reduction of wüstite (Eq.(8))10.
Here, the addends denote the moles of reducing gas (CO
and H2) that are introduced in the blast furnace or produced
Each of the addends of Eq.(20) can be depicted as a segment on through a reaction, per unit of Fe obtained (the meaning
the abscissa axis, whose total sum covers the interval 0<X<1 of each addend is identical to Eq.(20))10. The sum of these
(Figure 2). For convenience, the notation of Eq.(21) is used segments represents the total moles of reducing gas per unit of
for the units of the abscissas in the diagram, where the numera- Fe (denoted by μ)9. Each of the addends of Eq.(22) can be rep-
tor is the number of moles of reducing gas related to a particu- resented as a segment on the ordinate axis (Figure 2). In this
lar reaction or injection according to the sources of hydrogen case, the origin on the Y axis of the operating diagram is
(H2) and oxygen (0.5 mole of O2 giving 1 mole of CO), and arbitrary. For convenience, it is chosen so that the oxy-
the denominator is the total number of moles of reducing gas gen originally combined to iron appears on the positive side
according to the sources of hydrogen (H2) and carbon (1 mole (i.e., yd), whereas other sources of oxygen and hydrogen
of C giving 1 mole of CO)12. appear on the negative side (this ordinate is denoted by YE for
O + H2 convenience, Eq.(23))9.
X= (21)
C + H2
( )
YE = − yv + 2 ye + ∑ (a j + 2b j ) yj + y S i + yM n + yP + yS + yk (23)
Alternatively, the mass balance for the production of the reduc-
ing gas mixture can also be written with reference to the The units of the ordinate axis are set according to Eq.(24),
production of 1 mole of Fe in the blast furnace. Under this given as a function of the sources of hydrogen (H2) and oxygen
reference, the mass balance follows Eq.(22). (0.5 mole of O2 giving 1 mole of CO) for the production of the
reducing gas.
yv + 2 ye + ∑ ( a j + 2b j ) y j + yS i + yM n + yP + yS + yk + yd
(22) O + H2
= µ moles of reducing gas / mol F e Y= (24)
Fe
Page 6 of 30
The corresponding terms of Eq.(20) and Eq.(22) form sets of through calcination)12. Moreover, it should be noted that such
proportional numbers and, as such, they can be read on two a correspondence between the abscissa and the composition
rectangular axes as the projections of the same straight line. of the mixture does not exist in the interval 0<X<1, where the
The Figure 2 shows the straight line thus obtained, called the segments could be arranged in any order.
“operating line”9, whose slope has the units of Eq.(25).
3.3 Equation of the operating line
C + H2
µ= (25) According to the theory described above, the equation of the
Fe operating line can be written as Eq.(28). The slope, μ, is the
This corresponds to the total number of moles of reducing gas, number of moles of reducing gas required for the produc-
per unit of Fe, according to the sources of hydrogen and carbon. tion of 1 mole of Fe. The intercept, YE, represents the moles of
H2 and O coming from sources other than iron oxides that con-
3.2 Utilization of the reducing gas (Rist diagram in the tribute to the formation of the reducing gas (negative sign by
range 1<X<2) convention, Eq.(23))12.
Following the same principle, it is simple to depict the utiliza-
tion of the reducing gas mixture (Eq.(1) – Eq.(6)) by means of a Y = µ ⋅ X + YE (28)
segment representing the oxygen removed from the iron oxides.
The number of oxygen moles transferred from the iron oxides If the operating line is characterized, relevant information can
to the reducing gas is denoted by xi when referred to 1 mole be deduced from it. The slope accounts for the total reducing
of reducing gas mixture, and by yi when referred to 1 mole agent rate required (in terms of C and H2 per mole of Fe) so, if
of Fe (same convention than before). Thus, the ratio an auxiliary fuel is introduced, the decrease in the input rate
between both variables (i.e., yi /xi) is the number of moles of of coke can be computed5. The intercept stands for the hydro-
reducing gas mixture per mole of Fe produced. Since the gen and oxygen brought into the furnace (except for the O2 con-
reduction of iron oxides does not change the total number of tained in the iron ore), therefore the necessary air flow rate can
moles of the reducing gas, the ratio yi /xi is constant and equal to be calculated by subtracting the other O2 and H2 sources (mois-
μ. In other words, in all equations from Eq.(1) to Eq.(6) the gas ture, auxiliary fuels, coke and impurities)5. Also, the initial
gets oxidized without increasing or decreasing the number of oxidation state of the iron oxides introduced in the blast furnace
moles in the gas (1 mole of CO gives 1 mole of CO2, and 1 mole (YA) allows to know the final degree of oxidation of the gas leav-
of H2 gives 1 mole of H2O). Therefore they can also be read as ing the top of the furnace (XA – 1). Finally, the ratio between
projections of the same straight line of slope μ (segment in direct and indirect reduction is identified by construction. The
the range 1<X<2 of the Rist diagram, Figure 2)9. abscissa X = 1 gives the oxygen removed by direct reduc-
tion, yd (Figure 2), and then the oxygen removed by indirect
This segment in the range 1<X<2 is particularly useful because reduction is easily calculated as yi = YA – yd.
it provides information on the average oxidation state of
the reducing gas mixture (abscissa) and of the iron oxides 3.4 Equilibrium line
(ordinate)12. The abscissa can be interpreted as the reducing gas In the blast furnace, the reducing gas can never oxidize the sol-
having an average oxidation state equal to X – 1 (see Eq.(26)). ids. For this reason, the operating line in the segment 1<X<2
This means that at the abscissa X = 1, we find a reducing must necessarily remain on the left of the equilibrium line of
gas mixture composed by CO and H2, while at the abscissa the Fe-O-H-C system (Figure 2). If we were at some point at
X = 2 the gas is completely oxidized to CO2 and H2O. On the the right of the equilibrium line, the way to reach equilibrium
other hand, the Y coordinates represent the oxidation state would be displacing us upwards (i.e., providing O to the Fe)
of the iron oxides according to Eq.(27). This interpretation or leftwards (removing O from the gas), what in both cases
allow identifying the point A in the Rist diagram, whose ordi- means to oxidize the solids.
nate is the initial oxidation state of the burden (e.g., YA = 1.5
for Fe2O3)12 and whose abscissa is the final degree of The contour of the equilibrium line is delimited by five points,
oxidation of the gas leaving the top of the furnace plus 113. which we will denoted by F, W, W2, M, M2. The point W is of
special interest since it corresponds to the chemical equilib-
CO 2 + H 2 O
X =1+ (26) rium between gases and solids at the beginning of the middle
CO + CO 2 + H 2 + H 2 O zone, where pure wüstite is found if the blast furnace oper-
ates under ideal conditions. The coordinates of these points are
O
Y= (27) given in Table 1. The ordinates of the five points are easily cal-
Fe
culated as the ratio of the oxygen and iron atoms of the corre-
The necessary condition to understand the segment 1<X<2 sponding components (Eq.(27))24. The abscissae (Xw Eq.(29)
in this way is that the total number of moles of reducing gas and XM Eq.(30), which are equivalent to Eq.(26)) depend on
keeps constant and that the oxygen supplied to the gas must the molar fraction Xh that relates the hydrogen and water con-
come only from the reduction of the iron oxides (i.e., no addi- tent of the reducing gas mixture (Eq.(31)). This is used to com-
tional injections in the middle or upper zone, and no CaCO3 bine the state of oxidation at equilibrium ω for the individual
introduced, which would decompose into CaO and CO2 CO-CO2 and H2-H2O mixtures (Figure 3). It should be noted
Page 7 of 30
Table 1. Delimiting points of the equilibrium that the molar fraction Xh is independent of the state of oxi-
line for the Fe-O-H-C system in a Rist diagram. dation of the reducing gas (i.e., independent of the abscissa
X), and can be calculated as a function of ye, yk, ajyj and μ.
Abscissa X Ordinate Y
XW = 1 + (1 − x h ) ωWC+ x h ωWH (29)
F Iron Fe XF=XW YF=0
W Wüstite Fe0.95O XW= Eq.(29) YW=1.05 X M = 1 + (1 − x h ) ωM C+ x hωM H (30)

W2 Wüstite Fe0.89O XW2=XM YW2=1.12
H 2 + H 2O ( ye + yk + ∑ a j y j )
M Magnetite Fe3O4 XM= Eq.(30) YM=1.33 xh = = (31)
CO + CO 2 + H 2 + H 2O µ
M2 Magnetite Fe3O4 XM2=2 YM2=1.33
For computing ω, Chaudron diagrams or tabulated data must
be used9. In our case, we adjusted the data from 10,23 to a
polynomic equation where T is given in °C (Eq.(32)).
2
ω = a 0 + a1 T + a 2T + a 3T 3+ a4 T 4 + a 5T 5 (32)
The coefficients are presented in Table 2. The temperature at

which ω is calculated corresponds to the temperature of the
middle zone (normally between 800 and 1000°C), where the
chemical equilibrium between the gas and the solids occurs.
We denote this temperature as TR.
4. Calculation of the operating line

In practice, and especially when predicting new operating con-
ditions, the equation of the operating line cannot be directly
computed by calculating μ and YE because the required data
is missing. The operating line must be obtained through two
characteristic points denoted as R (coordinates XR, YR) and P
(coordinates XP, YP). The former represents the equilibrium
Figure 3. Equilibrium of the Fe-O-C and Fe-O-H systems. The between gases and solids reached in the middle zone. The lat-
variable ω stands for nCO2/(nCO+nCO2) in the case of ωWC and ωMC, and ter is a fixed point imposed by the energy balance of the blast
for nH2O/(nH2+nH2O) in the case of ωWH and ωMH. furnace. When these two points of the operating line are
Table 2. Coefficients for the calculation of the oxidation state at equilibrium in Fe-O-C and Fe-O-H systems
(Eq.(32)). Valid from 500 to 1100°C.
T (°C) Equilibrium a0·10 a1·103 a2·105 a3·108 a4·1011 a5·1015
>565 Iron-Wüstite 4.0894101 3.8856440 -1.3778206 1.7924558 -1.0465659 2.3054702

ωWC
<565 Iron-Magnetite 6.3672662 -0.2230216 0 0 0 0
>565 Wüstite-Magnetite -7.8765294 3.6286637 -0.2811151 0.0772069 0 0

ωMC
<565 Iron-Magnetite 6.3672662 -0.2230216 0 0 0 0
>565 Iron-Wüstite -0.4957779 -0.5074581 0.4367340 -0.6744924 0.4402173 -1.0668513

ωWH
<565 Iron-Magnetite -1.4558633 0.6611511 0 0 0 0
>565 Wüstite-Magnetite -215.36181 115.54294 -24.611536 26.555149 -14.341369 30.845286

ωMH
<565 Iron-Magnetite -1.4558633 0.6611511 0 0 0 0
Page 8 of 30
known, it is easy to compute the slope and the Y-intercept of the In practice, a blast furnace does not operate under ideal condi-
operating line (Eq.(33) and Eq.(34)): tions, so a zone of pure wüstite cannot be distinguished (the
operating line no longer passes through the point W). For these
YR − YP
µ= (33) cases, it is defined the chemical efficiency of the furnace, r,
XR − XP representing the oxygen actually exchanged to the oxygen the-
oretically exchangeable (typically, r is around 0.92)5,10. The
 Y − YP 
YE = YR − XR  R  (34) coordinates of the new point R, through which the operation
 X R − XP  line passes, is calculated by Eq.(35) and Eq.(36) as a function
of the point W, the chemical efficiency r, and the initial
In the following subsections, it is explained how to calcu-
oxidation state of the burden YA.10.
late the points R and P. The additions and corrections to the
original work of Rist are introduced mainly during the calcu-
X R = 1 + r ( X W − 1) (35)
lation of the energy balance (explained more in detail in the
appendixes25). These are the following:
YR = YA + r ( YA − YW) (36)
▪ ll calculations are given as a function of the temperature of
A
the middle zone, TR (i.e., of the temperature of the thermal Despite there is no chemical equilibrium, the temperature is
reserve zone where thermal equilibrium exists). still nearly constant in the middle zone (thermal reserve zone
▪ ach auxiliary fuel can enter at different temperatures
E
where thermal equilibrium exists), so this temperature is used
for the calculations (TR).
because they are now treated separately, rather than as an
overall injection.
4.2 Point P: energy balance in the elaboration zone
▪ he heat associated to the direct reduction of FeO is now
T The operating line, Eq.(28), depends on different parameters
corrected taking into account the moisture of the hot blast. which are not all independent. In particular, any energy balance,
whether global or partial, imposes a relationship between them.
▪ he sensible heat of the hot metal is calculated as a function
T An option is to use the energy balance of the elaboration zone
of its composition. (i.e., middle zone plus lower zone), which follows Eq.(37).
▪ he sensible heat of the slag is calculated as a function of
T
As in the original work of Rist, we are going to work in kcal
per mole of Fe10. Moreover, the reference temperature for the
its SiO2, Al2O3, CaO and MgO content.
energy balance is chosen at TR, i.e., at the temperature of the
▪ he heat of carburization is calculated as a function of
T thermal reserve zone.
the austenite and cementite content in iron.
qc yv + qv yv + ( qiwYW − δ ) = qg ( yd − ye ) + qk yk + qe ye +
▪ he heat associated to the lack of thermal ideality is calculated
T
∑ qj yj − δ ′ + qSi ySi + qM n yM n + (37)
as a function of the burden and coke composition.
qP yP + qγ γ + f + l + p + C∆ TR
▪ he heat associated to the lack of chemical ideality is
T
calculated as a function of the burden in the thermal The input/production of energy is on the left side of the equa-
reserve zone. tion, and the output/consumption is on the right side of the
equation. Regarding the former, we have the term qcyv that
▪ he heat associated to the lack of chemical ideality now
T represents the heat released by the incomplete combustion
accounts also for the hydrogen coming from auxiliary fuels and of carbon, qvyv for the sensible heat of the air, qiwYw as the heat
for the moisture of the hot blast. released by the reduction of wüstite, and δ to account for the
▪ supplementary model is added to compute the heat of
A
lack of chemical ideality in wüstite reduction. In the right
side of the equation we have qg (yd – ye) which is the heat
decomposition of coal when injected as auxiliary fuel.
absorbed during direct reduction because of CO2 dissociation,
▪ n additional energy balance in the upper zone of the blast
A qkyk as the heat consumed due to the hydrogen entering with
furnace is added to compute the final composition of the the coke, qeye for the overall heat absorbed by the moisture of
blast furnace gas, instead of only computing the final the air, ∑ q j yj to quantify the overall heat absorbed by the
oxidation state. auxiliary injections, δ ′ accounting for the lack of chemical ide-
ality in the conversion of H2 to H2O, (qSiySi + qMnyMn + qPyP)
4.1 Point W and point R: chemical and thermal reserve for the heat absorbed by the reduction of the accompanying ele-
zones ments SiO2, MnO and P2O5, then qγγ as the heat absorbed by
In an ideal blast furnace, the reducing gas and the burden are the carburization of the iron, f denoting the heating and melt-
in chemical equilibrium after the upper zone. This is known ing of the hot metal, l for the heating and melting of the
as the chemical reserve zone, in which wüstite is the only iron slag, p for the heat removed by the staves and, lastly, (CΔTR)
oxide present. This point is denoted by W and was already accounting for the lack of thermal ideality (in case the tem-
identified during the construction of the equilibrium line perature of the gas and the solid is not the same at the thermal
(Table 1). reserve zone).
Page 9 of 30
All the addends of Eq.(37) are thoroughly explained in the A 

Appendix A25 to avoid breaking here the flow of the explanation. ∆1 =  + 1 + 2e  X − (1 + 2e) (45)
Besides, they are compared with the calculation method appear- B 
ing in Rist’s original work when appropriate to highlight the
C 
differences. The meaning and units of each variable is speci- ∆ 2 = − Y −  + YE*  X + YE* (46)
fied in the nomenclature list, and a table summarizing the B 
calculation of the heats denoted by q is available in Table 6 of From this operating line in the form of Eq.(44), which accounts
Appendix A25. for the energy balance, we know that the operating line will
pass through a point P of coordinates Xp and Yp fulfilling simul-
From the energy balance of Eq.(37), we can find a relation taneously Δ1 = 0 and Δ2 = 0. Applying this condition, we
between yd (number of O moles removed from iron oxides by can find from Eq.(45) and Eq.(46) the coordinates Xp and Yp
direct reduction) and yv (number of O moles brought by the air), (Eq.(47) and Eq.(48)). Now, the operating line of the blast
under given operating conditions defined by the inlet/outlet furnace is known.
temperatures, the chemical efficiency, the tuyeres injections,
and the composition of hot metal and slag. This relation can be B(1 + 2e)
XP = (47)
written as Eq.(38), where A, B and C are given by Eq.(39), A + B(1 + 2e)
Eq.(40) and Eq.(41).
C   B(1 + 2e) 
A yv − C YP = YE* −  + YE*    (48)
yd = (38) B   A + B(1 + 2e) 
B
A = qc + qv − eqe + eqk (1 − r ) + eqg (39) It is worth to mention that both coordinates of P depend on the
chemical efficiency of the furnace, r, through A and C. How-
B = qg (40) ever, Rist only considered the dependence on the chemi-
cal efficiency through C because he did not decompose δ ′.
Therefore, he found that Xp was independent of r10. Here we
(
C = − qiw Yw + δ + qk yk + ∑ q j yj − (1 − r ) yk + ∑ a j yj qk ) (41)
have shown that is not.
+ qS i yS i + qM n yM n + qP yP + qγ γ + f + l + p + C∆ TR
4.3 Additional results derived from the operating line
Here, the variable e denotes the moles of H2O per O moles in The relevance of characterizing the operating line comes
the air (i.e., e = ye/yv), which is a convenient notation to write from the possibility of deducing operational data such as the
the water injected with the air as a function of the air injected required reducing agent rate, the air consumption, the top gas
through the tuyeres (i.e., to include the term qeye in A). Simi- composition, the ratio between direct and indirect reduction,
larly, the term δ ′ was decomposed according to Eq.(92) to and the flame temperature.
separate the terms that depends on yv (see Appendix A.925).
It should be noted that Rist did not decompose δ ′ and there- 4.3.1 Reducing agent rate (coke consumption). The reduc-
fore he wrongly included a term that is actually dependent ing agent rate, μ, obtained from the operating line, denotes
on yv in C instead of adding it to A10. Moreover, Rist did not the number of moles of C and H2 needed inside the blast fur-
included the term +eqg that appears in A, which corrects the heat nace as reducing gas for the production of 1 mole of Fe as hot
absorbed during direct reduction (part of the direct reduction metal. When solving the Rist diagram, we assume the auxil-
takes place through Eq.(10), see Appendix A.5). iary injections to be known. Therefore, we can compute the
required amount of coke by subtracting the contributions of
Now, we can impose the relation of Eq.(38) from the energy the injections to μ. The carbon that ends up dissolved in the hot
balance to the operating line defined by Eq.(28). To do that, metal must be also taken into account (which increases the
we first rewrite Eq.(28) as Eq.(42), taking into account that required reducing agent rate), as well as the H2 that is pro-
μ = –YE + yd according to Eq.(22) and Eq.(23). duced when the H2O from the hot blast is dissociated (which
decreases the required reducing agent rate). Thus, the mass
Y = − YE (X − 1) + yd X (42) flow of coke is calculated by Eq.(49).
By substituting Eq.(38) in Eq.(42), and by using the conven- ( )

m K = µ + γ − eyv − ∑ (τ j + a j ) y j nHM,Fe ²coke (49)
ient notation of Eq.(43) to decompose YE on two terms (one
dependent of yv and another independent), we found Eq.(44) In this equation, γ is the number of moles of C dissolved in the
where Δ1 and Δ2 are given by Eq.(45) and Eq.(46). hot metal ((Eq.(50)), τj is equal to 1 when the auxiliary injec-
tion contains carbon and 0 when not, and 𝜖K is the ratio of C
YE* ≡ YE + (1 − 2e) yv = −∑ ( a j + 2b j ) y j − y si and H2 moles in coke per kg of coke (Eq.(51)). The variables
(43)
− y Mn − y P − y S − yk Ωj,i are the mass fraction of element i in compound j.
∆1 yv + ∆ 2 = 0 (44) γ = (106 Ω HM,C M C ) nHM,Fe (50)
Page 10 of 30
 ΩK,C ΩK,H  Most authors use the CO utilization ratio (ηCO ≡ nBFG,CO2/(nBFG,CO
�K = 103  + (51) + nBFG,CO2)) as the 15th equation to complete the system of
 M C M H2  equations, instead of using the energy balance in the upper
The term nHM,Fe is the number of moles of Fe in hot metal per zone. They assume to know this parameter, since in practice
ton of hot metal (Eq.(74)). they would be able to measure it at the flue gas of a real iron-
making plant. Indeed, in those cases in which the operating
4.3.2 Air flow rate. The intercept of the operation line, denoted line is characterized for a real operation where the ηCO infor-
by YE, represents the H2 and O brought into the furnace (except mation is reliable, to use this procedure instead of the energy
for the O contained in the iron ore) with negative sign by con- balance of the upper part makes the methodology easier.
vention. By subtracting the O and H2 sources other than the However, this is not a valid procedure when analyzing new oper-
hot blast, the necessary O flow rate as air can be calculated ating lines for potential blast furnace configurations. In such
(i.e., calculation of yv, Eq.(52)) case, the assumption of the value of ηCO would be arbitrary
and, almost certainly, it will lead to inconsistencies in the upper
−(YE + ∑ (a j + 2b j ) y j + ySi + yMn + yP + yS + yk ) zone (energy balance not fulfilled). Inconsistencies which are
yv = (52)
1 + 2e not detected because of not performing the corresponding
energy balance in the upper zone. For this reason, it is com-
Once we know yv, the mass of air (dry) per ton of hot metal is pletely necessary to use the energy balance of the upper zone
calculated by Eq.(53). instead of ηCO when proposing new operating lines.
yv nHM,Fe  0.79 
mvd =  M O2 + M  (53) 4.3.4 Amount of direct and indirect reduction. By construc-
2000  0.21 N 2  tion, the abscissa X = 1 allows computing yd (Figure 2), which
is the oxygen removed from the iron oxides by direct reduction
4.3.3 Blast furnace gas composition. Once the coke and air (Eq.(55)).
flow rate are known, the input streams to the blast furnace
become completely characterized. In order to characterize also yd = µ + YE (55)
the output streams, we have to find 15 unknown variables.
These are the mass flow rate of each component in the blast Then, the oxygen removed by indirect reduction is easily
furnace gas (mBFG,CO, mBFG,CO2, mBFG,H2, mBFG,H2O, mBFG,N2), the calculated as Eq.(56).
mass flow rate of hot metal mHM (the individual mass flow
rate of each component in hot metal is calculated through its yi = YA − yd (56)
mass fraction, which is assumed known from the beginning),
and the mass flow rate of each component in the slag (mSlag,SiO2, 4.3.5 Flame temperature. The flame temperature is the tem-
mSlag,Al2O3, mSlag,CaO, mSlag,MgO, mSlag,MnO, mSlag,CaS, mSlag,P2O5, mSlag,Fe2O3, perature that the raceway gas reaches when all oxygen from
mSlag,FeO). The system of 15 equations to solve the balance com- hot blast and injections has been used for the incomplete
prises 11 mole balances for Fe, Si, Al, Ca, Mg, Mn, C, H, N, combustion of C to CO, and all water has been dissociated
S, P (the O balance was already accounted in the elabora- to CO and H2. It can be considered as a control parameter to
tion of the operating line), two mass balances for mSlag,Fe2O3, check if the studied configuration of blast furnace is reason-
mSlag,FeO (they correspond to the Fe2O3 and FeO content of the able, since the injection of auxiliary fuels drops the flame
coal ashes, which enter at the tuyeres and are not reduced), temperature as a consequence of their lower C/H ratio com-
one equation related to the final oxidation state of the blast pared with coke (flame temperature should be kept between
furnace gas (information coming from the operating line, 2000 and 2300°C for a proper operation). In such cases, blast
Eq.(54)), and one energy balance of the preparation zone (i.e., oxygen enrichment may be required to maintain a suitable flame
of the upper zone). temperature.
nBFG,CO + n BFG,H YA − YE From a theoretical point of view, this flame temperature can
2O
ηCO − H ≡ 2
= − 1 (54)
2 n BFG,CO + n BFG,CO + n BFG,H + n BFG,H µ be calculated from an energy balance in the raceways. We use
2 2 2O
Eq.(57), where we made a similar construction to that of
Eq.(37). The term qcyv stands for the combustion of C to CO
It should be noted that knowing the final oxidation state of the
by using the O from the hot blast, the term qvyv represents
gas exiting the top of the furnace (i.e., Eq.(54)) is not suffi-
the sensible heat that the dry hot blast is providing, while the
cient to compute the final composition of the top gas because
term qs,CyC is the sensible heat of the coke carbon used in com-
the gas is not in equilibrium at the upper part of the fur-
bustion (which comes at Tf from the lower zone). At the right
nace. In other words, the water–gas shift reaction ((Eq.(7))
side of the equation, we have (qer + qes)ye which is the con-
changes the BFG composition without modifying ηCO–H2,
tribution of the moisture of the hot blast (decomposition
but the extent of this reaction is unknown. For this reason,
the energy balance of the preparation zone is required. This ( )
and sensible heat), also ∑ j q jd + q js − 2b j qc y j for the aux-
energy balance is detailed in Appendix C25. iliary injections (decomposition, sensible heat and combustion
Page 11 of 30
of the O entering with this injections), and qs,N2yrg,N2 + qs,COyrg,CO Where Vv is the dry blast volume per ton of hot metal, Tv is the
+ qs,H2yrg,H2, as the energy required to heat the reducing gas temperature of the blast, ωv,O2 is the oxygen content in the
up to the temperature of the flame Tfl. Lastly, it is included blast, ηnat is the natural moisture in the blast, η is the total mois-
the heating from TR to Tfl of the ashes from coal injections ture in the blast, VNG is the natural gas consumption, mPC is
( )
∑ j Z j qs , Z y j . the pulverized coal consumption, ΩPC,C is the carbon content
in pulverized coal, ΩPC,H is the hydrogen content in pulver-
ized coal, ωNG,CH4 is the methane content in natural gas, and
qc yv + qv yv + qs ,C yC = ( qer + qes ) ye
Cp,v, CP,H2O and Cp,rg are the specific heats of blast, moisture and
+ ∑ ( q jd + q js − 2b j qc ) y j reducing gas. The units are provided in the nomenclature list.
j (57)
+ ∑ qs ,i yrg,i + ∑ z j qs ,Z y j 5. Model validation
i j
In order to validate the model, we are going to use three differ-
ent data sets. The first one comes from the original work of Rist10,
We can say that the flame temperature is a result indirectly
corresponding to a conventional air-blown blast furnace with-
derived from the operating line since for its computation we need
out auxiliary injections. The second one is elaborated from
to know the amount of air injected, the amount of coke, and the
the work of Babich et al.18, for an air-blown blast furnace with
amount and composition of the reducing gas (obtained from the
pulverized coal injection and O2-enriched air. The last one is
composition of the BFG). The variables yv, yC, yrg,N2, yrg,CO and
taken from the work of Sahu et al.27 for an oxygen blast furnace
yrg,H2 are calculated by Eq.(52), and Eq.(58) to Eq.(61). In
with top gas recycling. When solving the operating diagram,
the case of yC, we can compute it as the oxygen available for
we assume the composition of iron ore, coke, auxiliary injec-
combustion minus the C coming from the injections (because
tions and hot metal to be known. For iron ore and injections,
1 mole of O consumes 1 mole of C), or as the C coming from
the total mass flow is also known. For the hot blast, the mois-
coke minus the C used in reactions other than combustion. The
ture is fixed. Regarding energy balances, all the inlet and outlet
variable τj is equal to 1 when the auxiliary injection contains
temperatures are known. Finally, the operating conditions on
carbon and 0 when not.
chemical efficiency, heat removed by the staves, the proportion
of heat evacuated between the preparation and elaboration
yC = yv + ∑ (2b j − τ j ) y j
j zone, and the temperature of the thermal reserve zone are set
(58) to known values. Under this framework, the model allows to
103 Ù K,C m K
= − (γ + y Si + y Mn + y P + y S + yd ) compute the mass flows of coke, hot blast, hot metal and blast
M C nHM , Fe furnace gas. Moreover, the composition of the blast furnace
gas and slag can be calculated. Regarding operation condi-
yrg , N 2 = n BFG,N n (59) tions, the slope and intercept of the operating line, the amount
2 HM,Fe
of direct and indirect reduction, the flame temperature and the
yrg , CO = (n BFG,CO + n BFG,CO2 ) n HM,Fe (60) oxidation state of the BFG are obtained. The list of inputs and
outputs are summarized in Figure 4 together with a concep-
yrg ,H2 = (n BFG,H + n BFG,H O ) n HM,Fe tual scheme of the blast furnace. Exceptionally, for those cases
2 2
(61)
in which we are not introducing air in the blast furnace, we
assume the mass of the host blast to be known (mv = 0) and we
The calculation of the rest of the terms were already explained
calculate instead the mass flow of the injection that carries the
in Appendix A25 for the energy balance of the elaboration
main oxygen input (mj).
zone. All the q terms are tabulated in Table 6 according
to the adjustment to Eq.(113) or Eq.(114). The variable T in
these equations must be substituted by TR for qc and qer, by
Tv for qv and qes, by Tf for qs,C, by Tj for qjd and qjs, and by Tfl
for qs,i and qs,Z. Thus, the only missing variable in Eq.(57) is Tfl.
In practice, different authors have developed formulae for

the calculation of the flame temperature as a function of
different operating parameters16. Here we present the equa-
tion developed by Babich16,26, which accounts for natural gas
and pulverized coal injections (Eq.(62)). We will use it for
comparison and validation purposes.
44.455Vv Tv ( c p ,v + 0.0012c p ,H2Oηnat ) + 3146Vv ωv ,O
2
− 1170VNG ωNG ,CH4 − 600mPC Ω PC ,C − 1.65Vv η
Tfl = (62)
(0.2387Vv + 0.24Vvωv ,O + 0.48VNG ωNG ,CH4
2
Figure 4. Conceptual diagram of a blast furnace, indicating
+ 6mPC Ω PC ,H + 0.0006Vv η)186.785c p ,rg
the input and output data of the model.
Page 12 of 30
5.1 Air-blown blast furnace without auxiliary injections 5.2 Air-blown blast furnace with pulverized coal
(Rist, Data set 1) injection and O2-enriched air (Babich, Data set 2)
This data set was elaborated from the original work of Rist10, This data set was elaborated from the work of Babich et al.18,
corresponding to an air-blown blast furnace without auxiliary corresponding to an air-blown blast furnace with pulver-
injections. The input mass flow of iron ore and its composition ized coal injection and O2-enriched air. We consider the O2-
was calculated through mass balances based on Rist’s results, enriched hot blast as an auxiliary injection. The proximate
assuming typical mass fractions for those oxides other than analysis of the coal is 74.1% ΩFC, 17.2% ΩVM, 7.6% ΩZ and
iron. Also, it was assumed a typical mass fraction distribution 1.2% ΩM18. Typical mass fractions for iron ore and coke were
for oxides in coke28. The outlet temperature of BFG was assumed. Moreover, since the operating parameters r, TR
assumed to be 180°C to estimate the gas composition. and θst are not provided in the work of Babich et al., typical
values are chosen.
As explained through the model description and appendixes25,
three potential errors were identified in the original model All results show a discrepancy below the 1% with respect
provided by Rist: (1) underestimation of the heat required to the data of Babich et al.18, except for the coke consump-
inside the blast furnace by not accounting for the heating of tion, which varies a 2.1%. The flame temperature calculated by
slag between TR and Tf (see Appendix A.1225), (2) overestima- Eq.(62) gives the same result than the one provided by
tion of the heat required because of wrongly computing the Babich, since he developed that formula. The error in the
term l with Cp,SiO2 in wrong units (see Appendix A.1325) and flame temperature calculated by our model is 1%. The oper-
(3) overestimation of the heat required because of considering ating line of this blast furnace is depicted in Figure 5, which
twice the heat absorbed during direct reduction for a number of no longer passes through the point W of the equilibrium line
moles equals to Ye (see Appendix A.525). For the sake of com- (chemical efficiency is 0.92). The direct reduction represents
parison, we intentionally introduced the same three errors a 30.6% and the indirect reduction a 69.4%.
in our model (third column in Table 3). This way, the model
reproduces the results of Rist with a discrepancy below 3.5%, 5.3 Oxygen blast furnace with pulverized coal injection
thus validating the consistency of the model. and top gas recycling (Sahu, Data set 3)
In order to validate the model also under oxygen regimes, a
third data set from the literature is used. The availability of
The results of the model are also presented with the three men-
complete data sets in literature is limited (probably because
tioned corrections included (fifth column in Table 3). In
of non-disclosure agreements) and the information gets even
this case, the variation with respect to the data provided by Rist
more scarce when it comes to oxygen blast furnaces. For this
is beyond 5% in some cases, without overpassing the 6%. For-
reason, we take the only full data set we found (Sahu et al.27),
tunately for Rist, the three errors counterbalanced, and reason-
despite it has some underlying inconsistencies (which are con-
able results could be achieved despite of them. Making the
sequently reflected in the results of our model). Neverthe-
comparison fair, the variation between the results of our model
less, it gives a good idea on the possibilities of the model when
with and without the corrections is in the range 1–2%. This
assessing oxygen blast furnaces. The data set corresponds to an
clearly shows how well the three errors counterbalanced.
oxygen blast furnace with pulverized coal injection and top
gas recycling (Figure 6). The proximate analysis of the coal
Looking for further validation, we compare the flame tempera- is 58% ΩFC, 27% ΩVM, 10% ΩZ and 5% ΩM.
ture computed through our model with the calculated by Eq.(62).
The latter gives 1898°C (see Appendix D25) and we obtained The results of the model are compared to the reference data in
1879°C with our model, what means we have a discrepancy Table 4. Most of the results have an error below the 8%, so it
of only 1.0%. In both cases, the flame temperature is below can be considered validated. The greatest discrepancy comes
2000°C, which is not suitable for blast furnaces. Neverthe- from the nitrogen content of the blast furnace (38% error)
less, the purpose of this data set is validation only, which can be because the nitrogen mass balance is not correct in the data
assumed achieved. The type of configuration provided by this set provided by Sahu et al.26. The total inlet mass of nitrogen is
data set does not correspond to a state-of-the-art blast furnace, 17.6 kg/tHM (from coal and top gas injection), while the total
since nowadays most blast furnaces use auxiliary injections outlet mass was reported as 26.7 kg/tHM (in the BFG). Assum-
like pulverized coal and burdens of greater quality that lead ing that the correct content of nitrogen in the BFG should
to lower slag productions. be 17.6 kg/tHM, the relative error of the result of the model
drops to a reasonable 6%. Other relevant inconsistencies are
The operating line of this blast furnace is depicted in the incorrect mass balances of Fe, Mn and P. The former
Figure 5, showing that 23% of the oxygen bonded to iron leads to an overestimation of the hot metal produced, and the
oxides is removed by direct reduction, and the remaining 77% latter to negative mass flows of MnO and P2O5 in the slag (the
through indirect reduction. The chemical efficiency was assumed inlet mass flows of MnO and P2O5 are not enough to reach the
1, so the operating line passes through the point W of the specified Mn and P content in the hot metal). Despite these
equilibrium line. issues, the model can reproduce the behavior of the oxygen
Page 13 of 30
Table 3. Comparison of model results with literature data sets for air-blown blast furnaces, for validation
purposes. *This column shows the results of the model when corrections are not included (see text).
DATA SET 1 DATA SET 2
Input streams (kg/tHM) Rist10 Model* Δ (%) Model Δ (%) Babich18 Model Δ (%)
Iron ore (25°C) 2276.4 2276.4 - 2276.4 - 1558.0 1558.0 -
# Fe2O3 947.4 947.4 - 947.4 - 1146.9 1146.9 -
# FeO 357.3 357.3 - 357.3 - 187.3 187.3 -
# SiO2 327.5 327.5 - 327.5 - 69.9 69.9 -
# Al2O3 133.1 133.1 - 133.1 - 107.2 107.2 -
# CaO 446.0 446.0 - 446.0 - 26.9 26.9 -
# MgO 4.0 4.0 - 4.0 - 16.2 16.2 -
# MnO 19.9 19.9 - 19.9 - 3.6 3.6 -
# P2O5 41.2 41.2 - 41.2 - 0.0 0.0 -
Coke (25°C) 598.9 612.8 2.3 619.9 3.5 283.0 289.0 2.1
# C 509.0 520.9 2.3 526.9 3.5 251.4 256.7 2.1
# H 3.0 3.1 2.3 3.1 3.3 - - -
# S 8.2 8.4 2.3 8.5 3.6 - - -
# Fe2O3 - - - - - 1.7 1.8 2.1
# SiO2 26.5 27.1 2.3 27.4 3.5 19.7 20.1 2.1
# Al2O3 10.8 11.0 2.3 11.2 3.5 9.1 9.3 2.1
# CaO 36.1 37.0 2.3 37.4 3.5 0.8 0.8 2.1
# MgO 5.4 5.5 2.2 5.5 3.6 0.3 0.3 2.1
Coal (25°C) - - - - - 200.0 200.0 -
# C - - - - - 153.6 153.6 -
# H - - - - - 8.3 8.3 -
# O - - - - - 10.2 10.2 -
# N - - - - - 3.1 3.1 -
# S - - - - - 0.9 0.9 -
# H2O - - - - - 2.4 2.4 -
# SiO2 - - - - - 12.3 12.3 -
# Al2O3 - - - - - 8.9 8.9 -
# CaO - - - - - 0.3 0.3 -
Hot blast (700°C Rist / 1200°C 2125.6 2198.7 3.4 2242.5 5.5 1077.8 1086.6 0.8
Babich)
# N2 1618.0 1673.6 3.4 1706.9 5.5 826.7 833.5 0.8
# O2 491.0 508.2 3.5 518.3 5.6 251.1 253.1 0.8
# H2O 16.6 16.9 2.0 17.3 4.1 0.0 0.0 -
O2 enrichment (1200°C) - - - - - 94.3 95.1 0.8
Page 14 of 30
DATA SET 1 DATA SET 2
Output streams (kg/tHM) Rist

10
Model* Δ (%) Model Δ (%) Babich18 Model Δ (%)
Hot metal (1400°C Rist / 1500°C 1000.0 1000.0 0.0 1000.0 0.0 1000.0 1000.0 0.0
Babich)
# Fe 937.0 937.0 0.0 937.0 0.0 947.2 947.2 0.0
# C 38.0 38.0 0.0 38.0 0.0 45.0 45.0 0.0
# Si 4.0 4.0 0.0 4.0 0.0 5.3 5.3 0.0
# Mn 3.0 3.0 0.0 3.0 0.0 2.5 2.5 0.0
# P 18.0 18.0 0.0 18.0 0.0 0.0 0.0 0.0
Slag (1450°C Rist / 1550°C Babich) 1000.0 1002.8 0.3 1003.8 0.4 260.0 261.8 0.7
# SiO2 - 346.1 - 346.4 - 90.4 91.0 0.7
# Al2O3 - 144.1 - 144.3 - 124.6 125.4 0.7
# CaO - 468.4 - 468.6 - 26.3 26.5 0.7
# MgO - 9.5 - 9.5 - 16.4 16.5 0.7
# MnO - 16.0 - 16.0 - 0.4 0.4 0.7
# CaS - 18.8 - 19.0 - 1.9 1.9 0.7
# P2O5 - 0.0 - 0.0 - - - -
BFG (180°C Rist / 150°C Babich) 3000.0 3085.2 2.8 3135.1 4.5 1953.2 1966.9 0.7
# N2 - 1673.6 - 1706.9 - 830.0 836.6 0.8
# CO2 - 743.1 - 735.4 - 678.8 684.4 0.8
# CO - 653.1 - 672.0 - 414.7 416.2 0.4
# H2O - 11.8 - 17.7 - 23.9 23.8 -0.6
# H2 - 3.6 - 3.0 - 5.9 5.9 0.0
Operating conditions
Chemical efficiency, r (-) 1.000 1.000 - 1.000 - - 0.92 -
Thermal reserve zone temperature, 1000.0 1000.0 - 1000.0 - - 800 -

TR (°C)
Flame temperature, Tfl (°C) - 1879.0 - 1881.0 - 2117.0 2138.6 1.0
Heat evacuated by the staves 418.4 418.4 - 418.4 - 701.1 701.1 -

(MJ/THM)
Heat evacuated in the elaboration 0.700 0.700 - 0.700 - - 0.800 -

zone, θst (-)
Oxidation state of the BFG, ηCO–H2 (-) - 0.411 - 0.410 - 0.486 0.487 0.2
blast furnace described by Sahu et al.27 within reasonable dis- one reported by Sahu et al.27 (2126°C). Although they did
crepancy limits. Moreover, the model has turn out to be a useful not explain how they calculated this temperature, they prob-
tool to identify potential inconsistencies in data sets. ably did not account for the heating of the injected top gas, while
our model does. In fact, one of the reasons of recirculating
Regarding the flame temperature, in this case we cannot use top gas is to substitute N2 as heat sink during oxygen regimes,
the Eq.(62) to compute it since this formula does not account so probably that is why Sahu et al.26 had to set the inlet tem-
for top gas injections. By using our model, we found a flame perature of the oxygen to 25°C (otherwise they would found
temperature of about 1770°C, which is a 17% lower than the excessive flame temperatures because of not accounting for
Page 15 of 30
Figure 5. Operating lines obtained from the Data sets 1, 2 and 3 (Table 3 and Table 4).
Figure 6. Conceptual schemes summarizing the mass flows and relative errors obtained during the validation of the model for
Data set 1, 2 and 3 (the complete data sets are presented in Table 3 and Table 4).
the recycled gas). If we calculate in our model the temperature 6. Predicting the operating line for an oxygen blast
of the flame without taking into account the sensible heat of furnace integrated with PtG
the recycled gas, we found temperatures between 2200 and Once the model has been validated, we are going to analyze
2300°C, which are closer to that provided by Sahu et al.26. a potential configuration for a blast furnace operation under
an oxygen regime, with top gas recycling, and injections of
The operating line of this blast furnace is depicted in Figure 5. pulverized coal and synthetic natural gas. The data set was
It passes through the point W of the equilibrium line because inspired in the works of Sahu et al.27 and Jin et al.29, aiming to
it is assumed chemical ideality. It can be seen that that the reproduce similar results to them, but keeping reasonable
direct reduction represents only a 0.3% of the total reduc- operating conditions (e.g., flame temperature between 2000–
tion, which is unrealistic for a real operation. Therefore, for 2300°C, direct reduction about 10–15%, slag production above
this reason and the other mentioned inconsistencies, we do not 200 kg/tHM). The proximate analysis of the coal for this data
recommend using this data set for further analyses. set is 70.7% ΩFC, 17.2% ΩVM, 10.8% ΩZ and 1.2% ΩM.
Page 16 of 30
Table 4. Data sets for oxygen blast furnaces with top gas recycling. The Data set 3 is taken from Sahu et al.27
and compared with the results of our model. The Data sets 4, 5 and 6 were elaborated in the present paper.
DATA SET 3 DATA SET 4 DATA SET 5 DATA SET 6

Input streams (kg/tHM) Sahu27 Model Δ (%) OBF-PtG OBF-PtG OBF-PtG
with coke with coal
replacement replacement
Iron ore (25°C) 1689.4 1689.4 - 1500.0 1500.0 1500.0
# Fe2O3 616.4 616.4 - 954.7 954.7 954.7
# FeO 771.8 771.8 - 369.2 369.2 369.2
# SiO2 78.8 78.8 - 58.9 58.9 58.9
# Al2O3 58.4 58.4 - 70.8 70.8 70.8
# CaO 129.4 129.4 - 15.7 15.7 15.7
# MgO 34.6 34.6 - 21.5 21.5 21.5
# MnO - - - 9.2 9.2 9.2
Coke (25°C) 234.9 234.1 -0.3 261.3 238.5 261.3
# C 195.7 195.0 -0.3 217.7 198.7 217.7
# S 1.2 1.2 -0.3 1.3 1.2 1.3
# SiO2 22.8 22.7 -0.3 25.4 23.1 25.4
# Al2O3 13.6 13.6 -0.3 15.1 13.8 15.1
# CaO 1.1 1.1 -0.3 1.2 1.1 1.2
# MgO 0.5 0.5 -0.3 0.6 0.5 0.6
Coal (25°C) 200.0 200.0 - 185.0 185.0 154.8
# C 147.3 147.3 - 142.1 142.1 118.9
# H 9.0 9.0 - 5.9 5.9 4.9
# O 8.9 8.9 - 9.4 9.4 7.9
# N 4.0 4.0 - 4.7 4.7 3.9
# S 1.1 1.1 - 0.8 0.8 0.7
# H2O 10.0 10.0 - 2.2 2.2 1.9
# FeO 0.7 0.7 - - -
# SiO2 11.9 11.9 - 11.4 11.4 9.5
# Al2O3 6.2 6.2 - 8.2 8.2 6.9
# CaO 0.5 0.5 - 0.3 0.3 0.3
# MgO 0.3 0.3 - - - -
# P2O5 0.1 0.1 - - - -
O2 injection (25°C Sahu / 1200°C 337.6 355.3 5.2 334.7 345.4 340.0
Bailera)
# O2 330.7 348.1 5.3 318.1 328.2 323.0
# H2O 6.9 7.3 4.6 7.7 8.0 7.8
# N2 - - - 9.0 9.3 9.1
Recycled gas injection (900°C Sahu / 613.6 613.6 0.0 600.0 600.0 600.0
1200°C Bailera)
# N2 13.6 12.5 -8.0 27.0 24.1 24.6
# CO2 34.2 31.7 -7.1 53.1 45.0 48.7
# CO 554.4 558.2 0.7 512.5 524.7 518.7
# H2 11.5 11.2 -2.5 7.5 6.3 8.0
Page 17 of 30
DATA SET 3 DATA SET 4 DATA SET 5 DATA SET 6

Input streams (kg/tHM) Sahu27
Model Δ (%) OBF-PtG OBF-PtG OBF-PtG
with coke with coal
replacement replacement
Synthetic methane injection (25°C - - - - 21.8 21.8
Bailera)
# CH4 - - - - 21.1 21.1
# CO2 - - - - 0.5 0.5
# H2O - - - - 0.1 0.1
# H2 - - - - 0.1 0.1
Output (kg/tHM)
Hot metal (1425°C Sahu / 1500°C 1000.0 1078.1 7.8 1002.3 1002.3 1002.3
Bailera)
# Fe 949.5 1023.7 7.8 951.2 951.2 951.2
# C 42.3 45.6 7.9 44.7 44.7 44.7
# Si 5.8 6.3 7.9 5.8 5.8 5.8
# Mn 0.6 0.7 8.3 0.6 0.6 0.6
# P 1.8 1.9 0.0 - - -
Slag (1500°C Sahu / 1550°C Bailera) 347.8 341.3 -1.9 226.1 222.4 222.8
# FeO - 0.7 - -
# SiO2 - 100.1 - 83.2 81.0 81.4
# Al2O3 - 78.1 - 94.1 92.8 92.8
# CaO - 127.0 - 13.5 13.5 13.6
# MgO - 35.4 - 22.1 22.0 22.1
# MnO - -0.8 - 8.4 8.4 8.4
# CaS - 5.2 - 4.8 4.5 4.5
# P2O5 - -4.3 - -
BFG (100°C Sahu / 150°C Bailera) 1668.1 1672.0 0.2 1652.7 1666.0 1652.7
# N2 26.7 16.5 -38.2 40.6 38.0 37.6
# CO2 798.7 838.1 4.9 799.8 710.7 745.0
# CO 762.2 737.0 -3.3 772.1 828.6 793.4
# H2O 66.7 65.7 -1.5 28.9 78.8 64.5
# H2 13.8 14.7 7.0 11.3 9.9 12.2
Operating conditions
Chemical efficiency, r (-) - 1.000 - 0.920 0.920 0.920
Thermal reserve zone temperature, TR 807.6 807.6 - 950.0 950.0 950.0
(°C)
Flame temperature, Tfl (°C) 2126.0 1768.9 -16.8 2082.9 1995.6 2014.2
Heat evacuated by the staves (MJ/THM) 500.0 500.0 - 700.0 700.0 700.0
Heat evacuated in the elaboration zone, - 0.770 - 0.800 0.800 0.800
θst (-)
Oxidation state of the BFG, ηCO-H (-) 0.391 0.403 3.2 0.374 0.373 0.374
2
Page 18 of 30
The proposed oxygen blast furnace would be integrated with to recycle the top gas, which can benefit from the exothermal
a PtG plant, which renewably produces the synthetic methane. heat available from the methanation process. Furthermore,
This methane is used to reduce the consumption of coke or the electrolyzer by-produces 87 kg/tHM of O2 that can be used
coal, thus substituting a fossil fuel by a renewable fuel. The in the blast furnace, thus reducing the energy requirements
conceptual scheme of the blast furnace is the one depicted in in the air separation unit that enriches the hot blast. For
Figure 7 (Data set 5 when coke is replaced and Data set 6 these calculations, it was assumed an electrolysis efficiency
when coal is replaced). We assume a 150 MW electrolyzer and of 68%30.
a 280 tHM/h blast furnace. This means that the electrolyzer
produces 11 kg/tHM of hydrogen, which are converted to For comparison purposes, the blast furnace was also modelled
21.8 kg/tHM of synthetic methane by consuming 60 kg/tHM of without the integration of the PtG plant, and therefore with-
CO2. This carbon is continuously recycled in a closed loop, out the injection of synthetic methane (Data set 4, which is
and therefore the corresponding emissions are avoided. The considered as the base case). In all cases, the mass flow of
CO2 would come from the carbon capture stage that is used injected top gas was kept constant at 600 kg/tHM (despite its
Figure 7. Conceptual schemes summarizing the mass flows obtained for Data sets 4, 5 and 6 (see Table 4).
Page 19 of 30
composition changes). The three data sets are presented in These values of energy penalization for the avoidance of CO2
Table 4. In the base case (Data set 4), the total CO2 that would are clearly above the typical consumptions of conventional
be emitted after the combustion of the BFG is 1154 kgCO2/tHM, amine carbon capture, which are usually in the range
of which the 41.4% (i.e., 478 kgCO2/tHM) could be directly cap- 3.7–4.8 MJ/kgCO233,34. Nevertheless, the integration of PtG
tured since they come from the carbon capture stage. When presents the additional benefits of diminishing the coke/coal
implementing PtG, 60 kg/tHM of CO2 are recycled in closed loop, consumption in the blast furnace, reducing the electricity
which allow to reduce the coke consumption by 8.7% or alter- consumption in the air separation unit, and suppressing the
natively the coal consumption by 16.3%. In case of substituting requirement of geological storage for the avoided CO2 (it is
coke, the total emissions become 1083 kgCO2/tHM, of which the kept in a closed carbon loop thanks to PtG). Therefore, an over-
31.8% can be directly captured and stored (i.e., 345 kgCO2/tHM). all economic and energy analysis of the whole integrated steel
Thus, in overall terms, the CO2 is diminished by 71 kgCO2/tHM plant should be necessary to reach farther conclusions. Fur-
with respect to the base case by using 1.93 GJ/tHM of electric- thermore, there exist other potential PtG integrations that may
ity in the electrolyzer, so the energy penalty of the CO2 avoid- lead to lower energy penalizations, such as the utilization of
ance is 27.1 MJ/kgCO2. This value is line with the results of the BFG in the methanation stage rather than the captured CO2
Perpiñán et al.8 for similar PtG integrations in the steel indus- (which allow producing more SNG with the same amount
try (he reported 34 MJ/kgCO2). Actually, since we have cut the of H2) or the injection of the H2 in the blast furnace without
coke consumption by 22.8 kg/tHM, which, in terms of electric- considering a methanation stage.
ity, is equivalent to a reduction of 0.24 GJ/tHM (assuming a
coke heating value of 27.3 MJ/kg and a subcritical power plant Regarding the flame temperature, it is reduced about 90°C when
net efficiency of 38%31), and additionally we diminished the injecting 22 kg/tHM of synthetic methane for replacing coke.
O2 that has to be produced in the air separation unit by This is a reduction of 4.0°C per kgSNG/tHM, which is in good
77 kgO2/tHM (we need inject 10 kgO2/tHM more than in the base but agreement with the value reported by Babich et al. for natural
we have 87 kgO2/tHM available from electrolysis), which translates gas (4.5°C per kgNG/tHM16). When we replace coal by syn-
into a reduction of 0.05 MJ/tHM of electric consumption (assum- thetic natural gas, the temperature of the flame is reduced by
ing a typical ASU specific consumption of 0.61 MJ/kgO232), 3.1°C per kgSNG/tHM, which also matches the value reported by
the net energy penalization of the CO2 avoidance becomes Babich et al. for this type of replacement (3.0°C per kgNG/tHM16).
23.1 MJ/kgCO2. Alternatively, in the case of using the syn-
thetic methane to replace part of the coal, the total emissions Lastly, the percentage of direct reduction is 15% for the base
become 1068 kgCO2/tHM. Following the same calculations just case and about 12% when injecting synthetic natural gas. The
mentioned, the gross energy penalization of CO2 avoidance in decrease in this value was expected since direct reduction takes
this case would be 22.4 MJ/kgCO2 and the net energy penaliza- place through solid carbon, and the coke/coal input is dimin-
tion 17.9 MJ/kgCO2 (the heating value of coal is 29.4 MJ/kg, ished when PtG is integrated. The operating lines are presented
Eq.(130)). Table 5 summarizes these calculations. in Figure 8.
Table 5. Comparison of CO2 emissions, CO2 avoided and energy penalization between data sets 4
(oxygen blast furnace), 5 (oxygen blast furnace with PtG integration for the replacement of coke
by synthetic methane) and 6 (oxygen blast furnace with PtG integration for the replacement of
coal by synthetic methane).
OBF-PtG with coke OBF-PtG with

OBF Base case
replacement (Data coal replacement
(Data set 4)
set 5) (Data set 6)
Total CO2 emissions (kg/tHM) 1154 1083 1068
- From BFG combustion (kg/tHM) 676 738 690
- From CC stage (kg/tHM) 478 345 378
Total CO2 emissions avoided (kg/tHM) - 71 86
Total CO2 emissions avoidance ratio (%) - 6.1 7.4
Electricity for PtG (GJ/tHM) - 1.93 1.93
Electricity saved in the ASU (GJ/tHM) - 0.05 0.05
Fossil fuel saved (kg/tHM) - 22.8 30.2
- Equivalent electricity saved (GJ/tHM) - 0.24 0.34
Fossil fuel replacement ratio (kg/kgSNG) - 1.05 1.38
Gross CO2 avoidance penalization (MJ/kgCO2) - 27.1 22.4
Net CO2 avoidance penalization (MJ/kgCO2) - 23.1 17.9
Page 20 of 30
Figure 8. Operating lines of oxygen blast furnaces, obtained from Data sets 4, 5 and 6 (Table 4).
7. Conclusions corresponds to an air-blown blast furnace without auxiliary

The operating diagram, which was originally developed by injections (error <5.6%), the second one to an air-blown blast
Rist in 1963, is a useful methodology for predicting the oper- furnace with pulverized coal injection (error <2.1%), and
ating conditions in a blast furnace through a graphical rep- the third one to an oxygen blast furnace with top gas recy-
resentation which takes into account the mass and energy cling and pulverized coal injection (error <8.3%). However, it
balances. This methodology was described in a series of papers would be desirable to have a discrepancy below 5% in all
between 1963 and 1967, of which the most relevant were cases, we consider the model validated since the slightly
published in French. In this paper we have revisited the work variation above 5% is justified. In the first case, the data set
of Rist, summarizing his methodology and making some addi- corresponds to the results of Rist, therefore they include the
tions and corrections. We have presented a general model errors that were corrected in our model. When we deliber-
that considers multiple injectants separately, with all calcu- ately include in our model the same errors than Rist, the differ-
lations given as a function of the temperature of the thermal ence between both results becomes lower than 3.5%. In the
reserve zone. Besides, the model now calculates the sensible third case, the reference data set have some incorrect mass
heats of the hot metal and slag as a function of their composi- balances in origin that led to this higher error. Neverthe-
tion, and the heat of carburization as a function of the austen- less, these inconsistencies were properly identified by our
ite and cementite content in iron. Furthermore, it is added a model, and the overall behavior of the blast furnace could be
supplementary model to compute the heat of decomposi- correctly described.
tion of coal, an additional energy balance in the upper zone of
the blast furnace to compute the final composition of the blast The objective in revisiting the operating diagram of Rist is to
furnace gas, and other energy balance for the calculation of study a new concept for the reduction of CO2 emissions in blast
the flame temperature. Regarding corrections, the heat asso- furnaces. This concept combines oxygen blast furnaces with
ciated to the direct reduction of FeO now accounts for the PtG technology. The latter renewably produces synthetic
moisture of the hot blast, the heat associated to the lack of methane, which is used to replace part of the coke or coal.
chemical ideality now includes the influence of the hydrogen Carbon is thus continuously recycled in a closed loop, and
coming from auxiliary fuels and of the moisture of the hot the corresponding emissions are avoided without requir-
blast, and lastly, the sensible heats of hot metal and slag are ing geological storage. Furthermore, the electrolyzer of the
now correctly computed and accounted. PtG plant by-produces O2 that can be used in the blast fur-
nace to reduce the electricity consumption in the air separa-
The model elaborated in this paper has been validated with tion unit that enriches the hot blast. In this study, we presented
three different operation data sets from literature. The first one the first approach to this integration concept, comparing the
Page 21 of 30
performance of the blast furnace when coke is replaced to the CΔT sensible heat of the burden between TR – ΔTR and TR
R
performance when coal is replaced. It was assumed a 280 tHM/h (lack of thermal ideality), kcal/molFe
oxygen blast furnace producing 1154 kgCO2/tHM, coupled to a dj number of moles of S2 in injectant j per number of
PtG plant with 150 MW electrolysis power capacity that pro- moles of injectant j, molS2/molj
duces 11 kgH2/tHM of hydrogen (then converted to 21.8 kgSNG/tHM
e number of moles of H2O per number of moles of O
of synthetic methane by using pure CO2 from a carbon cap-
in the air (i.e., e = ye/yv), molH2O/molO
ture stage). The model shows fuel replacement ratios of
1.05 kg/kgSNG for coke and 1.38 kg/kgSNG for coal, which lead f sensible heat of the hot metal between TR and Tf
to CO2 emission reductions of 6.1% and 7.4%, respectively. (outlet temperature), kcal/molFe
As the electricity consumed in the PtG plant is 1.93 GJ/tHM, the gi specific Gibbs free energy of compound i, kcal/moli
gross energy penalization of the CO2 avoidance is 27.1 MJ/kgCO2 ΔG Gibbs free energy change of reaction, kcal/mol
when coke is replaced and 22.4 MJ/kgCO2 when coal is replaced.
Considering the energy content of the fossil fuel that is saved, h enthalpy, kcal/mol
and the electricity that is no longer consumed in the air Δhf enthalpy of fusion, kcal/mol
separation unit, the net energy penalizations are 23.1 MJ/kgCO2 Δch enthalpy of combustion, kcal/mol
and 17.9 MJ/kgCO2, respectively. These values are several times
Δfh enthalpy of formation, kcal/mol
greater than the specific consumption of amine carbon capture
(typically 3.7–4.8 MJ/kgCO2). However, the integration of Keq equilibrium constant of the water-gas shift reaction, -
PtG diminishes the coke/coal consumption in the blast fur- l sensible heat of the slag between TR and Tl (outlet
nace, reduces the electricity consumption in the air separation temperature), kcal/molFe
unit, and eliminates the requirement of geological storage for mj,i mass of compound i in stream j per ton of hot metal,
the avoided CO2. Therefore, a detailed economic comparison kg/tHM
between both methods should be necessary to reach firm
M molar weight, kg/kmol
conclusions. Furthermore, there exist other potential PtG inte-
grations that may lead to lower energy penalizations, such nj,i number of moles of compound i in stream j per ton
as the utilization of the BFG in the methanation stage rather of hot metal, mol/tHM
than captured CO2, what would allow producing more SNG p heat removed by the staves in the elaboration zone,
with the same amount of H2. kcal/molFe
p′ heat removed by the staves in the preparation zone,
Lastly, the present paper has provided six full data sets of dif- kcal/molFe
ferent blast furnaces operations, specifying the composition of qc heat released at TR by the reaction C (coke) + 0.5 O2 →
all streams, as well as the most relevant operating parameters CO, kcal/molO
(e.g., temperature of the thermal reserve zone, heat evacuated
by the staves, and the temperature of the flame). The availabil- qe heat required by the H2O in hot blast due to disso-
ity of this information in literature is very scarce, especially for ciation, reverse water-gas shift and sensible heat,
oxygen blast furnaces. kcal/molH2O
qer heat absorbed at TR by the reaction C + H2O → CO + H2,
Nomenclature kcal/molH2O
In this paper we used calorie as unit of energy for calculations qes enthalpy change of water between Tv and TR, kcal/molH2O
related to operating diagram in order to facilitate comparing qf,i heat required to melt and increase the temperature
results with the original work of Rist. Elsewhere, the SI unit is of compound i from TR to Tf, kcal/moli
used (Joule).
qFe sensible heat of wüstite between TR – ΔTR and TR,
0.95O
kcal/molO
Symbols
ai calculation parameter, 1/°Ci qFe C heat absorbed at TR by the reaction 3Fe + C → Fe3C,
3
kcal/molC
aj number of moles of H2 in injectant j per number of
moles of injectant j, molH2/molj qFe O sensible heat of magnetite between TR – ΔTR and TR,
3 4
kcal/molFe3O4
A calculation parameter, kcal/mol
qg heat absorbed at TR by the reaction C + CO2 → 2CO,
bj number of moles of O2 in injectant j per number of kcal/molC
moles of injectant j, molO2/molj
qim heat released at TR by the reaction 1/4 Fe3O4 + CO → 3/4
B calculation parameter, kcal/mol Fe + CO2, kcal/molO
cj number of moles of N2 in injectant j per number of qiw heat released at TR by the reaction Fe0.95O + CO → 0.95
moles of injectant j, molN2/molj Fe + CO2, kcal/molO
cp heat capacity, kcal/(mol·K) qj thermal demand by injectant j, CH2aO2bN2cS2dZz (or
C calculation parameter, kcal/mol H2aO2bN2c or O2bN2c) due to dissociation, sensible heat,
Page 22 of 30
reverse water-gas shift of the H2, incomplete com- T temperature, °C (unless otherwise specified)
bustion with the O2, and transfer of S to the slag, ΔTR difference of temperature between the gas and the
kcal/molj solid at the beginning of the middle zone, °C
qjd heat absorbed at Tj by the dissociation reaction of Vj volume flow of stream j consumed in the blast
injectant j, CH2aO2bN2cS2dZz → C + aH2 + bO2 + cN2 + furnace per ton of hot metal, Nm3/tHM
dS2 + zZ, kcal/molj
xd number of moles of O removed from wüstite by direct
qjs,i enthalpy change of element i from injectant j between reduction per total moles of reducing gas mixture,
Tj and TR, kcal/moli molO/(molC+molH2)
qk heat absorbed at TR by the total H2 in the furnace when xe number of moles of H2O in hot blast per total moles
considering that it is completely converted to H2O of reducing gas mixture, molH2O/(molC+molH2)
through the reverse water-gas shift reaction, kcal/molH2 xh molar fraction of hydrogen and water in the reducing
ql,i heat required to melt and increase the temperature of gas mixture, -
compound i (SiO2, Al2O3, CaO, MgO) from TR to Tl, xi number of moles of O transferred from the iron oxides
kcal/moli to the gas by indirect reduction per total moles of
qMn heat absorbed at TR by the reaction C +MnO → CO + reducing gas mixture, molO/(molC+molH2)
Mn, kcal/molO xj number of moles of injectant j (overall formula
qP heat absorbed at TR by the reaction 1/5 P2O5 ⋅ 3CaO + CH2aO2bN2cS2dZz, H2aO2bN2c or O2bN2c) per total moles
C + 6/5 Fe → 2/5 Fe3P + 3/5 CaO + CO, kcal/molO of reducing gas mixture, molj/(molC+molH2)
qrmc heat consumed by the reaction 1.5 Fe2O3 + 0.5 CO → xk number of moles of H2 in the coke per total moles
Fe3O4 + 0.5 CO2, including also the heat exchange of reducing gas mixture, molH2/(molC+molH2)
between reactants and products at different temperatures, xMn number of moles of O removed by direct reduc-
kcal/molFe3O4 tion of MnO per total moles of reducing gas mixture,
qrwc heat consumed by the reaction 0.5 Fe2O3 + 0.5 CO molO/(molC+molH2)
→ FeO + 0.5 CO2, including also the heat exchange xP number of moles of O removed by direct reduc-
between reactants and products at different temperatures, tion of P2O5 per total moles of reducing gas mixture,
kcal/molFeO molO/(molC+molH2)
qR,i sensible heat of compound i (SiO2, Al2O3, CaO, MgO, C) xS number of moles of O replaced by S in the slag per
between TR – ΔTR and TR, kcal/moli total moles of reducing gas mixture, molO/(molC+molH2)
qS heat absorbed at TR by the reaction 1/2 S2 + CaO + C → xSi number of moles of O removed by direct reduc-
CaS + CO, kcal/molS tion of SiO2 per total moles of reducing gas mixture,
qs,i sensible heat of component i between Tfl and TR, molO/(molC+molH2)
kcal/moli xv number of moles of O in hot blast per total moles
qs,nr,i sensible heat of non-reacting compound i, kcal/moli of reducing gas mixture, molO/(molC+molH2)
qSi heat absorbed at TR by the reaction C + 1/2 SiO2 + 3/2 X abscissa in the Rist diagram, (molO+molH2)/
Fe → CO + 1/2 Fe3Si, kcal/molO (molC+molH2)
qst heat removed by the staves from the blast furnace per yC number of moles of C (coke) that are consumed in
ton of hot metal, kcal/thot metal combustion in the raceways per mol of Fe produced,
molC/molFe
qv energy available from the sensible heat of the air
yd number of moles of O removed from wüstite by
between Tv and TR, kcal/molO
direct reduction per mol of Fe produced, molO/molFe
qy heat absorbed at TR by the carburization of the iron,
ye number of moles of H2O in hot blast per mol of Fe
kcal/molC
produced, molH2O/molFe
qyFe heat absorbed at TR by the reaction C(coke) →
yi number of moles of O transferred from the iron
C(austenite), kcal/molC
oxides to the gas by indirect reduction per mol of Fe
qε heat absorbed at TR by the reaction H2 + CO2 → H2O + produced, molO/molFe
CO, kcal/molH2
yj number of moles of injectant j (overall formula
q ′ε heat absorbed by the reaction H2 + CO2 → H2O + CO CH2aO2bN2cS2dZz, H2aO2bN2c or O2bN2c) per mol of Fe
taking into account the temperature of reactants and produced, molj/molFe
products, kcal/molH2(reacting)
yk number of moles of H2 in the coke per mol of Fe
r chemical efficiency of the blast furnace, - produced, molH2/molFe
R ideal gas constant, kcal/(mol K) yMn number of moles of O removed by direct reduction
Si specific entropy of compound i, kcal/(moli K) of MnO per mol of Fe produced, molO/molFe
Page 23 of 30
ynr,i number of moles of compound i that is traversing μ slope of the Rist diagram, i.e. , number of moles of reduc-
the preparation zone without reacting per mol of Fe ing gas per mol of Fe produced, (molC+molH2)/molFe
produced, moli/molFe τj calculation parameter that is 1 when the auxiliary
yP number of moles of O removed by direct reduction injection j contains carbon and 0 when not, -
of P2O5 per mol of Fe produced, molO/molFe ϕ percentage of H2 consumed in the preparation zone, -
yrg,i number of moles of component i in the reducing gas ω molar fraction, -
at the raceways per mol of Fe produced, moli/molFe
Ωji mass fraction of compound i in stream j, -
yrmc number of moles of Fe3O4 produced in the preparation
zone per mol of Fe produced, molFe3O4/molFe Subscripts and superscripts
yrwc number of moles of FeO produced in the preparation A initial oxidation state of the iron oxides at the inlet
zone per mol of Fe produced, molFeO/molFe of the blast furnace
yS number of moles of O replaced by S in the slag per BFG blast furnace gas
mol of Fe produced, molO/molFe C related to carbon or C-CO2 mixtures
ySi number of moles of O removed by direct reduction d dry basis (superscript), decomposition (subscript)
of SiO2 per mol of Fe produced, molO/molFe
e moisture in hot blast
yv number of moles of O in hot blast per mol of Fe
f hot metal (at the outlet)
produced, molO/molFe
FC fixed carbon
ywgs number of moles of H2 reacting in the preparation zone,
molH2/molFe Fe3C referred to the number of moles of C in hot metal
dissolved as cementite
Y ordinate in the Rist diagram, (molO+molH2)/molFe
fl flame
YE intercept of the operating line representing the moles
of H2 and O coming from sources other than iron H related to hydrogen or H2-H2O mixtures
oxides that contribute to the formation of the reduc- HM hot metal
ing gas per mol of Fe produced (negative sign IN inlet of solids at the top of the furnace
by convention), (molO+molH2)/molFe
IO iron ore
YE* terms of YE that are independent of yv, (molO+molH2)/
j injectant (overall formula CH2aj O2bj N2cj S2dj ZZJ or
molFe
stream
YM* number of moles of O per mole of Fe3O4 (i.e., YM* ),
K coke
molO/molFe3O4
slag (at the outlet)
Zj number of moles of ashes in injectant j per number
of moles of injectant j, molash/molj l magnetite or moisture
m natural moisture in blast
Greek symbols NG natural gas
γ number of moles of C dissolved in the hot metal,
nr non-reacting in the preparation zone
molC/molFe
P characteristic point of the operating line referring to
γFe C number of moles of C dissolved in the hot metal
3 the energy balance of the blast furnace
as cementite, molC/molFe
PM primary volatile matter
γγFe number of moles of C dissolved in the hot metal
as austenite, molC/molFe R characteristic point of the operating line referring to
the thermal reserve zone
δ decrease in the available heat due to the presence of
magnetite in the elaboration zone, kcal/molFe SM secondary volatile matter
δ ′ decrease in the heat absorbed by the reverse v hot blast / air
water-gas shift reaction because of the lack of chemical VM volatile matter
ideality, kcal/molFe W referring to wüstite or to the characteristic point
Δ1 calculation parameter, - of the equilibrium line in which pure wüstite is in
Δ2 calculation parameter, (molO+molH2)/molFe equilibrium with the gas
𝜖K number of moles of C and H2 in coke per kg of P ashes
coke, (molC+molH2)/molK γFe referred to the number of moles of C in hot metal that
η humidity in the air, (g/Nm )
3 are dissolved as austenite
ηCO–H oxidation state of the blast furnace gas leaving the Data availability
2
top, - Extended data
θst fraction of the total heat removed by the staves that Zenodo: Extended data for ‘Revisiting the Rist diagram for pre-
is coming from the elaboration zone (i.e., from the dicting operating conditions in blast furnaces with multiple
control volume of the energy balance), - injections’ https://doi.org/10.5281/zenodo.563758039
Page 24 of 30
The project contains the following extended data: Appendix D – Calculation of the flame temperature through
Appendix A – Terms of the energy balance in the elaboration Eq.(62)
zone DISIPO_OPEN DATA_1.xlsx
Appendix B – Heat of decomposition of coal (dry basis)
Data are available under the terms of the Creative Commons
Appendix C – Energy balance in the preparation zone Attribution 4.0 International license (CC-BY 4.0).
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Page 26 of 30
Open Peer Review

Current Peer Review Status:
Version 1
Reviewer Report 07 February 2022
https://doi.org/10.21956/openreseurope.15400.r28319
© 2022 Bargiacchi E. This is an open access peer review report distributed under the terms of the Creative
Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.
Eleonora Bargiacchi
IMDEA Energy Institute, Madrid, Spain
The paper investigates the integration of Power to Gas (PtG) technology into oxygen blast
furnaces (OBF). For this purpose, a corrected version of the Rist diagram is proposed to predict the
system operating conditions. The major novelties of the paper rely on the revisitation of the blast
operating diagram and on the integration of OBF and PtG technologies.
The paper is novel, well organized, clear, and scientifically robust. I hereby suggest some
modifications and corrections that the authors may wish to implement in future versions of the
paper:
○ In the introduction, a better contextualization of the advantages and disadvantages of OBF
with respect to other technologies would be useful to the reader. Similarly, the proposed
solution (OBF+PtG) should be better contextualized (advantages/disadvantages with respect
to other solutions). Overall, some useful references proposing advances in steelmaking
plants with respect to carbon capture and emission reduction should be added (e.g.: Arasto
et al.)
○ "Within this framework, several authors have studied the application of power to gas (PtG)
to ironmaking processes based on the reduction of iron ores with coke in a blast furnace
(BF)." The references to these authors/papers are missing.
○ After the integration of the blast furnace with the PtG plant the author states: "Thus, in
overall terms, the CO2 is diminished by 71 kgCO2/tHM with respect to the base case by using
1.93 GJ/tHM of electricity in the electrolyzer, so the energy penalty of the CO2 avoidance is
27.1 MJ/kgCO2. ". Are the impacts associated to the electricity supplied to the electrolyzer
accounted for? If not, I recommend including a discussion on the impacts of the electricity
supplied to the electrolysis process. Also, the avoided CO2 emissions and CO2 emissions
avoidance ratio should be recalculated by adding the impacts of the electrolysis (and table 5
should be modified accordingly).
Minor comment:
○ I recommend the use of the simple past instead of the present perfect (e.g.: in the
Page 27 of 30
"Conclusions" section).
References
1. Arasto A, Tsupari E, Kärki J, Lilja J, et al.: Oxygen blast furnace with CO 2 capture and storage at
an integrated steel mill—Part I: Technical concept analysis. International Journal of Greenhouse Gas
Control. 2014; 30: 140-147 Publisher Full Text
Is the work clearly and accurately presented and does it cite the current literature?
Yes
Is the study design appropriate and does the work have academic merit?
Yes
Are sufficient details of methods and analysis provided to allow replication by others?
Yes
If applicable, is the statistical analysis and its interpretation appropriate?

Not applicable
Are all the source data underlying the results available to ensure full reproducibility?
Yes
Are the conclusions drawn adequately supported by the results?

Yes
Competing Interests: No competing interests were disclosed.
Reviewer Expertise: Power-to-Fuel and hydrogen technologies
I confirm that I have read this submission and believe that I have an appropriate level of
expertise to confirm that it is of an acceptable scientific standard.
Reviewer Report 01 February 2022
https://doi.org/10.21956/openreseurope.15400.r28384
© 2022 Schenk J. This is an open access peer review report distributed under the terms of the Creative Commons
Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the
original work is properly cited.
Johannes Schenk
Montanuniversität Leoben, Leoben, Austria
Generations of blast furnace operators use the Rist diagram to evaluate the operating condition of
their furnace. With this publication, the authors have shown that this diagram can also be used to
Page 28 of 30
evaluate new alternative process variants for the blast furnace. They have extended the original
model approach of Rist to make the application more universal. In particular, the following
extensions were made: (1) nearly any auxiliary injection composition and material is possible, (2) a
new model approach for the energy balance that takes into account all possible energy sinks and
sources, (3) for the operating line, the chemical efficiency is taken into account for the position
relative to the Wüstit point W and in the determination of the energy balance point P.
With this publication, the authors have made a significant contribution to the future application of
the Rist diagram for the blast furnace process. The published model approach is universal. A
valuable contribution is the detailed description of submodels in appendixes A to D. In the case
studies presented, new blast furnace process and integration concepts are investigated and
evaluated. These results are scientifically and technologically new. I appreciate reviewing the
paper.
My recommendation is to approve this publication as fit to pass peer review.
I have some comments and questions that the authors might consider in the final version:
○ Equation (49) - The variable тj is not clear. Is the “+” operator after т_j correct, or should it be
“x”?
○ Final degree of oxidation of BFG, xi - Is the LOI and moisture of burden and coke
considered?
○ Calculation of flame temperature: Which temperature is assumed for the coke entering the
raceway?
Is the work clearly and accurately presented and does it cite the current literature?
Yes
Is the study design appropriate and does the work have academic merit?
Yes
Are sufficient details of methods and analysis provided to allow replication by others?
Yes
If applicable, is the statistical analysis and its interpretation appropriate?

Not applicable
Are all the source data underlying the results available to ensure full reproducibility?
Yes
Are the conclusions drawn adequately supported by the results?

Yes
Competing Interests: No competing interests were disclosed.
Reviewer Expertise: My area of expertise is ironmaking. I am dealing with blast furnace, direct
Page 29 of 30
reduction and smelting reduction technologies.
I confirm that I have read this submission and believe that I have an appropriate level of
expertise to confirm that it is of an acceptable scientific standard.
Page 30 of 30

Revisiting the Rist Diagram for Predicting Operating Conditions in Blast Furnaces With Multiple Injections

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Open Research Europe Open Research Europe 2021, 1:141 Last updated: 02 MAR 2023

Revisiting the Rist diagram for predicting operating

v1 First published: 29 Nov 2021, 1:141 Open Peer Review

requirement of geological storage.

This article is included in the Marie-Sklodowska-

This article is included in the Chemical

Corresponding author: Manuel Bailera ([email protected])

Plain language summary moderate reductions, water electrolysis power capacities of

The paper is divided in the following sections. First, a brief

description on how to find the equilibrium line for the diagram

3.1 Formation of the reducing gas (Rist diagram in the

In this equation, each addend denotes the number of moles of

The term xv denotes the CO produced when the O2 of the hot

W Wüstite Fe0.95O XW= Eq.(29) YW=1.05 X M = 1 + (1 − x h ) ωM C+ x hωM H (30)

The coefficients are presented in Table 2. The temperature at

4. Calculation of the operating line

T (°C) Equilibrium a0·10 a1·103 a2·105 a3·108 a4·1011 a5·1015

>565 Iron-Wüstite 4.0894101 3.8856440 -1.3778206 1.7924558 -1.0465659 2.3054702

>565 Wüstite-Magnetite -7.8765294 3.6286637 -0.2811151 0.0772069 0 0

>565 Iron-Wüstite -0.4957779 -0.5074581 0.4367340 -0.6744924 0.4402173 -1.0668513

>565 Wüstite-Magnetite -215.36181 115.54294 -24.611536 26.555149 -14.341369 30.845286

All the addends of Eq.(37) are thoroughly explained in the A 

By substituting Eq.(38) in Eq.(42), and by using the conven- ( )

∆1 yv + ∆ 2 = 0 (44) γ = (106 Ω HM,C M C ) nHM,Fe (50)

In practice, different authors have developed formulae for

DATA SET 1 DATA SET 2

Iron ore (25°C) 2276.4 2276.4 - 2276.4 - 1558.0 1558.0 -

# Fe2O3 947.4 947.4 - 947.4 - 1146.9 1146.9 -

# FeO 357.3 357.3 - 357.3 - 187.3 187.3 -

# SiO2 327.5 327.5 - 327.5 - 69.9 69.9 -

# Al2O3 133.1 133.1 - 133.1 - 107.2 107.2 -

# CaO 446.0 446.0 - 446.0 - 26.9 26.9 -

# MgO 4.0 4.0 - 4.0 - 16.2 16.2 -

# MnO 19.9 19.9 - 19.9 - 3.6 3.6 -

# P2O5 41.2 41.2 - 41.2 - 0.0 0.0 -

# C 509.0 520.9 2.3 526.9 3.5 251.4 256.7 2.1

# H 3.0 3.1 2.3 3.1 3.3 - - -

# S 8.2 8.4 2.3 8.5 3.6 - - -

# Fe2O3 - - - - - 1.7 1.8 2.1

Coal (25°C) - - - - - 200.0 200.0 -

# C - - - - - 153.6 153.6 -

# H - - - - - 8.3 8.3 -

# O - - - - - 10.2 10.2 -

# N - - - - - 3.1 3.1 -

# S - - - - - 0.9 0.9 -

# H2O - - - - - 2.4 2.4 -

# SiO2 - - - - - 12.3 12.3 -

# Al2O3 - - - - - 8.9 8.9 -

# CaO - - - - - 0.3 0.3 -

# N2 1618.0 1673.6 3.4 1706.9 5.5 826.7 833.5 0.8

# O2 491.0 508.2 3.5 518.3 5.6 251.1 253.1 0.8

# H2O 16.6 16.9 2.0 17.3 4.1 0.0 0.0 -

O2 enrichment (1200°C) - - - - - 94.3 95.1 0.8

DATA SET 1 DATA SET 2

Output streams (kg/tHM) Rist

# Fe 937.0 937.0 0.0 937.0 0.0 947.2 947.2 0.0

# C 38.0 38.0 0.0 38.0 0.0 45.0 45.0 0.0

# Si 4.0 4.0 0.0 4.0 0.0 5.3 5.3 0.0

# Mn 3.0 3.0 0.0 3.0 0.0 2.5 2.5 0.0

# P 18.0 18.0 0.0 18.0 0.0 0.0 0.0 0.0