Fuel 336 (2023) 127077

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Review article

A technical review on coke rate and quality in low-carbon blast

furnace ironmaking
Behnaz Rahmatmand a, Arash Tahmasebi a, *, Hannah Lomas a, Tom Honeyands a,
Pramod Koshy b, Kim Hockings c, Apsara Jayasekara a
a
Centre for Ironmaking Materials Research (CIMR), Newcastle Institute for Energy and Resources (NIER), University of Newcastle, Callaghan, New South Wales 2308,
Australia
b
School of Materials Science and Engineering, University of New South Wales, Sydney, New South Wales 2052, Australia
c
BHP, Brisbane, Queensland 4000, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: The blast furnace technology is still the main ironmaking route with a current global share of 70%. Reduction of
Blast furnace ironmaking fossil carbon consumption and CO2 emissions in blast furnace operations are essential for the decarbonization of
Metallurgical coke steelmaking. Potential solutions such as introducing renewable carbon-based materials (torrefied biomass,
Hydrogen reduction
charcoal), using hydrogen-enriched reducing gases (i.e., hydrogen gas, coke oven gas, reformed coke oven gas,
GHG emissions
Biomass
green methane), oxygen enrichment with top gas recycling, and carbon capture and storage/utilization have
Sustainability been considered to decrease emissions. The enhanced sustainability of blast furnace operations depends pri­
marily on improving the hydrogen-to-carbon replacement ratio. Hydrogen is an effective reducing agent, pro­
ducing steam during the reduction of ferrous burden. The replacement of coke and PCI with hydrogen leads to
reduced fuel rates and CO2 emissions. Although implementing the innovative ironmaking solutions reduces coke
and coal consumption, coke cannot be replaced entirely as it plays an irreplaceable role as a mechanical support
network and the permeable layer for gas movement in the blast furnace. The injection of alternative reducing
agents into the blast furnace alters the reaction environment by changing gas composition and temperature.
Therefore, understanding the impacts of new reaction conditions on coke rate and quality requirements is
important to both coal producers and steel manufacturers. This paper reviews the current understanding of how
the introduction of alternative reducing agents into the blast furnace influences the gasification behavior,
degradation mechanism, and consumption rate of coke. The review also identifies the knowledge gaps and future
research opportunities in the field.

1. Introduction improvement of living standards, leading to adverse environmental

impacts and global warming [1]. Based on the United Nations’ Inter­
Since the 1970s, greenhouse gas (GHG) emissions have increased governmental Panel on Climate Change (IPCC) statement in 2015, the
significantly due to industrialization, population growth and concentration of CO2 must be maintained at 450 ppm to avoid global

Abbreviations: AAEM, alkaline earth metal; AFT, adiabatic flame temperature; ARA, auxiliary reducing agent; Bb, bio-briquette; Bc, bio-coke; BF, blast furnace;
BOF, basic oxygen furnace; CC, charcoal; CCUS, CO2 capturing utilization and storage; CCS, CO2 capture and storage (CCS); COG, coke oven gas; CR, coke rate; CRI,
coke reactivity index; CSR, coke strength after reaction; DI, drum strength; DRI, direct reduced iron; E, comprehensive energy consumption; EAF, electric arc furnace;
Eta, efficiency of gas; FOBF, full oxygen blast furnace; GHG, greenhouse gas; GM, grain model; H2R, hydrogen rate; HM, hot metal; HPC, high performance caking
additive; HRG, hot reducing gas; IEA, International Energy Agency; IPCC, Intergovernmental Panel on Climate Change; ISM, integrated steel mill; M40, mechanical
resistance index of coke; Mtoe, million tons of oil equivalent; NG, natural gas; O/C, iron ore to carbon ratio; PC, pulverized coal; PCI, pulverized coal injection; PSA,
pressure swing adsorption; PU, polyurethane; Ri, iron ore reduction; RC, coke weight loss rate; RAFT, raceway adiabatic flame temperature; RAR, reducing agent
ratio; RCOG, reformed coke oven gas; RI180, reduction index of iron ore; RPM, random pore model; SEC, specific energy consumption; SLR, solution loss ratio; TF,
torrefied food residue; TFe, qualified iron grade; TFT, theoretical flame temperature; TGA, thermogravimetric analysis; TGR-OBF, top gas recycling oxygen blast
furnace; TSD, torrefied sawdust; TWM1, torrefied wood; VM, volumetric model; X, mass%; ϑinj, hydrogen injection temperature; φ, gas content.
* Corresponding author.
E-mail address: arash.tahmasebi@newcastle.edu.au (A. Tahmasebi).

https://doi.org/10.1016/j.fuel.2022.127077
Received 24 September 2022; Received in revised form 16 November 2022; Accepted 4 December 2022
Available online 15 December 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
B. Rahmatmand et al.
Fig. 1. The final energy demand of heavy industries and their sources of energy
supply [8].
warming above 2 ◦ C [1]; later, in 2018, the IPCC reduced the global
warming limit to 1.5 ◦ C by 2050 [1]. This highlights the essential need to
reduce GHG emissions across all energy and industry sectors [1].
Steel plays a pivotal role in the global economy, and global steel
demand continues to grow to fulfil the need for improvement in eco­
nomic and social welfare. Global steel consumption has doubled since
2000 and is expected to increase to approximately 2200 Mt by 2050 [2].
The increasing global steel demand imposes challenges for the iron and
steel industry to improve the sector’s sustainability. The iron and steel
sectors are among the most carbon- and energy-intensive industries.
About 75 % of energy demand in ironmaking and steelmaking is pro­
vided by coal, as presented in Fig. 1, leading to substantial CO2 emis­
sions [3,4]. The steel industry ranks second in energy demand with
900 Mtoe energy consumption per annum and emissions of approxi­
mately 2.6 Gt CO2 annually [4,5]. This is expected to increase signifi­
cantly since global steel production has risen dramatically during the
last ten years [6]. According to the stated policy scenario in the iron and
steel technology roadmap presented by the international energy agency
(IEA), steel production is projected to grow by 30 % by 2050 [4]. This
considerable increase in global steel production has resulted in a sig­
nificant rise in global energy consumption and CO2 emissions and this is
linked to increasing changes in the climate [7]. It is therefore critical for
the steel industry to significantly reduce GHG emissions.
To reduce CO2 emissions, three major routes have been identified,
including low-carbon blast furnace ironmaking, smelting reduction, and
direct reduced iron with steel scrap recycling and electric arc furnaces
(EAF) production [7]. Currently, 70 % of metallic raw material input to
Fig. 2. Decarbonising solutions for the BF.
2
Fuel 336 (2023) 127077
the steelmaking industry is provided by iron ore, and the rest is supplied
by recycled steel scrap [4]. The EAF production route accounts for 25 %
of global steel output and thus the use of steel scrap alone cannot meet
the demand for the global raw material input because of rapid growth in
steel demand and the limited availability of high-quality scrap [4,7].
Therefore, recycling alone cannot reduce CO2 emissions from the steel
industry to the extent required to meet the climate goals. Thus, there
exists a growing demand for the development of steelmaking processes
with lower cost, energy demand and CO2 emissions [4,9,10].
Steel is produced via two major routes, namely the blast furnace
(BF)/basic oxygen furnace (BOF) and the direct melting of scrap/DRI in
an EAF. In the BF/BOF process, steel is produced by reducing the ferrous
burden. In the EAF route, the feedstock can be direct reduced iron (DRI)
or steel scrap. DRI is the product of the direct reduction process using
iron ore and natural gas (NG) as feedstocks. Scrap-based EAF, DRI-EAF,
and BF-BOF produce 95 % of steel globally. The smelting reduction
process is the other steel production route developed to eliminate the
need for coke and sinter, aiming to use iron ore fines and coal. Several
smelting reduction processes have been developed, some under
demonstration and some commercially available. However, their
implementation rate in the industry has been very slow [2,4].
Although the development of alternative ironmaking and steel­
making routes, including direct reduction, smelting reduction, and EAF
have contributed to reducing CO2 emissions in the steel industry, the BF
process is still the main route of steel production with a 70 % share of the
steel market. This highlights the importance of developing innovative
solutions to the integrated BF ironmaking processes for decarbonising
BF operations as presented in Fig. 2, including:
(1) Introduction of waste plastic and renewable carbon-based mate­
rials such as biomass;
(2) H2-enriched reducing gases (i.e., coke oven gas, renewable
methane, and renewable ammonia);
(3) Oxygen-enriched BF with top gas recycling;
(4) H2 injection (e.g., electrolytic H2);
(5) Carbon capture utilization and storage (CCUS);
Based on the sustainable development scenario (SDS) in the iron and
steel technology roadmap presented by IEA in 2019, about 65 % of the
steel in the world will be produced by EAF and direct reduction using H2
with or without CCUS by 2050 [4]. CO2 capture and storage (CCS) is
understood to be one of the promising techniques for significant CO2
emissions mitigation from the steel sector [11]. In the CCS process, CO2
is separated from the off-gas and stored in a geological site [12].
B. Rahmatmand et al.
Fig. 3. Average age and geographic distribution of essential ironmaking assets [4].
Fig. 4. Supplementary fuels for BF injection.
However, according to the estimations, the capture process could ac­
count for 70–90 % of the overall operating costs of a CCS system [11].
The capturing technologies are categorized into molecular sieve and
membrane, carbonation, cryogenics, physical separation and chemical
and physical absorption and adsorption. Recently, the water-gas shift
process has received much attention due to its low energy requirement.
In a water-gas shift membrane reactor, CO is converted to CO2 and H2 is
separated from CO2. Chemical looping solutions have also attracted
much attention due to the high efficiency of these processes [13].
A number of studies have investigated the development and
deployment of CCS techniques in the steel sector under global CO2
breakthrough programs, such as COURSE50 in Japan and ULCOS in
Europe [11]. Recently, physical adsorption/absorption and chemical
absorption techniques have received much attention for CO2 separation
from the BF top gas. In the chemical absorption method, CO2 is removed
from the BF top gas using a liquid solvent in an absorber with a counter-
current flow pattern. Then, the CO2-lean gas returns to the BF, and the
CO2-reach solvent is sent to a stripper for regeneration. In the physical
adsorption process, CO2 is removed from the BF top gas by pressure
swing adsorption (PSA) technique in which a gas component is adsorbed
by a solid adsorbent under high pressure, followed by a reduced pressure
to release the adsorbed gas [14]. The main drawback of these techniques
is the high energy demand and cost of the process. Therefore, reducing
the energy demand for CCUS techniques can significantly contribute to
facilitating the utilization of these methods in the steel and iron in­
dustry. With this aim, sensible heat recovery from slag using an efficient
heat exchanger is a promising technique for providing the energy
required for the CCUS process [1].
3
Fuel 336 (2023) 127077
CCUS and H2 utilization can result in a 25 % reduction of global CO2
emissions in the steel industry by 2050 [4]. Therefore, based on the SDS
and stated policy scenario (STEPS) in the steel road map presented by
IEA, by 2050, it is estimated that about 35 %-50 % of the steel in the
world will be produced in BF operations including conventional BF
process (gas, charcoal, and coal-based) and H2-enriched BF operation
[4]. This can be attributed to the relatively young BF fleet in the major
steel-producing regions such as China and India, with an average global
age of 13–14 years, as presented in Fig. 3. Therefore, the likely scenario
is that in the short- to mid-term, the leading steel-producing regions are
willing to decarbonize current BF operations to enhance process sus­
tainability. In this context, the BF operation will remain one of the major
routes of producing steel even by 2050.
As illustrated in Fig. 4, the introduction of supplementary fuels such
as H2 and biomass-based renewables is proposed to increase the sus­
tainability of BF operations. Moreover, effective CO2 emissions reduc­
tion and sustainability enhancement of the BF processes will mainly
depend on increasing the hydrogen to carbon replacement ratio [15].
When H2 is used as the reducing agent, steam is produced instead of CO2,
decreasing the BF demand for fossil fuels (coke and coal). H2 is a more
effective reducing agent than carbon monoxide (CO) because of its
greater diffusibility, lower density and higher reduction rate of ferrous
oxides [15].
With the increased commitment of the steel industry to reduce
emissions, several solutions are being developed through intensive
research [2]. These include Japan’s COURSE50 program, the IGAR
program in France, the ROGESA program in Germany, the European
ULCOS program, and the Torero partnership project [4,7,14,16–19].
B. Rahmatmand et al.
COURSE50, IGAR, and ROGESA are examining the BF off-gas recovery
in large-scale prototypes to reduce the energy intensity of the process.
These projects employ different methods for reforming coke oven gas
(COG) or CO2 to H2-rich gas for use as the reducing agent in the BF. Due
to the limited CO2 emissions reduction (e.g., by 3 %) achieved by in­
jection of H2-enriched reducing gas to the BF and recycling top gas, the
prototype would allow carbon removal to be integrated, as was pre­
dicted in the European ULCOS program and the COURSE50 program.
Since 2019, Thyssenkrupp has examined H2 utilization for partial sub­
stitution of PCI. The project is in the pre-commercial demonstration
stage. In the Torero partnership program, torrefied waste wood injection
into the BF has been tested to partially replace coal in ArcelorMittal’s
plant in Belgium [4].
Although innovative ironmaking technologies reduce coke and coal
consumption in the BF, coke cannot be replaced entirely by alternative
reducing agents because it plays an irreplaceable role as the skeletal
support for the ferrous burden permeable layer for gas movement in the
BF [20]. The introduction of new reducing agents alters the reaction
environment in the BF, including gas compositions and temperature
distribution. Therefore, it is crucial to understand the impacts of these
new reaction conditions on both the coke rate and coke quality
requirements.
This paper provides an overview of the current understanding of the
impacts of introducing biomass, waste plastics, and H2-enriched
reducing gases (i.e., pure H2, COG and reformed coke oven gas (RCOG)),
as well as O2 enrichment with top gas recycling on coke gasification
reactivity and coal and coke consumption rates. The primary objective is
to review the current knowledge of coke quality requirements in low-
carbon BF operations and identify knowledge gaps and future research
opportunities.
2. Use of renewable carbonaceous materials and ferro-coke in
the blast furnace
Coke consumption reduction is considered a key factor towards en­
ergy consumption reduction and CO2 emission mitigation in the BF [21].
To significantly reduce coke consumption, Nomura et al. [22] confirmed
that the BF reaction efficiency can be drastically improved by reducing
the temperature of the thermal reserve zone by using ferro-coke. Ferro-
coke is one of the agglomerates with high reactivity that helps enhance
iron ore reduction and reduce CO2 emissions. Ferro-coke is the product
of the co-carbonization of coal and iron ore, which has extremely high
reactivity with CO2 in comparison with conventional coke due to the
catalytic impact of iron particles and the contact between carbonaceous
materials and iron ore [21]. The charging of the ferro-coke into the BF
along with iron-bearing materials has been examined by some re­
searchers to better understand this low-carbon ironmaking process. The
JFE steel corporation built a bench scale plant of 0.5 t/day and carried
out continuous experiments (over 24 hr) to confirm the reliability of this
process. JFE constructed a pilot plant of 30 t/d and started experiments
in 2011. BF operation with a ferro-coke charging amount of 43 kg/tHM
was carried out until 2012 [21]. In addition, other mathematical and
experimental studies have also been conducted to evaluate the impact of
utilizing ferro-coke on the reduction of iron oxides, the efficiency of the
BF, gasification reaction behaviour, and carbon consumption, which are
discussed in the subsequent section.
Decreasing the reducing agent rate in BF operations by improving the
shaft efficiency of the BF without saving energy at the downstream
processes can result in enhancing production costs due to increasing
purchased energy [23]. Partial replacement of carbonaceous resources
like coke and coal, which are the primary energy source in ironmaking,
by neutral and renewable carbon-based materials such as waste plastics
and biomass offers a viable solution for reducing CO2 emissions and the
dependency on fossil fuels in the integrated steel mills [24,25]. Waste
plastics have been proposed as an alternative reducing agent due to their
high H2 content [26,27]. Waste plastics injection at up to 60–80 kg/tHM
4
Fuel 336 (2023) 127077
rates has been successfully practiced in different countries including
Austria, Japan, and Germany [26,28–30]. Although the physical prop­
erties of waste plastic, such as porosity, shape and size affect the reaction
kinetics [31], the theoretical limit of waste plastic injection is estimated
at 70 kg/tHM. Approximately 750 kg of coke can be replaced by one ton
of plastics [24]. The use of waste plastics in the BF can decrease CO2
emissions by up to 30 % due to its higher H2 content compared to coal
and coke [32].
Biomass utilization in the BF has received much attention due to its
renewable nature and significant environmental advantages [24,33,34].
Biomass can be introduced to an integrated steel plant through bio-
sinter, bio-briquettes and/or bio-composites, bio-coke (partial substi­
tution of coal in coke-making), and partial replacement of pulverized
coal injection (PCI) or nut coke in the BF [35,36]. Biomass could be
either injected into the BF through tuyeres or charged to the BF from the
top to reduce coke consumption. Lump charcoal, torrefied biomass, bio-
composite, bio-sinter, and bio-coke are suitable materials for top
charging. In the case of biomass injection through tuyeres, bio-oil,
ground torrefied materials, and ground charcoal can be used [37].
However, utilizing renewable materials in the BF alters the conditions in
the furnace, influencing the coal and coke rate and quality requirements.
This raises the following questions:
• Raw material quality requirements depending on the method of
introducing biomass (top charging and injection through the
tuyeres).
• The effect of biomass injection into the BF on the coke reactivity and
degradation mechanism.
• Evaluating the capacity of decreasing reducing agent rates and
changes in in-furnace conditions depending on physical and me­
chanical properties of biomass.
Brazil is the only country that produces hot metal on a large-scale
using charcoal in BFs. Currently, charcoal mini-BFs (50–350 m3) pro­
duce 10 Mt of steel in Brazil. The current BFs require specific charac­
teristics for charged materials (pellets, sinter, coke) to maintain efficient
performance. Hot and cold burden strengths play a significant role in
sustaining the permeability of the shaft. Thus, bio-agglomerates (bio-
composite, bio-sinter, and bio-coke) must have a minimum strength to
maintain the quality of hot metal and the efficiency and stability of the
process. Moreover, changing input materials could influence the heat
and mass transfer mechanism, distribution of gases, and temperature
profile of the BF [37].
A large body of work has focused on bio-coke production by partial
replacement of coal in blends since bio-coke has a greater reactivity with
CO2. However, biomass addition (i.e., bio-oil, charcoal, tar, torrefied
biomass, cellulose, xylan, lignin, etc.) to coal blends in cokemaking has
been found to decrease the fluidity of the blends, increase coke reac­
tivity, and compromise cokes strength [38–42]. Charcoal addition to the
coal blend enhances the bio-coke reactivity due to the presence of alkali
metals which catalyze gasification reactivity [39]. Further, biomass
negatively impacts the mechanical properties of bio-coke due to its high
porosity, fibrous nature, and low mechanical strength [43]. The addition
of 3 % sawdust to the coal blend can reduce the coke strength by about
10 % [41,43]. Other studies suggest that up to 5 % biomass can be added
to the coal blend without having major negative impacts on coke quality
[39,41,44,45]. Therefore, conventional biomass can only be added to
coal blends at low proportions (2–10 %). Thus, producing bio-coke with
suitable strength and reactivity is a challenge [37].
Studies have shown that biomass compaction before the coking
process could mitigate the negative impacts on bio-coke strength
[45,46]. Biomass pyrolysis via temperature optimization has proven
effective in reducing the volatile matter and increasing the fixed-carbon
of the biomass, thus making it more suitable for blending with coal [37].
The density and size of biomass particles have also been important pa­
rameters when designing blends, due to their effects on the interaction
B. Rahmatmand et al. Fuel 336 (2023) 127077

and contact area between coal grains and biomass [46,47]. Further trials
and investigations are still needed to improve biomass utilization in
cokemaking without impairing coke quality. Identifying suitable coal
and biomass species for blending will be key to achieving these
objectives.
While biomass top charging has some drawbacks due to higher vol­
atile content and lower mechanical strength in comparison with coke,
biomass injection through the tuyeres has been identified as an efficient
means of introducing biomass into the BF [45]. Injection trials have
shown that biomass has greater combustion reactivity than pulverized
coal (PC) which influences the raceway adiabatic flame temperature
(RAFT) [45,46]. Moreover, biomass injection and accordingly ash pro­
duced by biomass combustion affect coke wettability and reactivity in
the furnace [48]. The substitution rate of coal by biomass-based mate­
rials such as raw biomass, torrefied biomass, and charcoal has been
studied using the static heat and mass balance models [49,50]. The PCI
substitution rates of raw wood pellet and torrefied biomass were much
lower in comparison with that of charcoal. PCI substitution with high
amounts of low ash charcoal reduces the coke rate and slag volume, thus Fig. 5. Starting and ending points of the normal coke and ferro-coke gasifica­
increasing the top gas volume and enhancing the BF productivity [51]. tion reactions under CO2 atmosphere [68].
According to the modelling results, PCI can be completely substituted by
charcoal at 200–220 kg/tHM, reducing CO2 emissions by up to 40 %
[45,52]. It is worth noting that together with the technical advantages of
injecting Bio-PC into the BF, there are practical issues that limit Bio-PCI.
Firstly, charcoal has a low bulk density that impedes the pneumatic
conveying at high injection flow rates. Secondly, literature data indi­
cated difficulties during milling. Therefore, it was necessary to
concentrate particles by screening. Thirdly, charcoals typically have
high alkali content [52]. In addition, injecting charcoal with high ash
content can negatively affect the BF productivity and coke rate,
depending on the properties of the reference PCI [53,54]. Injecting a
high volume of torrefied biomass with a low calorific value (17–20 MJ/
kg) and carbon content (50–56 %) and a high volatile matter (68–84 %)
also has a negative influence on the BF performance [51]. Thus, ac­
cording to Babich et al. [53], torrefied biomass could only substitute for
up to 50 % of PCI [51,53,55]. However, undesirable physicochemical
characteristics of biomass hinder their commercial utilization in BF Fig. 6. Effects of alkali (Fe and K) in the ferro-coke on weight loss curve (under
ironmaking. These undesired properties include low heating value and the gas condition of CO/CO2 = 70/30) in thermogravimetric analysis test [70].
density, high moisture content, and lower grindability than coal [45].
To conclude, ferro-coke made from the co-carbonization of coal and much attention because reducing the temperature and raising the rate of
iron ore is an alternative fuel to decrease carbon emissions of BF oper­ this reaction is understood to control the overall reactions in the BF
ations by reducing the thermal reserve zone temperature and enhancing [58,59]. It has been reported that lowering the thermal reserve zone
BF efficiency. Partial replacement of fossil carbon with biomass via in­ temperature in a BF by using coke with high reactivity is an effective
jection through the BF tuyeres and top charging to the BF can also play measure for reducing energy consumption and mitigating carbon
an important role in CO2 emissions reduction in integrated steel mills. emissions [59–62]. Iron-bearing materials are understood to be a
While biomass top charging has some drawbacks due to lower me­ preferred catalyst for the gasification reaction of coke [63]. Ferro-coke
chanical strength in comparison with coke, injection through the tuyeres can be produced through two processes. One process includes adding
has been identified as an efficient means of introducing biomass into BF. iron-bearing materials to a coal blend to be carbonized in a conventional
PCI substitution with low ash charcoal reduces the coke rate and slag coke oven [59]. In the other process, agglomerates of a coal blend and
volume and enhances the BF productivity. On the other hand, injecting a iron-bearing substances, made by briquetting, are carbonized in a shaft
high volume of torrefied biomass with a high volatile matter and low furnace [64–67]. The gasification reactivity of coke and ferro-coke has
carbon content has a negative influence on the BF performance. been compared in some studies [68–70].
Therefore, the physical and mechanical properties of biomass can affect Fig. 5 [68] shows that the ferro-coke has higher reactivity compared
the reducing agent consumption, coke reactivity and CO2 emissions to the normal coke and the start and end temperature of gasification of
reduction. The impact of charging ferro-coke and biomass injection on ferro-coke are lower than those of normal coke. Investigating the reac­
BF performance, coke reactivity and carbon consumption rates are dis­ tion behaviour of ferro-coke under simulated conditions, which was
cussed in the following sections. conducted by Higuchi et al. [69], also showed that the starting tem­
perature of ferro-coke gasification is 150 ◦ C lower than a conventional
3. Impact of ferro-coke on coke reactivity and carbon coke. Moreover, the use of ferro-coke was found to reduce the thermal
consumption in blast furnace reserve zone temperature by 186 ◦ C and improve the BF shaft efficiency
by 6.8 % [69]. In addition, as shown in Fig. 6, Nomura et al. [70] re­
Decreasing energy consumption and CO2 emissions of BF operations ported that the presence of alkali species (Na and K) in the ferro-coke,
is significantly important for improving the sustainability of the steel reduces the onset temperature of the coke reaction. Using coke with
sector. Adjusting and controlling the chemical reactions in a BF is an higher reactivity and reducing the thermal reserve zone temperature
important parameter that helps improve energy efficiency [56,57]. helps in controlling the reduction equilibrium of the BF [71]. The
Among these reactions, the carbon solution loss reaction has received reduction of iron-bearing burdens is greatly important for the smelting

5
B. Rahmatmand et al. Fuel 336 (2023) 127077

Table 1 raceway chemistry and coke reactivity. The wetting behaviour of ash
The ash composition and ash content (wt%) of torrefied food residues (TF1 and produced from renewable carbon-based materials and its influence on
TF2), torrefied sawdust (TSD), polyurethane (PU), and PC on a dry basis [48]. coke reactivity are discussed based on the research conducted by Ahmed
Components TF1 TSD TF2 PC PU et al. [48], who studied five ash samples including two torrefied food
Ash 22.50 0.50 16.30 10.8 15.0
residues (TF1 and TF2), torrefied sawdust (TSD), polyurethane (PU),
Mg 0.98 0.03 0.41 0.24 0.27 and pulverized coal (PC). The ash composition of these materials is
Ca 8.70 0.16 4.42 0.65 0.95 summarized in Table 1 [48].
Al 0.27 0.002 0.69 1.92 0.55 Investigating the wetting and melting behaviour of the ash samples
Si 1.44 0.009 3.79 3.84 0.00
on the coke surface at 1550 ◦ C showed that the ash generated by PC,
Na 0.25 0.002 0.14 0.04 0.09
Ti 0.02 0.0001 0.05 0.06 0.27 TSD, and TF1 had lower coke wettability compared to those of PU and
Fe 0.24 0.008 0.37 0.87 5.75 TF2 (Fig. 7) [48]. The different contact angles and wetting behaviour of
K 0.81 0.055 0.63 0.14 0.05 the ash samples are attributed to the ash composition [8]. It is worth
Ba 0.005 0.0025 0.005 0.00 0.13 noting that since the tests were done at 1550 ◦ C, it is possible that some
Mn 0.02 0.017 0.01 0.01 0.02
P 0.74 0.01 0.36 0.65 0.03
ash constituents such as alkalis are lost and they are not being consid­
Cr 0.001 0.00004 0.003 0.03 0.03 ered in the wetting behaviour. In addition, the impact of ash from
different renewable carbonaceous fuels on coke reactivity under CO2

and smooth operation of the BF. Charging ferro-coke into iron-bearing

burdens can significantly improve the reduction of iron oxides and the
efficiency of BF [59]. Yamamoto et al. [20] reported that the carbon
demand of the whole ironmaking process can be lowered by 6 % by
charging ferro-coke at the rate of 100 kg/tHM. Moreover, JFE steel
corporation has reported a 13–15 kg/tHM reduction in the rate of the
reducing agent when 43 kg of ferro-coke per ton of hot metal was
charged in a 5153 m3 BF [21]. To conclude, using the highly reactive
ferro-coke in the BF can reduce the temperature of the thermal reserve
zone and improve the iron oxides reduction and the BF efficiency, which
in turn lowers the reducing agent rate and carbon consumption of the
BF.

3.1. Impact of renewable carbonaceous materials on coke reactivity in

blast furnace

Upon injection into the BF, carbonaceous fuels undergo devolatili­

sation due to the high heating rates, followed by the combustion of the
released volatile matters [48]. The remaining char then combusts in the Fig. 8. Mass loss (wt%) of the coke substrates along with the molten ashes of
PC, TSD, TF1, TF2 and PU compared to that of the coke substrate that was not
raceway [48,72]. The ash present in biomass and plastics differs from
in contact with any ash under CO2 at 1000 ◦ C measured by Ahmed et al. [48]
that of coal in terms of composition, basicity, and fusion temperature
using TGA.
[48]. Thus, biomass and plastics injection is expected to influence the

Fig. 7. Contact angles between the coke surface and the different ash samples at 1550 C◦ [48]; Ash from two torrefied food residues (TF1 and TF2); torrefied sawdust
(TSD); polyurethane (PUR); PC.

6
B. Rahmatmand et al.
Fig. 9. The efficiency of gas in the reference periods (Ref 1 is the base case and
Ref 2 is the case including using bio-coke with 5% torrefied wood) and test
operations including torrefied wood and PCI [75].
Fig. 10. Amount of reducing agents including torrefied wood, PCI and coke in
the reference periods (Ref 1 is the base case and Ref 2 is the case including using
bio-coke with 5% torrefied wood) and operation including torrefied wood and
PCI [75].
was studied at 1000 ◦ C using thermogravimetric analysis (TGA), and the
results are shown in Fig. 8 [48]. These results indicated a limited
interaction between coke and TSD ash, while the melted PU and TF2 ash
reacted considerably with coke (Fig. 8) [48]. Although TF1 was ex­
pected to have limited interaction with coke due to its low wettability
property, it had the greatest coke reactivity as shown in Fig. 8. This can
be attributed to the greater content of alkalis in the TF1 ash sample.
Thus, the difference in coke reactivity can be attributed to the different
compositions of the ash samples. Alkaline earth metals (AAEMs) and
iron are known to catalyze coke gasification reactions. It has been
demonstrated that char reactivity is correlated to the AAEMs to carbon
ratio [48,73,74]. On the other hand, phosphates, alumina and silica
reduce the char reactivity. In addition to the biomass ash composition,
other factors such as coke structure, distribution of inorganic matter,
and wettability also affect coke reactivity [48].
To conclude, solid fuels with a lower degree of coke surface wetting
cause less coke degradation and are more suitable for utilization in the
BF. However, the ash composition including the concentration of AAEM
species plays an important role in coke reactivity. Therefore, different
parameters including coke structure, wettability, and biomass ash
composition should be considered when evaluating biomass species for
BF use. This highlights the importance of studying the interaction be­
tween different types of biomass and cokes with insight into their ash
composition and coke strength. However, the selection of the input
materials also depends on resource availability.
7
Fuel 336 (2023) 127077
3.2. Impact of biomass injection on PCI and coke rates
Auxiliary reducing agents (ARAs) are commonly injected into the BF
to reduce the coke rate. Injection through the tuyeres facilitates biomass
utilization in BF operations. However, the physical and mechanical
properties of biomass influence the reaction condition in the furnace, the
consumption of reducing agents, and CO2 emissions. This raises research
questions on the performance of different biomass materials as the
injectant considering their effects on coal burnout, gas efficiency, RAFT,
top gas temperature, PCI rate, and coke consumption. Therefore,
mathematical models have been developed to answer these questions
[49,50].
Results of a modelling investigation are presented in Fig. 9 and
Fig. 10 in which Ref 1 is the base case and Ref 2 is the case where bio-
coke was used (with 5 % torrefied wood). As presented in these fig­
ures, mixed injection of PCI and torrefied wood (TWM1) at up to 24 %
results in improving gas efficiency compared to the base case (Fig. 9),
contributing to decreasing the reducing agent consumption (Fig. 10) and
lowering CO2 emissions by up to 8 % [75]. Moreover, it has been re­
ported that 155 kg/tHM PCI can be fully substituted by 166.7 kg/tHM
charcoal, while wood pellets and torrefied biomass could partially
substitute 20 % and 22.8 % of PCI rate, respectively [50]. Charcoal
showed the greatest potential for PCI replacement without causing any
significant change in top gas temperature. On the contrary, it was found
that the top gas temperature decreased when injecting wood pellets and
torrefied biomass. The highest injection rates of wood pellets and tor­
refied biomass to satisfy the lowest feasible top gas temperature were
calculated to be 98.9 kg/tHM and 134.2 kg/tHM, respectively. The high
volatile matter content in wood pellets and torrefied biomass led to a
decrease in RAFT, indicating the need for O2 enrichment of hot blast
[76]. Based on these findings, charcoal injection appears as the most
feasible option for decreasing the CO2 emissions in BF operations
[76–78]. A complete replacement of PCI by a high carbon content
charcoal decreases the rate of reducing agents by up to 44 % [76].
Regarding the impact of utilising bio-briquette (Bb) and bio-coke
(Bc) in the BF on reducing agent consumption, bio-briquette utiliza­
tion reduces the fuel rate because of their higher carbon content
compared to residue briquettes without bio-coal (Fig. 11). Additionally,
in this case, the lower thermal reserve zone temperature leads to
improved gas efficiency and lower rates of reducing agents [75]. Fig. 11
also shows that charcoal injection decreases the total fuel rate compared
to other biomass materials due to the higher fixed carbon content and
heating value of charcoal. In addition, the low ash content and ash ba­
sicity of charcoal results in reducing the slag rate and the required
amount of limestone [75].
Fig. 12 compares the consumption rate of reducing agents for
different cases of biomass injection based on the mathematical model­
ling of the BF [76]. Although each case presented in Fig. 12 has different
assumptions about the characteristics of the input materials and oper­
ation condition of BF, this figure demonstrates that the coke substitution
ratio strongly depends on biomass type. The heating value and chemical
composition of the biomass injected into the BF can influence the
required O2 enrichment and coke substitution [76]. To conclude, char­
coal has a better performance than raw biomass in reducing coke and
coal rates. Bio-oil, torrefied biomass, and wood pellets may also be
effectively injected into the BF, however, their coke substitution ratios
are lower [76]. Injecting charcoal can enhance pig iron quality and
decrease coke and slag ratios. However, the presence of AAEM species in
charcoal ash may cause significant ash deposition and corrosion issues in
BF operation. Thus, charcoals with low ash content are more desirable
for BF injection [79].
4. Oxygen blast furnace with top gas recycling
In the oxygen blast furnace (OBF) technology, higher O2 concen­
trations (balanced with CO2) are utilized instead of air [80]. This
B. Rahmatmand et al.
Fig. 11. Bio-coal and reducing agent inputs in different cases studied by Ökvist et al. [75]. Gray/green colour is indicative of bio-coke, and gray colour demonstrates
coke. Bb, Bc and CC are indicatives of bio-briquette, bio-coke and charcoal [75]. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
technology is also referred to as the nitrogen (N2) free BF. The OBF is
typically integrated with top gas recycling (OBF-TGR). Previous
research on the OBF-TGR process through modelling and experimental
studies has raised the following research questions [81–86]:
• The capability of OBF-TGR technology in reducing energy demand
and CO2 emissions of the steelmaking process.
• The impact of O2 enrichment on the BF performance and carbon
consumption.
• The effects of OBF-TGR operation on coke consumption rate and
coke quality requirements.
The OBF-TGR is proposed as a promising ironmaking technology due
to its specific features including high PCI rate and productivity [81–83].
In addition, recycling the OBF top gas can provide further benefits
including lower energy demand and CO2 emissions in comparison with
the conventional BF due to enhancing CO content, the overall temper­
ature and reduction degree in the OBF [86,87]. To illustrate the lower
energy demand of the OBF-TGR, the specific energy consumption (SEC)
of the conventional BF is compared with the two different cases of OBF-
TGR in Fig. 13. SEC is the energy consumed per ton of product in the
process of ironmaking. In Fig. 13, Case 0 is the conventional BF, Case 1 is
OBF-TGR when recycled top gas is mixed with COG before injecting into
the furnace, and Case 2 is OBF-TGR without mixing with external fuels.
As seen, OBF-TGR reduces the energy demand of the process compared
to the conventional operation even if an external fuel such as COG is
introduced into the process for preheating the recycled gas [87]. It
should be noted that in Fig. 13, in case 1, 93.1 % of top gas is effectively
recycled, while this ratio is 87.9 % in case 2. Moreover, the flow rate of
the top gas in case 1 is higher than in case 2. Thus, the required energy
for preheating the recycled gas before injection in case 1 is higher than
in case 2. Therefore, the energy consumed per ton of product in case 1 is
higher than that in case 2.
It has been reported by many researchers that increased O2 con­
centration improves the productivity of the OBF [86,88–92]. Therefore,
the implementation of full O2 or O2 enrichment in the OBF-TGR has
8
Fuel 336 (2023) 127077
received much attention. However, the medium O2 enrichment (40 % –
60 %) strategy has not yet been evaluated in detail. According to the
mathematical results, 30–47 % O2 enrichment in the OBF-TGR leads to a
68 % reduction in CO2 emissions with the integrating carbon capture
strategy [83]. Thus, the medium O2 enrichment strategy in the OBF-TGR
process seems to have a great potential to reduce emissions from BF
operations in the short term [93].
In addition to mathematical studies, trials of OBF-TGR in steel plants
have been carried out successfully. In 1980, OBF-TGR trials were
implemented in the Soviet Union in a 1033 m3 BF at RPA Toulachermet
[83]. The ULCOS (ultra-low CO2 steelmaking) program was proposed by
48 European organizations and companies to decrease CO2 emissions.
The OBF-TGR process has been identified as one of the important stra­
tegies in this program [83]. A pilot OBF (8 m3) was fabricated for con­
ducting the experimental testing. Reductions in both fuel consumption
(coal and coke) and CO2 emissions by up to 140 kg/tHM and 76 %,
respectively, were achieved [83]. The injection of COG into an OBF was
successfully trialed at China’s Ying Steel in 2009 [94]. However, it has
been reported that the adaption of a full O2 blast often deteriorates the
furnace productivity, leading to BF shutdowns [83]. To explain this,
higher O2 enrichment ratios lead to enhanced solid and gas tempera­
tures below the cohesive zone, and lower temperatures over the cohe­
sive zone, leading to overheating in the lower section and thermal
shortage in the upper section [95,96].
Under similar bosh gas conditions, increasing oxygen content im­
proves productivity and accordingly decreases the volume of gas per
tonnage of hot metal, leading to less heat reaching the upper section.
However, higher flame temperature contributes to raising the temper­
ature of the lower section of the BF [95,96]. The Baowu Group is one of
the few companies that has made ground-breaking progress in OBF
operation at an industrial scale. In Xinjiang Bayi Iron & Steel Co., Ltd., in
the first phase, they achieved 35 % O2 enrichment at a daily coal in­
jection rate of 230 kg/tHM which is greater than the coal injection limit
of traditional BFs. They reported having overcome the technical prob­
lem of unbalanced furnace temperature. The company also plans to
advance toward 50 % O2 enrichment in the next phase [97]. Thus,
B. Rahmatmand et al.
Fig. 12. The rates of reducing agents in the BF in different cases of biomass injection [76,77]; Data set 1 [76]; Data set 2 [50]; Data set 3 [55]; Data set 4 [76]; Data
set 5 presented by [76]; Data set 6 [76]; and Data set 7 [54].
although several OBF processes have been developed [84,98–102],
further work is required to demonstrate the scale-up feasibility of the
OBF.
To conclude, the OBF technology and recycled top gas contribute to
reducing energy input and CO2 emissions of the process and enhancing
productivity compared to the conventional BF operation. In this tech­
nology, increasing the O2 content of the blast lowers the coke rate in the
BF while improving the productivity of the furnace. However, to achieve
high O2 enrichment ratios, the problems associated with the OBF,
namely, overheating in the lower section and thermal shortage in the
upper section need to be resolved. Some industrial trials have been able
to overcome this problem and evaluate the feasibility of the operation at
an industrial scale. Due to the important role of coke in the smooth
operation and productivity of the BF, the effects of O2 enrichment on
coke consumption rate have been studied to some extent and are dis­
cussed in the following section.
9
Fuel 336 (2023) 127077
4.1. Impact of OBF-TGR operation on coke consumption rate and coke
degradation
The OBF is introduced as a promising ironmaking process due to its
unique features including lower carbon emissions, the potential for
reducing furnace size, intense reduction atmosphere, and improved
furnace productivity [88,89,102–104]. In addition to the OBF, the
advanced OBF was also introduced by the researchers in which injecting
preheating gas like natural gas into the upper shaft leads to downsizing
the furnace and improving the calorific value of the BF top gas
[105–107]. Decreasing the inner volume of the BF can help relax the
strength requirements of the burden material and lead to the reduced
energy consumption of the total ironmaking process, including the sin­
tering machine, coke oven, and electric power plant [105,108]. More­
over, increasing the O2 concentration facilitates the utilization of new
and waste fuels [96,109,110]. One of the important benefits of O2
enrichment is improved PCI combustion [111–113]. Improved PCI
B. Rahmatmand et al.
Fig. 13. Energy balances for the TGR-OBF and conventional BF processes; cases 1 is OBF-TGR that recycled top gas is mixed with COG before injection into the
furnace, and case 2 is OBF-TGR without importing an external fuel like COG [87].
combustion and O2 enrichment affect the heat balance, the direct and
indirect reduction ratios, and the CO concentration in the furnace. These
changes in turn influence the carbon solution loss ratio, coke con­
sumption rate, and the cost of pig iron production [109,114–117]. This
section discusses how O2 enrichment can impact coke reactivity and
consumption rate.
Nie et al. [96] mathematically investigated the transition from con­
ventional BF to OBF to understand the impacts of O2 enrichment on
reaction conditions and carbon consumption. However, in this study, PC
injection was not considered and coke combustion in the raceway sup­
plied the heat required in the BF. Based on the results, increasing the O2
concentration of the blast from 21 % to 100 % increased productivity
while reducing the volume of gas per tonnage of hot metal, leading to
less heat in the upper section. This accounts for the lower temperature
above the cohesive zone in the OBF compared to the conventional BF,
while the higher flame temperature of the OBF heats the section below
the cohesive zone. The low solid temperature above the cohesive zone
shifts the indirect reduction zone down and narrows the cohesive zone
(Fig. 14a) [96]. As a result, the non-reduced iron oxides descend through
the furnace, where they get reduced by carbon in the lower part of the
furnace through direct reduction at higher temperatures. The gas
product of direct reduction is CO, leading to increased CO content in the
BF (Fig. 14b) [96]. Increasing the CO concentration by O2 enrichment
hinders the carbon solution loss reaction (Fig. 14c) [96]. This is aligned
with the results presented by other researchers [117].
Fig. 15a shows that by increasing the O2 concentration from 21 % to
25 %, the coke rate decreases initially by about 90 kg/tHM. Further
increase in oxygen concentration increases the coke rate [96]. Gener­
ally, the lower gas temperature in the BF upper section leads to lower
heat loss through the furnace walls and top gas. Conversely, increasing
the direct reduction ratio promotes heat loss through this endothermic
reaction. According to these trends, as shown in Fig. 15b, the rate of coke
required for combustion to supply BF heat decreases initially and then
increases with increasing O2 content. This corresponds to the effect of
increasing O2 content on the coke rate as can be seen in Fig. 15a [96].
Therefore, there exists an optimal O2 concentration to achieve the
minimal coke consumption rate. This trend is aligned with the theo­
retical and experimental results presented by other researchers
[88,89,118]. One of these theoretical studies was conducted by Ymaoka
10
Fuel 336 (2023) 127077
et al. [89] under conditions similar to that of Nie et al. [96]. In the
theoretical study conducted by Ymaoka et al. [89], only air and enriched
O2 were injected through the tuyeres and the blast temperature was in
the range of 30–1200 ◦ C and the results are presented in Fig. 16a. As
seen, the optimum O2 concentration to minimize the fuel rate is re­
ported. Further increasing of O2 concentration resulted in a higher fuel
rate [89]. Together with this mathematical study, Ymaoka et al. [88]
conducted an experimental study on the OBF combined with PCI and the
results are presented in Fig. 16b. This study was made in the test plant
with a production capacity of 15 t/d. As shown in Fig. 16b, in the case of
OBF combined with PCI, the fuel rate significantly increases when the O2
injection rate decreases below 200 Nm3/h. This is attributed to a relative
increase of heat loss to the production rate, thus the O2 injection rate
was set at 250 Nm3/h in this test. Moreover, a smooth operation of the
plant at a PCI rate of 1.2 kg/Nm3-O2 in the blast when the coal and coke
rates were 407 kg/tHM and 258 kg/tHM, respectively, was reported
[88]. A commercial-scale OBF was also characterized experimentally
and mathematically with injecting preheating gas into the shaft by Ohno
et al. [119]. Injection of preheated gas into the upper shaft helps heat up
the burden in the upper shaft and secure a high degree of reduction
progress in the lower part. In addition, the height of the furnace in this
case could be less than that of the hot blast furnace and the fuel rate
could vary between 500 (with preheating gas) and 1200 (without pre­
heating gas) kg/tHM [119].
It is important to note that the full OBF faces a significant challenge
of low volume of top gas that practically can lead to the process shut­
down. It has been reported that even recycling the top gas cannot alle­
viate this problem. Therefore, medium OBF (30–47 % O2 concentration)
with top gas recycling has been proposed as the preferred operating
condition [83]. Under these conditions, the top gas volume and the
flame temperature of the BF were close to those of the conventional BF.
Moreover, the minimum carbon consumption of 357 kg/tHM was ob­
tained by this technology at an O2 content of 30 %, leading to 14 % fuel
saving [83].
It is worth noting that increasing O2 content hinders indirect
reduction and the carbon solution loss reaction, leading to less coke
degradation. On the other hand, O2 enrichment accelerates the reaction
between carbon and iron oxides through direct reduction, promoting
coke structural damage. However, the total effect of these opposite
B. Rahmatmand et al.
Fig. 14. Impact of O2 enrichment on (a) indirect reduction, (b) CO concentration, and (c) carbon solution loss ratio [96].
trends on coke degradation in the furnace with O2 enrichment has not
yet been investigated. Thus, further research should focus on the impact
of OBF operation on the coke degradation mechanism and quality
requirements.
Although the O2 enrichment effect on coke degradation in the OBF
has not yet been fully understood, the impact of H2-enrichment and iron
ore to carbon ratio (O/C) in a full oxygen blast furnace (FOBF) on the
solution loss ratio of coke (SLR) and the strength of coke after reaction
(CRS) have been reported [120]. It was confirmed that the coke SLR
increases with increasing H2 content in a FOBF while decreasing the
coke CRS. Moreover, the threshold temperature of coke gasification
decreases to 900 ◦ C, significantly lower than that of the conventional BF
at 1100 ◦ C. This accelerates the indirect reduction of iron oxides by H2
enrichment, leading to higher H2O concentration and a higher ratio of
carbon solution loss reaction of coke. Thus, in the FOBF under H2-
enriched operation, the coke reactivity can be increased to a certain
11
Fuel 336 (2023) 127077
level, while the threshold temperature of coke gasification decreases.
To summarise, higher O2 concentrations in the OBF lead to over­
heating below the cohesive zone and thermal shortage above the
cohesive zone. As a result, the indirect reduction zone descends in the
furnace, accelerating direct reduction and enhancing CO concentration
which accounts for a lower degree of carbon solution loss reaction.
Regarding the effect of O2 enrichment on the coke rate, it has been re­
ported by some researchers that there is a minimum coke consumption
rate that can be achieved by increasing the O2 content. Given that coke is
a source of heat supply in the furnace, the opposite effects of decreased
heat loss through the walls and top gas and increased heat loss through
the endothermic direct reactions lead to minimizing the coke rate at an
O2 enrichment below 40 %. It is worth noting that increasing O2 content
accelerates direct reduction and hinders the indirect reduction of ferrous
oxides. However, the combined influence of these opposite effects on
coke structure damage and coke quality requirements is not fully
B. Rahmatmand et al.
Fig. 14. (continued).
Fig. 15. Impact of increasing O2 content in the OBF on (a) coke rate, (b) carbon consumption by combustion in the raceway [96].
understood. This creates a research opportunity for investigating how
reaction conditions in the OBF influence degradation mechanisms and
quality requirements in the promising OBF process.
5. Hydrogen-enriched gas injection – impacts on coke rate
To reduce CO2 emissions from the ironmaking operations, promising
technologies have been developed such as charging carbon composite
agglomerates, changing the pattern of coke charging, recycling the BF
top gas, and injecting H2-rich reducing agents [121–124]. Injecting H2-
rich materials can effectively reduce the CO2 emissions of BF operations
due to its superior reducing characteristics compared to CO, facilitating
the greater reduction of ferrous burden [2,121,123,125,126]. Moreover,
H2 has a lower viscosity and higher heat conductivity that facilitate the
heat exchange between the solid and gas phases, contributing to the
reduction of the ferrous burden and carbon solution loss reactions in the
BF [123]. The most important advantage of H2 over CO is that water
12
Fuel 336 (2023) 127077
(H2O) is produced instead of CO2 during the reduction of iron oxides and
this lowers the CO2 emissions [121,127]. Thus, the utilization of H2 and
H2-rich gases is a promising approach for reducing CO2 emissions and
energy demand and improving the productivity of the BF operation
[121]. COG, natural gas (NG), RCOG, and waste plastics are abundant
H2-rich materials that can have a significant impact on BF performance,
PCI and coke rate, and coke gasification reactions [121,123,128]. The
COG is produced in the coke-making process as a by-product of coal
carbonization. The net calorific value of COG is about 16.4–18 MJ/Nm3,
greater than other off-gases produced at other parts of the integrated
steelmaking process, such as the BF and the BOF [121].
However, some components in the COG do not combust properly
when injected into the BF due to the cracking of methane at high tem­
peratures, causing carbon deposition and deficiencies in BF permeability
[121]. Hence, COG can be reformed to produce RCOG by removing
ammonia, benzene, sulfur, naphthalene, and tar through partial oxida­
tion, steam reforming and dry reforming processes [129–131]. The
B. Rahmatmand et al. Fuel 336 (2023) 127077

Fig. 16. Effect of the O2 content of the blast in OBF on the fuel rate according to (a) the mathematical study where only air and enriched O2 injection through the
tuyeres was considered, and (b) experimental study where OBF was combined with PCI [88,89].

Fig. 17. Effect of COG injection and recycling of the BF top gas on coal and coke ratios and RAR in the four cases of conventional BF (Base case), COG injection
(COI12), COG injection and recycling BF top gas for tuyere injection (COI12-TI), and COG injection and recycling BF top gas for tuyere and shaft injection (COI12-TI-
SI) [135].

reforming of COG increases the H2 content, rendering RCOG an appro­
priate alternative for reducing gas [121,132].
According to the benefits of injecting an H2-rich reducing gas into the
BF, deploying this promising technique creates the following research
questions:
• The effect of H2-enriched gas injection on the distribution of H2
concentration in the furnace, pressure drop, temperature profile,
coke rate, and overall fuel rate;
• The impact of operating parameters including recycling top gas and
O2 enrichment on furnace reaction conditions and consumption of
reducing agent when injecting COG/RCOG;
• The effect of H2 injection ratio on different parameters including
raceway adiabatic flame temperature (RAFT), O2 enrichment, the
thermal state of the furnace, coke reactivity and rate, furnace pro­
ductivity, H2 utilization efficiency and fuel rate;
• The capacity of this technique to reduce CO2 emissions of the steel
mills;
Experimental and modelling studies have been conducted to address
these research questions [121,126,133–138]. The impact of COG/RCOG
injection has been investigated both mathematically and experimen­
tally. The introduction of COG injection enhances column permeability
and lowers CO2 emissions [126]. Based on the mathematical study,
injecting 152.35 Nm3/tHM of COG reduces the pressure drop by 31.5 %
and increases the productivity of hot metal by 26.36 %, while decreasing
CO2 emissions by 17.54 % [126]. It is worth noting that COG/RCOG
injection has a cooling effect on the furnace due to enhancing indirect
reduction reactions of iron oxides with H2 which is an endothermic

13
B. Rahmatmand et al.
Fig. 18. Effect of RCOG injection on the overall fuel rate including RCOG rate and coal and coke rates [121].
reaction. Recycling the top gas through the shaft injection can alleviate
the temperature drop in the furnace [139]. O2 enrichment can also affect
the reaction condition and the consumption rate of reducing agents.
Fig. 17 shows the impact of COG injection, O2 enrichment, and top
gas recycling on coal, coke and reducing agent ratio (RAR). In Fig. 17,
case (1) is conventional BF with 3 % O2 enrichment (Base case), case (2)
is COG injection with 19 % O2 enrichment (COI12), case (3) is COG
injection and recycling BF top gas for tuyere injection with 71 % O2
enrichment (COI12-TI), and case (4) is COG injection and recycling BF
top gas for tuyere and shaft injection with 71 % O2 enrichment (COI12-
TI-SI). In Fig. 17, RAR refers to the sum of recycled reducing gas, COG,
and injected coal and coke. Based on the results, COG injection reduces
the coke ratio due to an enhanced reduction atmosphere and a larger
amount of H2 involved in the indirect reduction. In addition, recycling
top gas and O2 enrichment further reduce the coke and coal rates,
leading to a lower overall rate of reducing agents [135]. According to
the modelling results, carbon emissions can be reduced by up to 39 % in
the case of COG injection and recycling top gas through tuyeres injection
[135].
In addition to COG injection, the RCOG shaft injection into the BF
and its impact on reaction conditions and productivity of the BF have
been mathematically investigated [121]. Based on the modelling results,
the reaction conditions in the BF are influenced by the reducing agents
and thermal energy input by RCOG injection. Increasing the injection
rate of RCOG improves both the H2 concentration and near-wall
reduction of ferrous oxides. This causes the cohesive zone to narrow
and move towards the upper part of the BF. Moreover, enhancing the
shaft injection rate of RCOG contributes to the reduction of the coke rate
and enhancement of the BF productivity [121]. Fig. 18 shows the impact
of RCOG shaft injection on the overall fuel rate at 2 % O2 enrichment, as
estimated by Zhao et al. [121]. The total fuel rate including PCI, coke,
and RCOG increases with the RCOG injection, while RCOG injection
decreases the coke rate. These findings are consistent with other studies
[121,123,139–141]. The RCOG injection enhances the thermal energy
in the furnace, reducing the amount of coke required for heat supply.
Moreover, the high H2 content in the RCOG can partially substitute coke
[121]. Coke gasification produces CO for the reduction of iron oxides.
RCOG injection increases the share of iron oxide reduction by H2. The
reduction reactions of iron oxide with CO and H2 are shown in equations
(1) and (2) [121]:
(1/3)Fe2 O3 (s) + H2(g) →(2/3)Fe(s) + H2 O(g)
Fuel 336 (2023) 127077
(1/3)Fe2 O3 (s) + CO(g) →(2/3)Fe(s) + CO2 (g) (2)
The rate of iron oxide reduction by H2 is faster than CO. Thus, it is
expected that with RCOG injected, less fossil carbon (coke and PCI) is
required to generate the CO needed for the reduction of the ferrous
burden [121]. However, the reduction in the coke rate is not propor­
tional to the amount of RCOG injected, suggesting that there is a limit on
coke rate reduction that can be achieved by increasing the rate of RCOG
shaft injection [121]. Although the total reducing agent rate can be
reduced by COG injection when top gas is recycled and the O2 enrich­
ment ratio is increased (i.e., 71 %), higher RCOG rates with low O2
enrichment (i.e., 2 %) lead to higher total fuel rate as shown in Fig. 18.
This reflects the reduction in gas utilization efficiency due to the nar­
rower chemical reserve zone and the low utilization efficiency of H2
with the limited penetration depth [121]. Thus, O2 enrichment and
recycling of BF top gas are important factors in achieving a greater
reduction in carbon consumption when utilizing COG/RCOG in BF
operations.
Besides the mathematical studies, successful trials of COG and RCOG
injection have been carried out as a part of the Japanese national
COURSE50 project. COURSE50 conducted successful COG and RCOG
injection trials at LKAB’s experimental BF in Lulea, Sweden, in collab­
oration with Swerea MEFOS and LKAB which have been reported to
reduce the total carbon emissions [139]. The RCOG/COG injection and
top gas recycling were trialed in the LKAB experimental BF to evaluate
the substitution of coal and coke by H2-rich reducing agents. The RCOG
was composed of 77.9 % H2 and 22.1 % N2, while H2, CH4 and N2
concentrations of COG were 57 %, 31.3 %, and 11.7 %, respectively. The
impacts of the new operating condition on the upper furnace tempera­
ture and decomposition of the sinter were investigated [121,139]. Based
on the mathematical and experimental results from the COURSE50
program [137,138], RCOG injection into the shaft reduces the upper
furnace temperature, however, COG injection into the tuyeres has a
minor impact on the BF temperature profile [14]. It was also shown that
the rate of carbon consumption was reduced by up to 3 % as a result of
COG tuyere injection (100 Nm3/tHM) or RCOG shaft injection
(150 Nm3/tHM) compared to the base case [137,138]. Therefore,
although a high level of CO2 emissions reduction by COG/RCOG injec­
tion into the BF has been estimated by mathematical studies, carbon
consumption reduction reported by COG/RCOG injection experimental
trials is practically low. Further enhancement in the rate of COG/RCOG
(1)
14
B. Rahmatmand et al. Fuel 336 (2023) 127077

required to maintain a suitable RAFT. In addition, higher H2 rates

enhance the ore/coke ratio and pig iron production (Fig. 20). A higher
ore/coke ratio is attributed to the enhanced reduction atmosphere and
greater participation of H2 in indirect reduction, leading to a lower coke
consumption rate and CO2 emissions of the furnace. The increased
productivity at elevated H2 rates can be attributed to the enhanced
burden reduction and reduced residence time in the furnace, as well as
the improved combustion at the raceway that provides more space for
burden descent. Therefore, at an H2 injection rate of 120 Nm3/tHM
(about 10 kg/tHM), productivity increases by 17 %, while coke rate and
CO2 emissions decrease by 13 % and 5 %, respectively [134].
Yu et al. [147] investigated the effect of H2 injection into the BF shaft
on the thermal state and coke rate at a constant coal ratio using a multi-
fluid BF model. According to the thermal conditions near the belly of the
BF, H2 was injected at 900 ◦ C to avoid a large fluctuation in temperature
around the H2 inlet [147]. The H2 inlet temperature can be controlled
using devices such as counter-current heat exchangers [147]. The gas
Fig. 19. Impact of the increasing rate of H2 injection on O2 enrichment and
thermal field at H2 injection rates of 0–30 m3/s obtained by Yu et al.
AFT [134].
[147] are presented in Fig. 21. The distribution of temperature is hardly
affected by H2 injection at low flow rates of 5–20 m3/s, while further
injection can further reduce the CO2 emissions but this can be chal­
increase in H2 injection rate to 30 m3/s has a more significant effect on
lenging because the COG injection was implemented at the highest
thermal features in the BF. Moreover, the temperature in the stack of the
production rate of COG in the coke plant [137].
furnace can be maintained in an acceptable range by adjusting the
In addition to studying the effect of injecting H2-rich gas such as COG
injected H2 temperature [147]. It was also confirmed by Yu et al. [147]
and RCOG into the BF on in-furnace conditions and carbon consump­
that increasing the H2 injection rate at 900 ◦ C into the BF shaft at a
tion, some studies have focused on the impact of enhancing the H2 in­
constant coal ratio leads to a decrease in coke rate as shown in Fig. 22.
jection ratio on the mass and heat transfer and distribution of gas and
This is due to the improvement of both thermal conditions in the BF shaft
solid flows in the furnace. These changes influence different parameters
and reduction degree of iron oxides [147].
including raceway adiabatic flame temperature (RAFT), bosh gas vol­
As discussed above, high H2 injection rates reduce the RAFT and thus
ume, O2 enrichment, column permeability, indirect and direct re­
O2 enrichment and reducing blast volume are necessary to maintain the
ductions, coke reactivity and degradation, productivity, and fuel rate.
thermal balance in the furnace. Yilmaz et al. [145] evaluated the CO2
Some mathematical modelling investigations have been conducted to
emissions and coke rate reduction by H2 injection using FactSage/
investigate these impacts and to estimate the optimum H2 injection level
ChemApp as well as Aspen Plus based on commercial operating data
and the carbon consumption and CO2 emissions reduction that can be
(Fig. 23). It should be noted that in Fig. 23, H2 is used as the only ARA.
achieved. However, these studies have different assumptions including
The blast O2 concentration was increased, and the blast volume was
constant PCI rate or constant coke rate [134,142–146].
reduced to control the RAFT. Fig. 23 shows the influence of H2 rate and
Tang et al. [134] investigated the BF operation with H2 injection at a
blast temperature on the reduction of the coke rate. At an injection
constant PCI rate and found that at elevated H2 rates, the column
temperature of 80 ◦ C, the lowest coke rate was achieved at the H2 rate of
permeability increases and accordingly the pressure drop decreases.
20 kg/tHM. Further increase in the H2 rate led to higher coke rates to
However, enhancing the H2 rate reduces the RAFT in the raceway due to
compensate for the lowered sensible heat of the blast. Therefore, at
H2 decreasing the sensible heat. Moreover, an increase in the H2 rate
elevated H2 rates (greater than 20 kg/tHM), O2 enrichment and lower
enhances the volume of bosh gas. Accordingly, mass and heat transfer,
blast volume are insufficient in maintaining the thermal state of the
burden descent, and distribution of gas flow change due to changes in
furnace. Therefore, increasing the injection temperature is suggested to
the bosh gas volume and RAFT. To maintain the raceway stability,
compensate for the reduced sensible heat, leading to a reduction in the
thermal compensation is required. Thus, as shown in Fig. 19, at an H2
coke rate [145]. However, from a practical point of view, H2 injection at
injection rate of 120 Nm3/tHM, approximately 10 % O2 enrichment is

Fig. 20. Impact of H2 rate on (a) ore to coke ratio, and (b) productivity [134].

15
B. Rahmatmand et al. Fuel 336 (2023) 127077

Fig. 21. Thermal field of gas stream in the BF at different H2 injection rates into the shaft at 900 ◦ C and constant coal ratio: (a) 0 m3/s, (b) 5 m3/s, (c) 10 m3/s, (d) 15
m3/s, (e) 20 m3/s, (f) 25 m3/s and (g) 30 m3/s [147].

Fig. 22. Effect of increasing H2 injection rate into the BF shaft at constant coal ratio on coke rate saving [147].

a high temperature is questionable. The auto-ignition temperature of H2
is about 535 ◦ C, indicating the lowest temperature at which hydrogen
gas spontaneously ignites without the presence of a spark or flame
[148]. Thus, elevated H2 injection temperatures can increase the risk of
fire and explosion.
The majority of the mathematical investigations on H2 injection into
the BF have been conducted with the assumption of a constant PCI rate
that leads to decreasing the coke rate. However, it should be taken into
account that coke plays important and irreplaceable roles in maintaining
the permeability of the shaft and supporting the burden. In addition, in
modern BFs, coke rates are minimized by higher PCI rates [146]. In a
recent modelling study by Barrett et al. [146], the replacement of PCI
with H2 at a constant coke rate (364 kg/tHM) was found to have minimal
effect on BF operation. Through heat and mass balance simulations, a
maximum H2 injection rate of 19.5 kg/tHM was determined, restricted
by BF top gas temperature and RAFT (Fig. 24), which led to a 37.5 kg/
tHM reduction in PCI rate. It is worth noting that the source of H2 is
critically important in achieving a net emission decrease around the BF
[146,147]. If H2 is produced from renewable sources of energy, at a
maximum H2 injection rate of 19.5 kg/tHM, a 9.46 % decrease in CO2
emissions of the BF can be achieved [146]. Another parameter to
consider is the H2 utilization rate, which Barrett et al. [146] calculated
to be about 50 % under the conditions discussed above. The multi fluid
model simulation results presented by Yu et al. [147] also showed that,

16
B. Rahmatmand et al.
Fig. 23. Rate of coke consumption as a function of H2 injection rate at different
( )
H2 injection temperatures ϑinj [145].
Fig. 24. The maximum H2 injection rate constrained by RAFT and top gas
temperature at a constant coke rate (364 kg/tHM) [146].
at constant coal ratio and H2 injection temperature of 900 ◦ C, the uti­
lization efficiency of H2 is lower than 30 %, while that of CO can reach a
level much higher than 45 %. H2 utilization of 38–42 % has been re­
ported in some commercial trials [149]. In this context, solutions such as
recycling BF top gas to increase H2 utilization efficiency may be required
[146].
To summarize, modelling studies have shown that the introduction
of H2 affects the heat and mass balance, burden descent and gas flow
distribution in the BF. This is attributed to the negative impact of H2 on
sensible heat and RAFT. Consequently, O2 enrichment is required to
compensate for the low sensible heat. Moreover, increasing H2 con­
centration accelerates the indirect reduction of ferrous oxides, leading to
a lower coke consumption rate and CO2 emissions. In addition, the
enhanced burden reduction decreases the residence time in the furnace,
resulting in improved BF productivity. It is worth noting that although a
high level of CO2 emissions reduction by injecting H2-enriched gases
such as COG/RCOG into the BF (i.e., up to about 17–40 %) has been
reported based on the mathematical studies, carbon consumption
reduction reported in the COURSE50 program at the ultimate rate of
COG/RCOG injection into the experimental BF is practically low (i.e.,
about 3 %). Therefore, this creates the need for developing comple­
mentary technologies to improve the H2 and CO reduction efficiencies
and to remove CO2 from the top gas stream, contributing to further CO2
17
Fuel 336 (2023) 127077
emissions reduction of the BF operations. Moreover, the available
literature suggests an optimum H2 rate to minimize the coke rate.
Further increase in H2 rate leads to higher coke rates to maintain the
furnace thermal stability. Increasing H2 temperature has been suggested
to decrease the coke rate. However, H2 injection above its auto-ignition
temperature raises safety concerns.
Although most of the studies have focused on the constant PCI rate
assumption, others have investigated replacing PCI with H2 at a constant
coke rate due to the important roles of coke in sustaining the perme­
ability of the shaft and supporting the burden. Some modelling results
show an H2 injection limit of 19.5 kg/tHM, which can replace 37.5 kg/
tHM of PCI. However, a high H2 utilization efficiency is not expected. It
is worth noting that CO2 emissions reduction by this promising tech­
nique mainly depends on the method of producing H2. For instance,
injecting 19 kg-H2/tHM can lower CO2 emissions of the BF process by up
to about 9.5 % only if green H2 is used in the process. However, the
current capacity of green H2 production is not sufficient to supply the
steel industry demand. Therefore, according to the current prices of both
metallurgical coke and H2, the H2 rich BF ironmaking process is envi­
ronmentally competitive but not economically. The economic costs such
as H2 production and storage should be taken into account when
assessing this new ironmaking technology. In addition, some measures
can be taken to compensate for the low utilization efficiency of H2 such
as tuning the pressure of the top gas to limit the gas velocity. Imple­
menting a top gas recycling strategy can also help to enhance the
feasibility of this technology on an industrial scale. Most available data
in the literature on evaluating H2 injection into the BF are based on
mathematical modelling efforts. Therefore, larger-scale demonstration
trials are required to understand the benefits and limitations of the
process. This enables researchers to validate the mathematical models
more accurately and to better understand the potential of this technol­
ogy for reducing carbon consumption and operational limits.
6. Coke gasification behaviour under hydrogen-enriched BF
conditions
Coke is the only material that maintains a solid phase in the high-
temperature zone of the BF. Thus, the coke strength is important to
provide support for the ferrous burden and to minimize the generation
of coke fines to maintain gas permeability through the burden
[150,151]. CSR and CRI indices are commonly used in the industry to
assess the reactivity and strength of coke at high temperatures. Cokes
with low CRI and high CSR are more favorable for the smooth operation
of the BF, especially larger BFs [152]. The coke strength at high tem­
peratures has a direct impact on liquid and gas permeability in the BF,
the molten iron quality, coal injection rate, and the coke rate [153].
Coke gasification reactivity in the BF is the most important param­
eter that affects the coke strength and degradation at high temperatures
[154]. The main gasifying agents of coke –H2O and CO2– form during
the indirect reduction of ferrous oxides with H2 and CO. Coke gasifica­
tion results in the degradation of coke structure, decreasing the metal­
lurgical strength of coke and deteriorating BF productivity [114,155].
To decrease coke consumption and CO2 emissions in BF operations, re­
searchers have introduced co-injection of H2-rich gas (green H2, COG
and NG) with PCI [82,83,156,157]. In these techniques, the H2 con­
centration in the bosh gas can reach 10–20 % [156,158–161], acceler­
ating reduction of iron oxide with H2 and substantially increasing H2O
concentration in the BF, which alters the reaction environment for coke
gasification. Thus, it is important to gain a better understanding of coke
gasification behaviour under H2-enriched BF ironmaking conditions and
address the following research questions:
• The impact of H2-enriched operation on kinetics and mechanism of
coke gasification.
• The influence of elevated H2O concentration on coke reactivity,
structure degradation and post-reaction strength.
B. Rahmatmand et al.
Fig. 25. Schematic diagram of the four steps of gasification reaction between the carbon and CO2 and H2O gases.
Fig. 26. Rate of coke gasification with (a) CO2, and (b) H2O at various temperatures [167].
• Coke quality requirement to withstand the intensified gasification
atmosphere under H2– enriched operation conditions.
The coke gasification process is a solid-gas reaction including four
steps (Fig. 25): (1) external diffusion and adsorption of the gasifying
agent on the coke surface; (2) internal diffusion of gas through the pore
structure to the interior of the coke; (3) reaction between gas and carbon
at the interface; (4) desorption of product gases from the coke structure
[161,162]. Given that increasing H2 concentration in the BF and
accelerating iron ore indirect reaction with H2 lead to producing more
H2O in the furnace, increasing H2O content in the gas phase directly
affects coke gasification behaviour. This is attributed to the different
rates of internal diffusion and the interfacial reaction of H2O when
reacting with coke compared to those of CO2 [163,164]. This causes
differences between the mechanism of coke gasification with H2O and
CO2 that account for the change in coke features including microstruc­
ture, porosity, and macro-strength.
The importance of producing coke with high strength to be used
under COG injection conditions was highlighted in the COURSE50
program. In the first phase, a high-strength coke with drum strength (DI)
greater than 88 % was targeted to maintain the required gas perme­
ability for the intense H2 reduction environment at lower coke rates in
comparison with conventional BF operation [124]. To produce a high-
strength coke, high-performance caking additives (HPC) were utilised
in the coke-making process. HPC softening and melting start below
300 ◦ C, filling gaps and packing coal particles effectively. The combined
effects of introducing HPC and increasing the packing density improve
18
Fuel 336 (2023) 127077
coke strength [138].
Furthermore, thermogravimetric analysis has been applied to
investigate the interfacial reactions and gas diffusion, developing reac­
tion laws for the coke gasification process, and evaluating reaction
mechanism, coke structure degradation and macro-strength after gasi­
fication with H2O compared to CO2 [161]. The majority of the studies
use pure H2O and CO2 in coke gasification reactions. However, to better
understand the effect of the H2-enriched reaction environment on coke
reactivity, gas mixtures that simulate these conditions should be used.
Wang et al. [165–167] investigated the differences between coke
gasification with H2O and CO2 as shown in Fig. 26. The rate of coke
gasification with H2O was found to be 1.3–3.2 times higher than CO2. In
addition, the threshold temperature of coke gasification with H2O was
37 ◦ C lower than CO2 [167]. Some studies focused on the mathematical
and experimental investigation of the gasification behaviour of coke in
gas mixtures simulating the reaction environment inside the BF
[168,169]. H2O and CO2 are generated during the reduction of iron ore
with H2 and CO [170], which depends on the temperature and con­
centration of reducing gases. Coke gasification and iron oxide reduction
are synergetic reaction processes in the BF. Current estimates show that
H2 enrichment can vary between 10 % and 20 % [156,158–161]. With
the addition of H2, CO and H2 compete for the reduction of ferrous
burden. This results in the variation of H2O and CO2 volume fractions,
which in turn influence coke gasification reactions [171].
Dynamic gasification tests at simulated BF shaft conditions show that
the presence of H2O and H2 in the reaction atmosphere at 800–1200 ◦ C
can promote the coke gasification rate by up to 119 % compared to the
B. Rahmatmand et al.
Fig. 27. Changes in the range of carbon gasification temperature with CO to H2 ratio [171].
Fig. 28. Relative resistances of internal diffusion and interfacial reaction versus reaction ratio at different temperatures and reaction conditions of (a) CO2; (b)
H2O [163].
base case [172]. Similar results were reported by Haapakangas et al.
[169], who showed that partial substitution of CO2/CO with H2O/H2
increases coke reactivity. Although some studies report that H2O lowers
the threshold temperature of coke gasification [167], Haapakangas et al.
[169] showed that partial substitution of CO2/CO with H2O/H2 at
simulated BF reaction condition does not have a considerable impact on
the threshold temperature of coke gasification [169]. A different trend
was reported by Lan et al. [171], who observed that decreasing the CO/
H2 ratio lowers the start and end temperatures of coke gasification
steadily, and the carbon gasification temperature range shifts to the
lower temperature zone, as shown in Fig. 27. It can be concluded that
increasing H2 and H2O content of the BF gas phase results in enhancing
coke gasification reaction rate, while the impact of H2 and H2O on the
threshold temperature of coke gasification depends on gas phase
composition and coke type.
Some studies have reported that the choice of kinetics model – grain
model (GM), volumetric model (VM), and random pore model (RPM) –
for explaining the coke gasification mechanism under a simulated BF
reaction condition yield similar results [173]. Other studies have re­
ported different coke gasification mechanisms with H2O and CO2 [173].
19
Fuel 336 (2023) 127077
Coke gasification involves two main steps: the internal gas diffusion
through the porous structure of coke and the interfacial reaction be­
tween gas and carbon. Previous studies show that the controlling step in
the reaction between coke and H2O is different from that of CO2 [163].
As shown in Fig. 28, the resistance against internal diffusion of CO2
molecules through the coke pores is greater than H2O, indicating a
better diffusivity of smaller H2O molecules into the porous structure of
coke. In addition, CO2 gasification of coke at low temperatures
(900–1000 ◦ C) is controlled by interfacial reaction in the early stages of
the reaction, internal diffusin of gas and interfacial reaction in the
middle stage, and internal diffusion of gas in the final stage, shifting to
primarily interfacial reaction control at above 1000 ◦ C. In contrast, coke
gasification with H2O in the temperature range of 900–1100 ◦ C is
entirely controlled by interfacial reaction between carbon and H2O
[163]. Therefore, it is expected that the impacts of CO2 and H2O on the
degree and mechanism of coke degradation are different.
Wang et al. [166] investigated the effects of CO2 and H2O gasifica­
tion on coke porosity. Fig. 29 shows that coke porosity decreases after
gasification at higher temperatures. This is attributed to the accelerated
reaction rate and connection of smaller pores as the gasification reaction
B. Rahmatmand et al.
Fig. 29. Comparison of apparent coke porosity after reaction with pure CO2 and H2O between 950 and 1250 [166].
Fig. 30. (a) The schematic diagram of coke cross-sectional area for measuring porosity; (b) coke porosity in zones 1 and 2 at different CO and H2 concentra­
tions [171].
proceeds. Fig. 29 also shows that the porosity of coke after reaction with
CO2 is greater than that of H2O. Given that the coke gasification rate
with H2O is greater than that with CO2, at a similar solution loss, the
reaction with H2O mainly takes place at its exterior layers of coke,
leading to less damage to the internal pore structure [166].
The changes in coke porosity after gasification with gas mixtures
containing N2, H2, CO, CO2 and H2O were investigated by Lan et al.
[171]. In this research, the gas mixture passed through a ferrous bed,
where the reduction of iron oxides produces both H2O and CO2 for coke
gasification in the upper bed [171]. The changes in porosity after gasi­
fication in the interior and exterior of coke show that the elevated H2/
H2O concentrations lead to increased porosity at the coke exterior and
less influence on internal porosity (Fig. 30) [171]. This accords with
apparent coke porosity measurements by Wang et al. [166]. On the other
hand, Xu et al. [151] showed that compared with CO2, coke gasification
with H2O results in more damage to both coke interior and exterior, as
shown in the panoramagrams in Fig. 31. Therefore, coke characteristics
of microstructure, microtexture, and ash chemistry should be taken into
20
Fuel 336 (2023) 127077
account when evaluating the impacts of H2/H2O enrichment on its
reactivity and degradation mechanism.
The differences in coke gasification with H2O and CO2 on post-
reaction strength have been investigated. The relationship between
coke solution loss ratio (SLR) and coke strength after reaction (CSR)
after reaction with H2O and CO2 is presented in Fig. 32, showing a
negative correlation. A 1 % increase in SLR leads to a 1.2 % and 0.8 %
decrease in the coke CSR under CO2 and H2O environments, respec­
tively. This indicates that, at a similar SLR, the CSR of coke after reaction
with CO2 is lower than that of H2O [167]. As discussed above, the re­
action between coke and H2O can take place more on the coke exterior,
leading to less damage to the coke interior compared to CO2. This is
understood to account for higher coke CSR after reaction with H2O.
Similar results were reported by Shin et al. [174], who investigated the
effect of gasification with H2O and CO2 on coke macro-strength, as
shown in Fig. 33. Coke porosity after reaction with CO2 was found to
significantly differ from that of H2O. Due to its lower reactivity, CO2 can
diffuse into the coke pores and react at the internal pore interface, while
B. Rahmatmand et al. Fuel 336 (2023) 127077

Fig. 31. Coke panoramagrams presented by Xu et al. [151] at different conditions: (a) unreacted coke A, (b) coke A gasified with CO2, (c) coke A gasified with H2O,
(d) unreacted coke B, (b) coke B gasified with CO2, (c) coke B gasified with H2O.

Fig. 32. Correlation between CSR and SLR of coke after reaction with CO2 and H2O [167].

H2O tends to react at the coke surface. The interparticle reaction be­
tween coke and CO2 weakens the core matrix of coke, leading to lower
strength after reaction. Conversely, the H2O reactivity at the coke sur­
face causes less damage to the integrity of the coke [174].
The findings of Wang et al. [167] and Shin et al. [174] that coke
reactivity with H2O caused less damage to coke integrity conflicted with
those of Xu et al. [151] who reported that coke gasification with H2O led
to a drastic increase in CRI and decrease in CSR (Fig. 34). These con­
flicting results suggest that in addition to the reaction environment, coke
properties such as microstructure, ash chemistry, and microtexture
should be taken into account when evaluating the influence of the re­
action environment on the coke gasification and degradation

21
B. Rahmatmand et al.
Fig. 33. Coke residues after the tensile experiment at different reaction degrees and environments at 1200 ◦ C: (a) 25 % reaction degree with CO2, (b) 25 % reaction
degree with H2O, (c) 50 % reaction degree with CO2, and (d) 50 % reaction degree with H2O [174].
mechanism. It is also worth noting that most of the investigations
around this subject have been conducted in H2O and CO2 which do not
represent the actual reaction condition in H2-enriched BF operation.
Therefore, future research should focus on understanding the impact of
coke structure, texture, and ash chemistry on gasification and degra­
dation mechanisms, and the strength after reaction under H2-enriched
BF reaction conditions.
To summarize, the introduction of H2 to BF leads to the generation of
H2O during the reduction of ferrous oxides, which in turn increases the
coke gasification rate and lowers the temperature range of coke gasifi­
cation [171,172]. Table 2 summarizes the literature results on the effect
of H2/H2O addition on coke gasification mechanism, reaction rate, and
coke porosity and strength compared to the conventional BF operation.
Depending on the mechanism of coke gasification and reaction mode,
H2-enriched operations may result in the generation of large pores
leading to reduced coke strength or, conversely, reaction at the coke
exterior may maintain the strength of the coke core matrix. In addition
to the reaction environment, coke properties of microstructure, ash
chemistry, and microtexture should be taken into account when evalu­
ating the coke gasification and degradation mechanisms. Addressing
these knowledge gaps will provide the information required to under­
stand the coke quality requirements in hydrogen-enriched BF
operations.
7. Conclusions and research outlook
This review has assessed the current progress in decarbonizing blast
furnace ironmaking technologies and provides a comprehensive un­
derstanding of fuel requirements, in particular coke rate and coke
quality requirements in low-carbon BF operations. An overall conclusion
is that different approaches taken to reduce CO2 emissions from BF
ironmaking will influence the coke rate and quality requirements
differently. Some important findings of this review are summarised
below:
• Although the implementation of innovative blast furnace ironmaking
technologies contributes to reducing coke and coal consumption,
coke cannot be completely replaced by alternative reducing agents
because it plays an irreplaceable role as the skeletal support and
permeable layer in the BF. Introducing new reducing agents to the BF
can affect the reaction condition, gas composition, and temperature
22
Fuel 336 (2023) 127077
which can result in changing the coke gasification mechanism and
the rate of coke degradation reaction and accordingly coke quality
requirements and consumption rate.
• Ferro-coke charging to the BF is understood to be a promising
technique to decrease carbon emissions of BF operations by reducing
the thermal reserve zone temperature and enhancing BF efficiency.
• Regarding biomass injection into the BF, the coal substitution rates of
raw wood pellet and torrefied biomass are much lower than char­
coal. According to modelling studies, PCI can be completely
substituted only by charcoal, leading to a CO2 emissions reduction of
up to 40 %. In addition, based on the experimental investigation,
biomass injection can influence coke microstructure, wettability, and
reactivity depending on biomass properties such as ash content and
composition.
• According to the results achieved by the ULCOS (ultra-low CO2
steelmaking) program, the oxygen blast furnace with top gas recy­
cling (OBF-TGR) process can lower CO2 emissions by up to 76 %.
However, due to the well-known problems related to OBF technology
recognized as overheating in the lower section and thermal shortage
in the upper section, the adaption of full O2 blast in the long term
requires further understanding through larger-scale trials. In addi­
tion, based on the modelling results, a minimal coke rate with
increasing O2 concentration has been reported.
• The injection of COG/RCOG as the H2-rich reducing gas into the BF
has some advantages including reduction of both the coke rate and
CO2 emissions. However, COG injection, due to its high H2 content,
can promote coke degradation by increasing the rate of carbon so­
lution loss reaction. Modelling studies have shown that to maintain a
high RAFT and top gas temperature, COG should be injected at
higher temperatures, thus coke of greater quality, i.e., higher CSR, is
required to withstand harsher reaction conditions. The understand­
ing of these changes to coke quality requirements is limited and re­
quires further investigation.
• The introduction of H2 gas into the BF leads to the generation of H2O
during the reduction of the ferrous burden, which in turn increases
the coke gasification rate, reduces coke strength after reaction, and
lowers the temperature range of coke gasification. The experimental
studies in the literature show that coke gasification with H2O leads to
greater damage to the coke structure compared to CO2 due to the
higher rate of coke reaction with H2O. This results in the generation
of larger pores throughout the coke, leading to faster degradation of
B. Rahmatmand et al.
Fig. 34. (Top) CRI and (Bottom) CSR of different coke samples after gasification with pure H2O and CO2 at 1100 ◦ C [151].
its structure. However, based on the experimental investigation, H2O
gasification increases the porosity of coke’s outer layers without a
significant impact on the inner layers. Thus, further research is
needed to determine the quality of coke suitable for such operations.
• Literature data indicate that H2 injection can decrease the overall
CO2 emissions by replacing part of PCI and coke. However, the
determination of the maximum possible injection level of H2 into the
BF and the subsequent emissions reduction requires further research.
• Reducing CO2 emissions of the ironmaking industry through H2 rich
BF ironmaking mainly depends on the method of producing H2.
According to the low utilization efficiency of H2 in the BF and high
price and limited supply of green H2, the H2 rich BF ironmaking
process is environmentally competitive but not economically. This
might be solved when the price of H2 becomes reasonable by
employing new technologies for H2 production in the future.
• Shifting away from conventional BF to low-carbon ironmaking
technologies creates a need for investigating the effects of intro­
ducing new reducing agents on coke quality requirements. Future
research should address these knowledge gaps by focusing on:
➤ Investigating the effects of biomass ash and coke wettability on
gasification reactivity and degradation mechanism of coke to
allow selection of suitable coke and biomass for co-use in blast
furnace ironmaking.
23
Fuel 336 (2023) 127077
➤ Understanding the changes in the coke structure under OBF-TGR
and H2-enriched operation conditions and benchmarking against
the conventional BF operation to improve the understanding of
coke quality requirements in these low-carbon BF operations.
➤ Formulating associations between coke properties and micro­
structure evolution during OBF-TGR and H2-enriched operations,
to explain the coke degradation mechanism.
➤ Gaining a deeper understanding of how coke quality indices relate
to its degradation mechanism under low-carbon BF operation
conditions.
➤ Evaluating the mechanism of coke degradation under conven­
tional and H2 reduction BF conditions and exploring links be­
tween coke reactivity and kinetics and coke quality indices and
parent coal properties under an H2-enriched reaction environ­
ment to better understand suitable coal properties and coke
qualities that can withstand the intensified gasification environ­
ment by injection of H2 into the BF.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
 B. Rahmatmand et al.
Table 2
Summarised literature results about the effect of H2/H2O-enriched BF operation on coke gasification mechanism, reaction kinetics, porosity and strength [151,163,167,169,171–174].
Parameter Reacting gas Note

Pure H2O or pure CO2 Gas mixture (CO, CO2, N2, H2 and H2O)

Reaction rate • The rate of coke gasification with pure H2O is up to about 1.3–3.2 times • At simulated BF shaft conditions, CO2/CO partial –
greater than that of pure CO2 [167]. substitution with H2O/H2 has a positivize effect on coke
reactivity [169]
• Presence of H2O and H2 in the reaction atmosphere at
800–1200 ◦ C near the BF wall can promote the coke
gasification rate by up to 119 % [172].

Threshold • The threshold temperature of coke gasification with H2O has been reported to • Partial substitution of CO2/CO with H2O/H2 at simulated BF –
temperature of be 37 ◦ C lower than CO2 [167]. reaction condition does not have a considerable impact on
coke gasification the threshold temperature of coke gasification [169]

Coke gasification • Internal diffusion of CO2 molecules through the coke pores is slower than H2O • Under a simulated BF reaction condition, the kinetics model –
mechanism [163]. choice – GM, VM, RPM – does not significantly differ in
• At 900–1000 ◦ C, CO2 gasification of coke is controlled by interfacial reaction explaining the coke gasification mechanism [173].
in the early stages of the reaction, internal diffusion of gas and interfacial
reaction in the middle stage, and internal diffusion of gas in the final stage
[163].
• At 1000–1100 ◦ C, coke gasification with CO2 shifts to primarily interfacial
reaction control [163].
24

• At 900–1100 ◦ C, coke gasification with H2O is entirely controlled by an

interfacial reaction between carbon and H2O [163].

Reaction mode • Reaction mode between coke and CO2 is the intraparticle reaction because CO2 The changes in the reaction mode by partial substitution of
diffuses into the pores of coke due to its low reactivity [174]. CO2/CO with H2O/H2 is not understood yet.
• Reaction mode between coke and H2O is surface reaction due to the high
reaction rate [174].

Coke porosity after There are opposite results in the literature:
the reaction • The porosity of coke after reaction with pure CO2 is greater than that of pure
H2O [166].
• Coke gasification with pure H2O results in more serious damage to both coke
interior and exterior compared to pure CO2 [151].
• Elevated H2/H2O concentrations lead to the increased coke This suggests that initial coke properties and micro-structure
exterior porosity, but the decreased coke interior porosity affect coke interior and exterior porosity after gasification under
[171] H2/H2O-enriched conditions.

Coke macro-strength There are opposite results in the literature:
after the reaction • At a similar reaction degree, the CSR and macro-strength of coke after reaction
with pure CO2 is lower than that of pure H2O [167,174].
• Coke gasification with pure H2O leads to a drastic decrease in CSR compared
to CO2 [151].
The effect of partial substitution of CO2/CO with H2O/H2 on This suggests that, in addition to the reaction environment,
the coke macro-strength after reaction is not understood yet. initial coke properties such as microstructure, ash chemistry, and
micro-texture influence the coke strength after the reaction.

Fuel 336 (2023) 127077

B. Rahmatmand et al.
Data availability
Data will be made available on request.
Acknowledgments
This study was funded by the Australian coal industry’s Research
Program (ACARP) (C33060). The PhD scholarship from BHP and the
University of Newcastle is greatly appreciated. We gratefully acknowl­
edge the tremendous technical support from the industry mentors,
Cameron Tasker (Xcoal Energy & Resources), Nick Andriopoulos (Anglo
American), Stephen Brant (BHP), and ACARP coordinator Ashley
Conroy.
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