Fuel 366 (2024) 131277

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Physical and chemical properties of metallurgical coke and its evolution in

the blast furnace ironmaking process
Wenquan Niu , Yan Li , Qiang Li , Jingsong Wang *, Guang Wang , Haibin Zuo , Xuefeng She ,
Qingguo Xue
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China

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

Keywords: Pursuing green, low-carbon ironmaking technology primarily aims to reduce fuel ratios, specifically coke ratios.
Metallurgical coke Concurrently, as coke ratios decrease, coke deterioration becomes more pronounced; this significantly affects the
Blast furnace ironmaking smelting process and increase the demand for high-quality coke. Coke plays an irreplaceable role in blast fur­
Coke properties
naces (BFs), acting as both the skeleton of the stock column and the permeable layer of the gas flow. Thus,
Multi-phase reactions
Alkali metals
examining the structural characteristics of coke and evolutionary behavior of its properties within the BF is
Graphitization crucial. To thoroughly comprehend the properties of coke and its evolution in BFs, this article divides the
structure and composition of coke into four aspects: pore, matrix, and microcrystalline structures and mineral
compositions. First, the behavior of coke in the BF is addressed, examining the evolution of its performance at
different positions and its involvement in multiphase reactions. Subsequently, the effects of alkali metals and zinc
accumulation in the furnace on the properties of coke are summarized in detail. Finally, the graphitization
phenomenon of coke within the furnace is introduced. As the temperature increases, the degree of graphitization
of coke deepens; this has a significant effect on its structure and composition. This review also identifies the
knowledge gaps and outlines potential future research opportunities in this domain.

replacement of coke with alternative reducing agents remains unfeasible

1. Introduction
Blast furnace (BF) ironmaking continues to dominate the ironmaking
industry, accounting for approximately 70 % of the global share [1].
Steel, a cornerstone of modern civilization, is extensively utilized in
sectors like transportation, construction, and infrastructure. As one of
the most carbon- and energy-intensive sectors, the steel industry faces a
direct correlation between increased steel production and increased
greenhouse gas (GHG) emissions [2–5]. Notably, emissions from the
steel sector constitute 7 % of total global emissions and 16 % of indus­
trial GHG emissions [6,7], placing a significant responsibility on this
industry regarding resource management, energy efficiency, and
pollution emission reduction.
The substitution of charcoal with coke in BF ironmaking marked a
revolutionary shift in the history of metallurgy. Coke, one of the most
costly raw materials [8], coke plays, fulfills four primary roles in BF: as a
reducing agent for iron ore, a heat source, a carburizing agent for hot
melt, and as the skeleton of the stock column [9–13]. Despite centuries
of advancements in BF ironmaking technology, the complete
due to its irreplaceable role as both a structural component and a
permeable layer for gas flow [14]. In pursuit of the “double carbon”
objective, it is imperative to develop an innovative, intensive BF iron­
making model to minimize coke consumption [15,16].
Accurately characterizing the transformation of coke’s macroscopic
properties at the microscopic scale holds both theoretical and practical
importance for precisely controlling coke quality. Beginning with an in-
depth initial characterization of coke’s structure and composition, this
study meticulously explores the qualitative and quantitative relation­
ships between coke’s structure, composition, and properties. We sum­
marize the mechanisms underlying coke quality deterioration in various
regions of the BF, along with the influencing factors. This is done to offer
insights and perspectives to enhance coke quality and reduce its
consumption.
2. Structure and composition of coke
When heated to (950 to 1050) ◦ C under air-isolated conditions,
bituminous coal undergoes stages of drying, pyrolysis, melting, bonding,

* Corresponding author.
E-mail address: wangjingsong@ustb.edu.cn (J. Wang).

https://doi.org/10.1016/j.fuel.2024.131277
Received 19 December 2023; Received in revised form 30 January 2024; Accepted 22 February 2024
Available online 4 March 2024
0016-2361/© 2024 Elsevier Ltd. All rights reserved.
W. Niu et al. Fuel 366 (2024) 131277

Nomenclature GHG Greenhouse gas

BET Brunauer-Emmett-Teller
BF Blast furnace DFT Density functional theory
BJH Barret-Joyner-Halenda OTI Optical anisotropy index
DH Dollimore-Heal CRS Coke strength after reaction
CRI Coke reactivity index La Average extension width
Lc Average stacking height d002 Interlayer spacing
g Graphitization degree TEM Transmission electron microscope
XRD X-ray diffraction HRTEM High-resolution TEM
HR High resolution XPS X-ray photoelectron spectroscopy
LTA Low-temperature ashing FTIR Fourier transform infrared
M10 Micum index 10 M40 Micum index 40
RAFT Raceway adiabatic flame temperature MCI Mineral catalytic index
MBI Mineral basicity index HTT Heat treatment temperature
DI Drum intensity PC Pulverized coal
NG Natural gas

curing, and shrinkage, and ultimately forms coke. Coke can be charac­
terized as a nonhomogeneous composite material comprising organic
carbon, inorganic minerals, and numerous pores [17]. Coke burns with a
short blue flame and without smoke, releasing substantial heat; the
combustion is slow and enduring, often forming an ash shell on its
surface. As showed in Fig. 1, macroscopically, coke is a hard, porous,
cracked material, silvery-white or grayish black with a metallic luster.
Microscopically, it comprises pores, microscopic cracks, and a solid
carbon matrix embedded with inorganic minerals and organic inert
materials [18].
Statistically, over 90 % of global coke production is utilized in BFs,
rendering it a fundamental component of the steel industry. In the past
six decades, the structure of coke has been extensively characterized and
documented [19–22]. Recent fundamental research reveals that coke’s
performance primarily depends on its structure, encompassing aspects
like the ratio of isotropic carbon to inert matter, the size and shape of
anisotropic carbon units, the intersection of various structural organi­
zations, and the porosity and ash composition [23–25]. The forthcoming
sections offer detailed insights into coke’s pore structure, matrix struc­
ture, microcrystalline structure, and mineral composition, thereby
enhancing the understanding of coke and contributing to producing
higher-quality coke for BF operations.
2.1. Pore structure
The porous structure of coke primarily develops during the high-
temperature dry distillation phase of coking coal, occurring at (350 to
500) ◦ C, where volatile components are actively decomposed, resulting
in a general porosity of 50 % to 60 % [26]. This structure ranges from
macropores, with diameters exceeding several hundred micrometers, to
ultra-micropores, with diameters less than 1 nm, dispersed throughout
the coke. The pore structure serves as a focal point for stress concen­
tration, potentially impairing coke strength, and acts as a conduit for
reaction gases to permeate the coke. Consequently, this structure
significantly influences the coke’s mechanical strength and thermal
properties [27]. Hence, the pore structure is a critical indicator of its
mechanical strength and thermal characteristics. The primary tech­
niques for assessing coke’s pore structure encompass vacuum drainage,
microscopic image analysis, pressed mercury assays, and gas adsorption
methods.
Different research tools are essential for examining the various sizes
of coke pores. The mercury porosimeter can detect pore sizes ranging
from (0.003 to 500) μm. Pores larger than 500 μm are measurable
through microscopic image analysis, while those smaller than 0.003 μm
are detectable via the gas physical adsorption method [28–31]. Fig. 2
illustrates the capacity to characterize coke pores from the nanometer to
millimeter scale using this diverse detection [32,33].
The vacuum drainage method utilizes Archimedes’ principle to
determine coke porosity. This is calculated based on the weight of the
coke before and after water absorption, a technique formalized as a
national standard (GB/T 4511.1–2008) [27]. Wu et al. [34] employed
this method to measure coke’s apparent porosity. Their unidirectional
test revealed that the accuracy of the measurements is influenced by
several process parameters, including the vacuum degree, resting time,

Fig. 1. Samples of coke: (a)macroscopic sample; (b)microscopic sample.

2
W. Niu et al.
Fig. 2. Techniques for recognizing pores in solid materials [32].
and suction time, as depicted in Fig. 3.
The microscopic image analysis method employs an optical micro­
scope to examine the polished surface of coke. This technique involves
setting a specific grayscale threshold for segmentation and identifica­
tion, distinguishing between the pores and their walls. A computer then
statistically determines the pore structure parameters, such as pore
diameter, wall thickness, and distribution across the entire measure­
ment areacomputer [27]. Nyathi et al.[35] utilized optical microscopy to
analyze the pore structure of coke with varying grain sizes. An image
processing program was employed to obtain parameters like pore area,
wall thickness, and diameter. Fig. 4 showcases an example of how these
pore parameters are determined.
In Japan, 3D imaging of coke’s internal structure was achieved using
X-ray transmission scanning. This method allows for reconstructing
arbitrary tomographic images, thereby completing the 3D internal [36]
coke structure. The internal structure data obtained through comput­
erized tomography was then used to model coke, enhancing the simu­
lation of the model [37]. However, the effectiveness of this approach
depends on the scanning equipment and image processing software,
necessitating further research for its widespread application.
The pressed mercury assay operates on the principle of mercury’s
surface tension, assuming that the internal pores of porous materials are
cylindrical of varying sizes and extend to the sample’s outer surface.
This method analyzes the distribution of pores in porous materials by
calculating the amount of mercury pressed at different pressures. The
pore distribution in coke is determined based on the varying pressures
applied during mercury pressing [38]. Yamamoto et al.[39] explored the
relationship between coke pore configuration and tensile strength using
mercuric pressure. They found that an increase in stomata below 100 μm
helped maintain the tensile strength of coke at consistent reaction rates.
The gas adsorption method leverages the phenomenon of capillary
condensation and the principle of volume equivalent exchange for
Fig. 3. Orthogonal test results: (a)measurement results of apparent porosity of
coke under different vacuum levels; (b)coke water absorption as a function of
time [34].
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Fuel 366 (2024) 131277
assessing pore size distribution. Using various theoretical models, this
technique computes the specific surface area, pore volume, and pore size
distributions. The Brunauer-Emmett-Teller (BET) model, for instance, is
employed to ascertain the adsorption amount of a single molecular layer
on the specimen, thereby facilitating the calculation of the specimen’s
specific surface area. Further, pore size distribution is derived using
Barret-Joyner-Halenda (BJH), Density functional theory (DFT), and
Dollimore-Heal (DH) models. In the gas-adsorption method applied to
coke’s pore structure analysis, N2 and CO2 are predominantly used. CO2,
under laboratory conditions, exhibits superior diffusion capability
compared to N2. This attribute enables CO2 to readily attain adsorption
equilibrium and effectively penetrate slit-like micropores smaller than
0.7 nm [40]. Grigore [41] measured the specific surface area of nine
coke types using N2 and CO2 as adsorbents. The study revealed that the
specific surface area determined through CO2 adsorption was markedly
greater than that measured via N2 adsorption. A detailed comparison of
these methods, including the sizes of pores they can detect and their
respective advantages and disadvantages, is provided in Table 1.
2.2. Matrix structure
The coke matrix, or pore wall, constitutes the primary component of
coke, with its structure critically influencing coke’s most essential
properties. This solid portion of coal remains after parts of the coke oven
gas and coal tar are released during dry distillation. During the coking
process, the active components of coal such as vitrinite and lipidome
soften and melt, forming a continuous pore wall. In contrast, inert
components like inertinite, opaque, and semi-vitrinite are retained in
the pore wall alongside the softened active components [42]. The optical
organization composition of coke can be ascertained from the varied
morphological characteristics of the coke matrix structure, observable
through polarized light microscopy [43]. The optical organization of
coke is investigated by isolating the matrix portion remaining in the pore
structure, classifying it based on microscopic characteristics (shape, size,
color) using polarized light microscopy.
International optical organization classification schemes, including
those by Patrick, Sugimura Hidehiko, and Marsh, are widely recognized.
Reflecting the characteristics of China’s coking coal and metallurgical
coke, Chinese researchers revised the national metallurgical industry
standard YB/T077–1995, “Determination Methods of Optical Tissue of
Coke,” in 1994. Coin et al. [44] identified typical visual textures of coke,
such as isotropy, mosaic structure, schistose, fibrous, banding, anisot­
ropy, and pyrolytic carbon. To streamline matrix structure character­
ization, the optical organization of coke was simplified to classifications
of isotropic or anisotropic. All optical textures are considered aniso­
tropic except for isotropic and inertinite [32]. The degree of optical
W. Niu et al. Fuel 366 (2024) 131277

Fig. 4. An example of the determination of pore parameters in a coke matrix: (a)original image; (b)measurement procedure [35].

Table 1
Comparison of coke pore structure characterization methods.
Method Sample size Pore size Parameters Type Advantages Disadvantages

Vacuum drainage 15–60 mm >2.2um Porosity Open pores Convenient and fast Parameter less
Microscopic image 30 × 30 mm >100 nm Porosity, shape, size Open and close High resolution Broken samples, plane
pores representation issues
3D scanning Cylindricity >500um Porosity, shape, size Open and close 3D structure without breaking Complex process, imperfect
pores the sample methodology
Pressed mercury 0.02 mm 0.3um- Size distribution Open pores Fast measuring speed Possible collapse
assay 400um
Gas adsorption 0.02 mm 0.4 nm-100 Size distribution, fractal Open pores Avoiding interference from Small detection range
nm dimension chemisorption

anisotropy varies among different optical tissues. As coal deterioration

intensifies, the isotropic organization in the resultant coke diminishes,
the anisotropic organization and size incrementally increase, and the
microcrystalline large-particle structure becomes more prevalent.
The various optical organization structures in coke are assigned
distinct optical anisotropy values. The coke optical anisotropy index
(OTI) is derived by weighing the coke according to its content. This
index reflects the degree of anisotropy in coke, indicating the level of
order of the carbon atoms within it. Zhang et al. [45] evaluated the
optical structure of coke from six different manufacturers, adhering to
the Chinese standard YB/T 077–2017 (determination of the optical or­
ganization of coke). The study assessed the matrix structure of coke from
these manufacturers, as delineated in Table 2. It was observed that coke
with a higher content of isotropic structure exhibited increased reac­
tivity. All isotropic textures appear black due to extinction, whereas
anisotropic weaves exhibit brightness as the reflected light partially
penetrates the bias detector. The results of this study, illustrated in
Fig. 5, indicate that coke with a higher degree of anisotropy corre­
sponded to a lower Coke Reactivity Index (CRI).
In conclusion, various scholars have employed many methods to
investigate the coke matrix structure, significantly enhancing our un­ Fig. 5. Content of eight coke anisotropic structure types [25].
derstanding of coke’s microstructure. These studies have established a
qualitative and quantitative relationship between the structure of the multiple dimensions.
coke matrix and its macro properties. Nonetheless, given the complexity
of the coke matrix structure, continued development of diverse meth­
odologies is essential to comprehend the structure of the coke matrix in 2.3. Microcrystalline structure

During the high-temperature pyrolysis of coking coal, an increase in

Table 2
temperature leads to the continuous shedding and decomposition of side
Optical tissue content and CRI values [45].
∑ ∑ chains on aromatic rings. This process results in the condensation and
Coke ISO a/% CRI/% Coke ISO/% CRI/% thickening of these aromatic rings, forming a microcrystalline structure.
C1 28.8 18.4 C4 47.4 34.4 This structure is the most fundamental structural unit of the coke matrix
C2 31.0 21.3 C5 45.3 36.5 (stoma wall) and is akin to the structure of graphite crystals. The
C3 23.0 20.6 C6 79.9 46.2
investigation of the microcrystalline structure of coke often involves
a
Σ ISO=%Isotropic+%Inert. comparisons with graphite crystal structures, as schematically

4
W. Niu et al.
illustrated in Fig. 6. Carbon, the predominant component of the coke
matrix constitutes over 80 % of coke’s mass and exists in various forms
microcrystalline [11]. The carbon structure within coke is primarily
discerned through its microcrystalline structure [46].
Among the different dimensions of coke structure, the microcrys­
talline structure of the matrix holds significant importance. It is instru­
mental in guiding coke production, understanding coke performance,
and promoting efficient utilization in the BF. Therefore, obtaining the
parameters of the microcrystalline structure through characterization
methods and establishing its correlation with coke performance be­
comes a crucial indicator for evaluating coke.
Utilizing Scherrer’s formula and Bragg’s equation enables the
computation of various microcrystalline parameters. These calculations
facilitate the determination of vital microcrystalline attributes,
including the average stacking height (Lc), average extension width (La),
the graphitization degree (g), and interlayer spacing (d002) as follows:
Kλ
L= (1)
βcosθ
λ
d002 = (2)
2sinθ002
0.3340 − d002
g= (3)
0.3340 − 0.3354
where K represents the constant specific to the given reflection plane
(L002: A = 0.91; L10: A = 1.84); λ is the wavelength of the X-rays, nm; β is
the half-peak full width; θ signifies the Bragg angle; and 0.3440 nm is the
layer spacing for completely non-graphitized carbon. The g value of the
coke is determined by comparing the relative difference between the
calculated d002 value and the layer spacing of ideal graphite, which is
0.3354 nm.
The microcrystalline structure of coke can be characterized by
several methods, including X-ray diffraction (XRD), transmission elec­
tron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photo­
electron spectroscopy (XPS), and Raman and Fourier transform infrared
(FTIR) spectroscopies. XRD and TEM are the most commonly used for
studying coke’s microcrystalline structure. The geometry of ideal mi­
crocrystals is depicted in Fig. 7. XRD allows for the quantitative analysis
of layer spacing, stacking height, and lamella size in coke microcrystals.
Images of coke microcrystals obtained through TEM and HRTEM un­
dergo Fourier transformation, noise reduction, and mathematical and
statistical computation to derive parameters characterizing their struc­
ture. These parameters include microcrystalline stripe length, curvature,
and inclination angle, collectively providing insights into the size,
ordering degree of coke microcrystals, and their impact on coke reac­
tivity. XPS technology is instrumental in characterizing the bonding
states of carbon and oxygen in coke, including graphitized carbon, C-O
Fig. 6. Schematic crystal structure of graphite [47].
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Fuel 366 (2024) 131277
bonds, C = O bonds, and COO bonds. It is also used for fitting various
ratios and determining the graphitized carbon content, which serves as a
parameter for assessing the degree of graphitization [48]. Raman spec­
troscopy, with its focus on G (graphite) and D (defect) bands, is typically
found near (1580 to 1600) cm− 1 and 1350 cm− 1, respectively [49]. For
detailed information on the carbon structure of coke, the Raman spectra
are curve-fitted in the range of (800 to 1800) cm− 1, as shown in Fig. 8 for
coal samples post-carbonization at 700 ◦ C [50]. FTIR analysis primarily
involves identifying and attributing absorption peaks [33], which helps
to discern the various functional groups and their relative contents
within the coke structure.
The parameters of coke’s microcrystalline structure indicate the size
and ordering degree of coke microcrystals and their influence on coke
reactivity. Researchers have garnered significant insights into its struc­
ture through qualitative and quantitative studies of coke’s microcrys­
talline structure using these characterization methods. This knowledge
is vital for understanding the nuances of coke’s microcrystalline struc­
ture, guiding coke production processes, and optimizing BF ironmaking
techniques.
2.4. Mineral composition
Coke minerals originate from the ash composition of coking coal and
exist primarily as minerals expressed in oxide forms. The type and
content of these minerals not only influence the dissolution loss reaction
of coke, which subsequently affects its thermal properties but also, as
domestic and international studies have indicated, the distribution
mode of these minerals [51]. Although the mineral content in coke is
typically less than 15 % by mass, its distribution within coke can be
categorized into three primary forms: (a) typical discrete distribution,
(b) decentralized distribution, and (c) stomatal inclusions, as illustrated
in Fig. 9. Despite their small proportion, these minerals significantly
impact the interaction between coke and the gas–solid–liquid phases in
the BF. Their roles in the coke dissolution loss reaction can be catego­
rized as increasing the dissolution loss reactivity (positive catalysis),
decreasing it (negative catalysis), or having no effect.
Alkaline elements such as Fe, Ca, and Mg, and alkali metals like K
and Na are highly reactive at elevated temperatures, affecting coke’s
structure and catalyzing its dissolution reaction [52]. Boron, conversely,
exerts a negative catalytic effect on coke solvation and is utilized for
coke passivation. Spraying boron modifiers onto coke has been shown to
reduce coke reactivity and enhance its strength post-reaction [53]; the
addition of TiO2 decreases the proportion of active carbon sites in coke,
leading to reduced reactivity during gasification and increased strength
post-gasification [54]. Aluminosilicates in coke, being stable at high
temperatures, exhibit no catalytic effect [11]. Certain metals and alkali
metals are recognized as effective catalysts for coke gasification,
particularly at temperatures below 900 ◦ C, accelerating the reaction
W. Niu et al.
Fig. 7. Geometry of ideal microcrystals: (a)top view; (b)side view [32].
Fig. 8. Fitted Raman spectra of carbonized samples [50].
rate. However, the presence of SiO2 and Al2O3 in coke reduces its
reactivity[55]. Huang et al.[56] investigated conducted research on the
reactivity of alkali, alkaline earth, and transition metals in semi-coke
gasification, finding that the order of metals in terms of catalytic
Fig. 9. Forms of mineral distribution within coke: (a)typical discrete distribution; (b)decentralized distribution; (c)stomatal inclusions[17].
6
Fuel 366 (2024) 131277
effectiveness was K > Na > Ca > Fe > Mg.
Researchers [57,58] have introduced the concept of the coke reac­
tivity catalytic index, quantifying the role of minerals in catalyzing the
coke dissolution reaction. This index serves as a predictive measure for
coke reactivity. Presently, domestic and international research recog­
nizes the MBI and MCI as catalytic indices. These two indices exhibit a
strong correlation and can be interchangeably applied under specific
conditions. Furthermore, Sakurovs et al. [59] employed the low-
temperature ashing (LTA) method [60,61] to quantitatively charac­
terize the mineral structure in commercial coke. This approach revealed
that the minerals in coke predominantly consist of amorphous alumi­
nosilicates and other amorphous minerals formed due to the removal of
bound water or volatile components.
3. Evolution of coke in the BF
3.1. Evolution of coke properties
Coke properties typically encompass particle size, strength, and
chemical composition. The primary indicators of coke quality are par­
ticle size, mechanical strength (M40, M10), thermal strength (CRI, CSR)
and composition. Performance indices for coke vary depending on the
size of the BF, and the ’Design Code for BF Ironmaking Processes’ stip­
ulates these indices for large BFs, as detailed in Table 3.
W. Niu et al. Fuel 366 (2024) 131277

BFs generally require a coke particle size range of (40 to 50) mm. The quicker charge renewal and, consequently, shorter residence times for
coke particle size must not be significantly larger than the ore size, coke in the lumpy zone. In this zone, coke and ore display a layered
aiming for close similarity between the two. Huge average particle sizes alternating distribution. The charge remains granular, the coke is not
in coke can lead to easy breakage, excessive powder production, softened and melted, and there is no adhesion [64,65].
impaired gas and liquid permeability, and an elevated differential Owing to the lower temperatures, which do not reach the threshold
pressure in the BF. This may necessitate a reduced air volume, leading to for the dissolution reaction, in the lumpy zone, coke undergoes physical
decreased output and fuel ratio [45]. According to contemporary BF changes. It is subjected to friction and compression from the charge,
refining technology standards, the coke powder content less than 5 mm leading to a reduction in coke particle size and the production of pow­
should be below 5 %, and the proportion of (5 to 15) mm coke should be der. In this zone, coke experiences extrusion, mutual collision, and
under 30 % [62]. abrasion; however, the bulk layer’s static pressure is significantly lower
The mechanical strength of coke is a vital metric for assessing its than coke’s compressive strength. As a result, the forces of impact and
ability to support the BF’s framework and ensure smooth operation. abrasion are also diminished. Consequently, there are no significant
Coke’s thermal strength reflects its capacity to resist chemical erosion changes in coke strength reduction, lump size reduction, chemical
and protect the charge skeleton in the BF, serving as a critical index for composition, and deterioration of material column permeability.
evaluating its thermal stability. M10 is commonly used to indicate
coke’s wear resistance, while M40 denotes its fracture resistance [63]; 3.1.2. Cohesive zone
CRI and CSR are employed to characterize coke’s high-temperature re­ The cohesive zone, situated in the shaft and bosh of the BF, has a
action properties, with numerous studies indicating a negative correla­ residence time influenced by the type of BF, productivity, and the soft
tion between them [43]. The chemical composition includes ash, sulfur, melting characteristics of the charge. A higher softening temperature of
volatiles, and phosphorus. Increased ash content can deteriorate the the charge broadens the cohesive zone and extends the residence time of
internal structure of coke, leading to more cracks and facilitating CO2 the coke [66]. The charge begins to soften and deform within this zone,
diffusion into its interior, thus exacerbating thermal performance creating a soft-melting material that bonds the coke particles together.
degradation. High sulfur content can raise the sulfur level in pig iron, This close combination increases friction and extrusion among particles,
reducing its quality or increasing slag alkalinity, adversely affecting BF enhancing both chemical action and mechanical damage. Consequently,
operation indices. Elevated volatile content suggests under-processed the particle size of the coke significantly decreases, and its abrasion
coke. High phosphorus levels in coke can increase the brittleness of resistance is reduced.
pig iron when cold. Recent research indicates that coke deterioration is exacerbated in
The evolution of coke within the BF is a gradual and continuous large-scale BFs and with oxygen-rich blowing. This leads to an increased
process. In the upper part of the furnace, changes are observed in the coke load, heightened coke gasification reactions, destruction of the
coke’s particle size, which decreases; its strength, which worsens; its coke surface structure, and reduced coke particle size [67]; Hydrogen-
reactivity, which increases; and its chemical composition, which alters. rich smelting in the BF weakens the assimilation of the burden and de­
Dissecting BFs has proven to be the most effective method for studying creases the erosion of the coke during smelting reduction. This process
material properties inside the furnace, and this approach has been results in the downward movement and narrowing of the cohesive zone,
employed in dozens of BFs worldwide. Notably, in the 1970 s, three effectively improving the BF’s permeability [68–70].
Japanese BFs underwent dissection. Based on these studies, researchers As the charge descends, the coke endures not only extrusion and
analyzed changes in coke properties along the height inside the BF and friction but also high-temperature thermal stress. This leads to a marked
examined the effects of variations in coke properties and BF operational increase in porosity, thinning of pore walls, and a reduction in the
methods on furnace conditions, as depicted in Fig. 10. In the upper strength of the coke matrix, resulting in chalking that further reduces
section of the BF, where temperatures remain below 1000 ◦ C, the mean coke particle size and impairs the BF’s gas permeability. Coke undergoes
size, drum intensity, reactivity, and CSR of the coke do not exhibit sig­ a vigorous gasification reaction with CO2 produced by ore reduction.
nificant changes. However, in the middle part of the BF, at temperatures This reaction starts at the coke’s surface, causing the surface pores to
ranging from (1000 to 1400) ◦ C, the surface of the coke begins to enlarge and weakening the coke’s strength. The gasification reactivity of
deteriorate, and all indices start to degrade gradually. Above the tuyere coke in the cohesive zone is heightened due to the adhesion of iron-
level, where temperatures increase progressively, the deterioration of containing dust and the chemical composition of zinc and alkali
coke properties becomes markedly pronounced. metals compared to the incoming coke [28]. Alkali cycling in the BF
increases the potassium and sodium mass fraction, which catalytically
3.1.1. Lumpy zone accelerates coke gasification. Post-reaction, the strength of the coke
The lumpy zone between the charge level and the cohesive zone is diminishes sharply, leading to pulverization. This deterioration in coke
characterized by temperatures below 1000 ◦ C. The residence time of integrity compromises the BF’s permeability and seriously threatens its
coke and iron-containing charges in this area is contingent on the smooth operation [71].
furnace capacity and the utilization factor. Larger capacities entail
longer residence times, whereas the higher utilization factors lead to 3.1.3. Dripping zone
The dropping zone, situated below the cohesive zone, is where the
fully melted liquid slag and iron pass through the solid coke layer in
Table 3 droplet form before entering the furnace hearth. In this zone, the coke
Quality regulations of coke with different volumes in code for design of the BF
undergoes scouring by iron and slag and is impacted by high-
ironmaking process.
temperature furnace gases. This interaction leads to the evaporation of
Furnace melting level/m3 1000 2000 3000 4000 5000 some ash components in the coke, further increasing its porosity and
M40/% ≥ 78 ≥ 82 ≥ 84 ≥ 85 ≥ 86 continuing the decline in strength. However, it remains solid due to
M10/% ≤ 7.5 ≤ 7.0 ≤ 6.5 ≤ 6.0 ≤ 6.0 coke’s high melting point (3000 ◦ C) and its unburned state. The evolu­
CSR/% ≥ 58 ≥ 60 ≥ 62 ≥ 64 ≥ 65
tion of coke properties in the cohesive zone has been examined through
CRI/% ≤ 28 ≤ 26 ≤ 25 ≤ 25 ≤ 25
Ash/% ≤ 13 ≤ 13 ≤ 12.5 ≤ 12 ≤ 12
core drilling and sieving. Analyses of coke samples collected from the
St,d /% ≤ 0.85 ≤ 0.85 ≤ 0.7 ≤ 0.6 ≤ 0.6 tuyere reveal that the gasification reaction predominantly occurs on the
Size range/mm 25–75 25–75 25–75 25–75 30–75 surface of the coke. Internally, the coke remains largely undamaged by
Size overtakes upper limit ≤ 10 ≤ 10 ≤ 10 ≤ 10 ≤ 10 the chemical reactions inside the BF, especially when compared to the
Size overtakes lower limit ≤8 ≤8 ≤8 ≤8 ≤8
reducing effects of minerals in the ash.

7
W. Niu et al. Fuel 366 (2024) 131277

Fig. 10. Variation of coke properties in the direction of height in the BF [64].

In the dripping zone, the iron melt undergoes carburization, and the
coke experiences dissolution and particle size reduction. The carburi­
zation mechanism of the iron melt is influenced by various factors,
including hydrogen-rich conditions, which are known to enhance the
permeability of the layers [70]. In the hydrogen-rich upper part and
belly of the BF, there is a significant decrease in temperature, and the
high-temperature zone becomes narrower. Consequently, the direct
reduction of the iron-bearing burden and the solution loss of coke are
reduced, favoring an indirect reduction process [72].

3.1.4. Raceway and deadman

The hot blast emitted from each tuyere in the BF creates a raceway in
front of it, where coke particles and blowing materials interact at high
speed convolutedly. Around this raceway, coke is rapidly consumed due
to the gasification reaction, moving slowly towards the center of the BF Fig. 11. Gas temperature distribution in the center section of the raceway: NG
to form a “deadman.” In the BF raceway, the exothermic combustion and PC injection (top); only PC (bottom) [74].
reactions of coke and blowing fuel cause the raceway adiabatic flame
temperature to surge rapidly, exceeding 2273 K. When employing a
This temperature significantly exceeds the coking temperature. As a
process of blowing pulverized coal in the BF, the temperature at the
result, the ash in the coke begins to decompose. Sulfides and oxides
flame’s center in the tuyere’s raceway can rise substantially, reaching
within the ash react with the coke’s carbon. Concurrently, volatiles
approximately 2373 K [73]. Fig. 11 presents the temperature variation
precipitate from the pore walls under high-temperature conditions,
in the raceway during the numerical simulation of scenarios where
leading to a further weight loss of approximately 4 % to 5 %. This
natural gas and pulverized coal (PC) are mixed, as well as when only
process alters the lattice height and length of the carbonaceous matter,
pulverized coal is blown.
reducing the coke’s reactivity. The coke experiences substantial thermal

8
W. Niu et al.
stresses due to the temperature gradient between its surface and center
under high heat, forming numerous microcracks [75].
CO2 molecules and slag iron penetrate the coke through surface
pores, eroding its surface layer. Subsequently, the coke’s outer layer
undergoes several processes, including slag iron scouring, carburization,
and combustion. This leads to the layer-by-layer powdering and peeling
off the outer layer, progressing the reaction towards the coke’s core.
Consequently, the coke’s size gradually reduces until it completely
disappears.
In the raceway, coke gasification creates a deteriorated layer on the
coke surface. This layer is continuously shed during the rotating friction
process, generating a substantial amount of coke fines. These fines enter
the birdnest and deadman, impairing the gas and liquid permeability of
the BF, thereby affecting the BF’s stability [76].
Experimental results [77–79] indicate that the deadman is situated
in the central lower part of the BF, having a conical shape and a rela­
tively dense structure. The edge of the deadman represents the coke-
consuming area, where the internal coke moves towards the edge to
renew its state. The carbon is gradually eroded by the surrounding iron
melt and eventually disappears, with the ash integrating into the slag.
3.1.5. Hearth
In the lower central region of the BF, coke is less influenced by
combustion and raceway activity, resulting in larger coke sizes in this
area of the hearth. As the coke gradually descends to the furnace bottom,
its size decreases correspondingly—the closer to the bottom, the smaller
the coke size. Tuyere sampling and BF dissection studies have reported a
reduction of at least 50 % in the size of feed coke by the time it reaches
the tuyere level [80,81]. Studies at the tuyere level have revealed that
little or no slag infiltrates the macroscopic pores of the coke, suggesting
that the slag does not penetrate the internal structure of the coke.
Consequently, there is no reaction between the coke ash and slag,
leaving most of the coke intact at this level [28].
The extended contact duration between coke and slag at the slag
liquid level exceeds that at the tuyere level. This prolonged interaction
allows slag ample time to permeate the coke pores fully. Significant
reactions occur between the coke ash and slag, yet the coke’s structure
remains unchanged [82]. In contrast, at the iron melt level, the iron melt
erodes the coke, dissolving it. The irregular contact surface between iron
and coke evidences a reaction attributed to the robust impact of the iron
melt on the coke structure. This interaction ultimately leads to the
destruction and complete dissolution of coke [63]. Coke samples from
various depths and heights are commonly extracted through drilling to
analyze the evolution of coke properties in hearths. These morpholog­
ical changes are illustrated in Fig. 12. The study’s findings indicate that
the coke particle size diminishes with increasing sampling depth. This
size reduction is inversely correlated with the degree of graphitization
and the adsorption amount of alkali metals [83,84].
Coke graphitization facilitates the production of fine coke particles.
It has been observed that the finest coke particles exhibit the highest
degree of graphitization and contain the largest proportion of graphite
Fig. 12. Morphology of coke at different depths in core samples [83].
9
Fuel 366 (2024) 131277
crystals. As the sampling position progresses, the slag and iron contents
in the samples initially increase before stabilizing at a relatively constant
level [85,86]. Similarly, the particle size of coke diminishes, then levels
off as the location moves closer to the center. The alkali content
significantly increases with greater distance from the tuyere entrance.
This suggests that alkali vapors predominantly circulate and accumulate
in the central part of the BF, with the high-temperature conditions at the
tuyere being a primary factor in coke graphitization [46,87].
Meng et al. [88] used the drilling method to collect four sets of
samples at different hearth heights, as depicted in Fig. 13. Their findings
indicate an increase in coke size with greater distance from the sidewall.
Conversely, the closer the proximity to the hearth’s bottom, the smaller
the coke size. Enriching S and K elements at the interface contributes to
coke cracking and impedes the carburization reaction. Additionally, the
presence of slag and alkali metals in the coke’s pores leads to the
volumetric expansion of the coke.
3.2. Multiphase reactions of coke
3.2.1. Gas–solid reaction
The high-speed hot blast in front of the tuyere forms a cylindrical jet
space comparable in diameter to the tuyere, known as the combustion
zone. In this zone, coke is burned and gasified by the incoming hot blast,
leading to gasification and dissolution reactions that produce reducing
gases such as CO and H2. The ascending hot gas stream transfers heat to
the raw materials and engages in a reduction reaction with iron ore,
generating a significant amount of CO2. This process results in a pro­
nounced gasification reaction with coke [67]. Thus, in the ironmaking
process, coke participates in gas–solid reactions, primarily the gasifi­
cation reaction, the indirect reduction reaction of iron oxides, and the
combustion reaction.
(1) Gasification reaction
The gasification reaction of coke is a heterogeneous gas–solid reac­
tion, predominantly a chemical process occurring via the continuous
contact of CO2 produced by the indirect reduction of iron oxides, with
activation sites on the surface of solid coke. BF researchers often
describe carbon consumption in terms of a carbon dissolution reaction
[89]. Boudouard established the stoichiometry and reversibility of this
reaction in 1899 [90]. The reaction equation is as follows:
C + CO2 = 2COΔr Hmθ (298.15 K) = + 172.7 kJ⋅mol− 1 . (4)
The experimental methods for investigating the behavior and
mechanism of coke gasification reactions in BF encompass techniques
such as fixed beds, thermogravimetry, micro fluidized bed, and gas
analyzer combinations. The fixed-bed approach effectively simulates the
interaction of reacting gases traversing through the coke layer and the
interplay between gas and solid phases within the BF. Notably, the CRI
and CSR tests employ fixed-bed reactors. The reactivity and kinetic
characterization of coke gasification are primarily conducted using
thermogravimetry and micro-fluidized beds, enabling precise analysis of
the impact of diverse experimental parameters on the coke gasification
reaction behavior[32].
Coke dissolution is a gas–solid reaction, depicted in Fig. 14, and
predominantly proceeds through the following stages [91]: ① Diffusion
of CO2 and CO through the stagnant boundary layer to the coke’s outer
surface; ② Transfer of CO2 to the surface of reacting particles via the
outer layer, coupled with the movement of the carbon surface desorp­
tion product, CO, from reactive sites to the particle surface through
pores; ③Adsorption of the reactant CO2 onto the active sites on the
carbon surface, ensuing in a chemical reaction to produce CO. This re­
action encompasses three distinct parts: chemical control, transition,
and diffusion control [92] zones. Transition temperatures for these
processes vary across different coke types, with the three stages not
W. Niu et al. Fuel 366 (2024) 131277

Fig. 13. Schematic diagram of the hearth drilling of BF sampling positions [88].

Table 4
Thermodynamic data for the indirect reduction reaction of iron oxides.
Chemical reaction ΔH(kJ/mol) ΔS(J/Kmol) ΔG(kJ/mol) T
(K)

Hydrogen reduction
3Fe2O3 þ H2 ¼ 2Fe3O4 þ –6 +89 –33 298
H2O
Fe3O4 þ H2 ¼ 3FeO þ H2O +61 +95 –22 873
FeO þ H2 ¼ Fe þ H2O +31 +24 +10 873
Carbon monoxide
reduction
3Fe2O3 þ CO ¼ 2Fe3O4 þ –47 +47 –61 298
CO2
Fe3O4 þ 4CO ¼ 3Fe þ +19 +53 –26 873
4CO2
FeO þ CO ¼ Fe þ CO2 –12 –18 +4 873
Fe3O4 þ 6CO ¼ Fe3C þ –161 –159 –114 298
5CO2
Fig. 14. Schematic diagram of the coke dissolution reaction process [91].

(3) Combustion reaction

being sharply demarcated. Studies indicate that at temperatures below
900 ℃, the reaction is predominantly governed by chemical processes.
In the range of (900 to 1200) ℃, it enters a transition zone where control
shifts from chemical to diffusion processes. At temperatures between
(1200 to 1300) ℃, diffusion predominantly controls the reaction, and
above 1300 ℃, the reaction is entirely governed by the diffusion
process.
(2) Indirect reduction of iron oxides
Thermodynamic analysis of iron oxide reduction reveals that CO and
H2-driven reduction of hematite (Fe2O3) by CO and H2 influences the
microstructural evolution of iron ore. Table 4 details the thermodynamic
data for this reduction reaction. This process involves multiple steps,
including the formation of various structural modifications and complex
compositions in intermediate oxides, such as the transformation
sequence from hematite (Fe2O3) ⟶ to magnetite (Fe3O4) ⟶ floater
(Fex O) ⟶ and finally to iron (Fe). Typically, these reactions occur
simultaneously [93]. The reduction dynamics of iron oxides are
temperature-dependent, impacting the formation of Fex O [94]. Kinetic
studies have demonstrated that the reduction of Fe2O3 to metallic iron
follows either a two-step mechanism below 570 ◦ C or a three-step
(>570 ◦ C) mechanism. Initially, Fe2O3 is converted to Fe3O4, which
then forms Fex O at temperatures above 570 ◦ C [95]. Below 570 ◦ C,
magnetite directly to Fe [96], as Fex O is unstable below this threshold.
In the combustion zone, located in front of the tuyere, carbon reacts
with oxygen and undergoes gasification. This zone can be characterized
as a packed bed consisting of numerous coke particles and exhibiting a
certain degree of porosity. Here, airflow mobilizes coke and engages in
high-temperature reactions with oxygen. While unburned PC combus­
tion occurs in this zone, coke remains the primary combustible material.
The combustion of coke principally yields CO, a vital component in BF
ironmaking, providing both heat and a reducing agent for BF [88,97].
The combustion zone serves as the origin of the ascending hot gas stream
and facilitates a continuous reduction in charge, a result of the space
created by coke gasification. Coke oxidation within this zone is pri­
marily categorized into two processes [98]:
(i) Near the raceway front, adjacent to the tuyere, carbon undergoes
a complete combustion reaction with oxygen, facilitated by an
ample supply of O2.
C + O2 = CO2 Δr Hθm (298.15 K) = − 393.5 kJ⋅mol− 1
(5)
(ii) At the back end of the raceway near the deadman, a carbon
dissolution loss reaction occurs because of insufficient oxygen
and excess coke.
C + CO2 = 2CO Δr Hθm (298.15 K) = + 157.8 kJ⋅mol− 1
(6)

10
W. Niu et al.
The oxidation and reduction zones are the two distinct areas within
the combustion zone. The disappearance of CO₂ serves as a demarcation
for the boundary of the combustion zone. In practical production sce­
narios, pinpointing the exact point of CO2’s complete disappearance is
challenging; thus, the CO2 content is often reduced to as low as 1 % at
the boundary of the combustion zone. The reaction process unfolds in
the following manner: oxygen molecules initially adhere to the carbon
surface. As the temperature rises, carbon atoms and oxygen adsorption
intensifies, transitioning from physical to chemical adsorption. This
change weakens the bond between oxygen atoms, causing the oxygen
bond to elongate and ultimately break. Consequently, carbon atoms on
the surface form complexes. Due to the influence of surrounding airflow
and high temperatures, these surface complexes decompose into CO and
CO2. This phenomenon is referred to as the primary reaction of com­
bustion or the main reaction. The reaction formulas are as follows:
<1300 ◦ C 4C + 2O2 = (4C) ⋅ (2O2) (7)
(4C) ⋅ (2O2) + O2 = 2CO + 2CO2 (8)
>1600 ◦ C 3C + 2O2 = (3C) ⋅ (2O2) (9)
(3C) ⋅ (2O2) = 2CO + CO2 (10)
At temperatures ranging from 1300 ◦ C to 1600 ◦ C, two reactions
occur concurrently, with “complex decomposition” as the prevalent
control mechanism. CO and CO2 produced in the primary reaction
persist in reacting either with oxygen or carbon in what constitutes the
secondary or side reactions of the combustion process.
2CO + O2 = 2CO2 (11)
C + CO2 = 2CO (12)
Referring to the CO-CO2-C equilibrium system illustrated in the gas-
component change diagram (Fig. 15), it can be inferred that the ther­
modynamic and kinetic conditions of the coke in the tuyere area are
conducive to its complete reaction within this region. This reaction ul­
timately produces CO, which serves two critical roles: providing energy
and generating reducing gas for the process.
3.2.2. Solid–solid reactions
(1) Direct reduction of iron oxides
Fig. 15. Variation of CO and CO2 components in CO-CO2-C system under
different temperature and pressure conditions [16].
11
Fuel 366 (2024) 131277
Pavlov believed that indirect reactions accomplished all of the re­
action Fe2O3⟶Fe3O4⟶FeO in the BF and that the reduction of iron
from FeO depended partly on the indirect reduction of CO and H2, and
the rest on the direct reduction of carbon. In his view, the reduction of
iron from FeO partially relies on the indirect reduction by CO and H2,
with the remainder attributable to the direct reduction by carbon. He
quantified the directness of iron reduction as the ratio of iron produced
through the direct reduction of FeO to the total iron produced by all
reduction processes. In cases where solid carbon is the reducing agent
and the resultant product is CO, the process is termed “direct reduction.”
This reaction, characterized by strong heat absorption, involves the
direct consumption of solid carbon. However, the contact conditions
between the two solid phases are typically inadequate to sustain a
perceptible reaction rate. In reality, the direct reduction reaction is
achieved through the combined effects of carbon dissolution and the
water–gas shift reaction:
Indirect reduction FeO + C = Fe + CO2 ΔHθ298 = − 13190 J⋅mol− 1
(13)
Carbon Dissolution Reaction C + CO2 = 2CO ΔHθ298 = − 165390
J⋅mol− 1 (14)
Indirect reduction FeO + H2 = Fe + H2O ΔHθ298 = − 13190 J⋅mol − 1
(15)
Water gas reaction H2O + C = H2 + CO ΔHθ298 = − 124190 J⋅mol− 1
(16)
Direct restore FeO + C = Fe + CO ΔHθ298 = − 152200 J⋅mol− 1
(17)
(2) Reduction of silicon oxides
Since the 1970 s, perspectives on the reduction process of SiO2 in BF
have evolved significantly. It is now widely accepted that the silicon in
BF iron melts is derived from SiO2 in liquid slag and gaseous SiO [89]. In
the high-temperature region of the BF, conditions are conducive to
forming “SiO.” This gaseous “SiO” is primarily produced through two
key reactions.
(SiO2)slag + Ccoke = {SiO} + {CO} (18)
(SiO2)ash + Ccoke = {SiO} + {CO} (19)
Due to the higher activity of SiO2 in coke ash than in slag [99,100], it
is commonly acknowledged that SiO gas mainly results from reduced
SiO2 in coke ash. As illustrated in Eq. (18), this process is more likely to
occur than the one described in Eq. (19), leading to a greater production
of SiO gas. The SiO thus produced is ultimately reduced by solid coke, as
per the following reaction equation:
(SiO) + Ccoke = [Si] + {CO} (20)
It has been observed that the silicon content in iron droplets pre­
dominantly originates from the ash in coke [99]. Additionally, dissec­
tions of BFs have revealed that temperature significantly influences the
reduction of SiO2 [100]. The variation in SiO2 content in coke within the
BF as a function of temperature increase is depicted in Fig. 16. Notably, a
marked decrease in SiO2 content in coke begins from the soft molten
droplet fallout zone, coinciding with an increase in silicon content in the
iron droplets [101]. Therefore, controlling the SiO2 content in coke and
adjusting the operating temperature of the BF are vital strategies for
managing the silicon content in the iron metal.
3.2.3. Solid–liquid reaction
(1) Carburization reaction
Incorporating carbon into molten iron, known as carburization, is a
critical process in ironmaking. During the refining process, the carbon
content of coke is approximately 85 % to 90 %, influenced by the type of
coking coal used. Apart from carbon, coke contains about 10 % ash and a
W. Niu et al.
Fig. 16. Variation of SiO2 content in coke with increasing temperature in the
BF [89].
minor proportion of volatile substances. Notably, the carburization re­
action dissolves around 7 % to 10 % of this carbon into the pig iron. In
the lower region of the BF hearth, coke is the sole solid material. As the
iron descends from the dripping zone, it encounters coke and undergoes
the contact carburization reaction; this occurs at the base of the ’dead
man’ in the hearth and eventually leads to the dissolution of carbon into
the molten iron [89].
The carburization process comprises three primary stages, as illus­
trated in Fig. 17 [102,103]: ① Carbon atoms detach from the carbo­
naceous material matrix and form a reactive interfacial layer on the
surface of the carburizer. ② These carbon atoms then diffuse into the
molten iron through the interfacial layer. ③ Finally, the carbon atoms
dissolve in the liquid iron. Studies on the carburization process of
graphite have led to the formulation of a specific rate expression for its
carburization, which can be articulated as follows:
dCt A the iron melt. Ore, not fully reduced, falls into the high-temperature
= k (Cs − Ct ) (21)
dt V
where k denotes the first dissolution reaction rate constant (m/s); t is the
reaction time (s); A is the reaction contact area (m2); V represents the
volume of liquid ferric iron (m3); Cs represents the saturation concen­
tration of carbon in the ferric iron (wt.%); and Ct represents the
Fig. 17. Schematic diagram of the carburizing reaction process [102].
12
Fuel 366 (2024) 131277
concentration of carbon at the moment of the reaction time (wt.%).
Notably, the saturation concentration of carbon in the iron melt is pre­
dominantly influenced by the temperature and the presence of alloying
elements within the iron melt [104–106]:
CS = 1.3 − 0.00257T(◦ C) − 0.31 Si − 0.33 P − 0.45 S + 0.28 Mn (22)
The primary dissolution reaction rate was determined by integrating
Eq. (21), assuming that A, V, and K are independent variables, which can
be obtained as
∫ Ct ∫
dCt A t
=k dt (23)
C0 Cs − Ct V 0
Cs − Ct A
ln = − k t (24)
Cs − C0 V
where C denotes the initial carbon content of the iron melt.
The Fe-C phase diagram reveals that even trace amounts of carbon
significantly impact the melting point of iron. Enhancing the carburi­
zation rate of coke is crucial for facilitating the melting and reduction of
iron ore. The carburizing capacity of coke influences the saturation
degree of the iron melt in the furnace hearth and serves as an indicator of
the cleanliness of the deadman [107]. Theoretical. Both theoretical
calculations and experimental findings indicate that the saturated sol­
ubility of carbon in the iron melt is approximately 5.0 %. In practice, the
carbon content of the iron melt in the furnace hearth typically reaches
about 4.5 % after undergoing a series of complex carburization
reactions.
Understanding the carburization behavior of coke in iron melts is
vital for maintaining stable BF operations and making informed ad­
justments to the charge structure. Furthermore, this knowledge signifi­
cantly reduces fuel costs and is integral to the GHG emission reduction
strategies. By optimizing the carburization process, ironmaking can be
more efficient and environmentally sustainable [108].
(2) Direct reduction of iron oxides
In another form of direct FeO reduction, the FeO-containing liquid
slag directly contacts solid coke or reacts with the saturated carbon in
zone, softens, melts, and results in an initial slag with high FeO con­
tent, which then flows downward through the coke voids. Due to
effective contact between the liquid slag and coke surface and the lesser
diffusion resistance compared to gas diffusion in zigzagging micropo­
rous spaces, coupled with high temperatures, the reaction rate constant
is considerably large. Consequently, this type of reaction proceeds
rapidly. By the end of the process, the slag’s FeO content is reduced to
less than 0.5 %, and the total iron recovery exceeds 99.7 %.
Thermodynamic studies indicate that the direct reduction reaction
yields a single gas-phase product, CO, as per the following equation:
(FeO) + C = Fe + CO (25)
The equilibrium constant of the reaction can be expressed as:
PCO Ptotal ⋅φ(CO)
K= = (26)
α(FeO) α(FeO)
where K is a function of both temperature, total system pressure (Ptotal ),
and the activity of FeO in the slag.
Kinetic testing of this reduction process has shown that if the
composition of the primary slag is ω(FeO) = 70 %, ω(CaO) =
15 %, ω(SiO2 ) = 15 %, and this slag flows through a red-hot coke
layer with a (20 to 25) mm height. The FeO in the primary slag can be
completely reduced within 3 min when flowing through the coke layer
at system temperatures of 1400 ◦ C and 1500 ◦ C.
W. Niu et al.
3.3. Influence of alkali metals and zinc on coke properties
3.3.1. Effect of alkali metals on coke properties
Alkali metals, specifically K and Na, are introduced into the BF
through the ore. Due to their chemical stability, these metals do not
begin to reduce below the cohesive zone. A significant amount of alkali
metals cannot be expelled from the BF; instead, they accumulate cycli­
cally in various forms throughout different regions of the BF, as depicted
in Fig. 18. In the different areas of the BF, alkali metals exist in distinct
forms: silicates are predominant in the hearth; elemental vapor is the
main form in the furnace shaft and bosh, as well as the lower part of the
hearth; and carbonates are prevalent in the upper and middle parts of
the shaft [109]. K and Na in the process of rising at different. They can
interact with other substances as temperatures increase, forming K2O,
Na2O, or even further reactions that produce silicates and carbonates
[71]. This indicates that alkali metal carbonates are primarily formed
from alkali vapors that rise with the gas flow and circulate in the upper
part of the BF.
The presence of alkali metals in the BF influences the reaction rates
of its components. Specifically, the reaction rate of the isotropic
component diminishes, while that of the anisotropic component in­
creases. This could be due to alkali metals embedding within the
anisotropic structure, forming a looser structure with the carbon atoms
of the carbon layer, thereby facilitating the reaction of carbon dioxide
with it [97]. The reactivity of coke notably escalates when the gas–solid
mass ratio of K vapor to coke exceeds 3 %. At 1100 ◦ C, the adsorption,
degradation, and catalytic gasification reactions of K vapor in coke are
significantly more pronounced than those of sodium [109]. The struc­
ture of coke is compromised when the proportion of alkali metals rea­
ches 3 %; notably, when the mass ratio of K to Na is 3:7, the CRI peaks,
and the CSR hits its lowest [111].
Circulating enriched alkali metals in the BF act as catalysts in the
coke dissolution reaction. They increase the rate of this reaction,
accelerating coke gasification. Consequently, coke strength significantly
declines after reacting, leading to increased coke pulverization and
decreased permeability in the BF. Alkali metal-catalyzed coke dissolu­
tion mechanisms include the oxygen transfer mechanism, the theory of
interlayer compounds, and the electrochemical mechanism. Mckee et al.
[112] have proposed the oxygen transfer mechanism based on graphite-
CO2 reaction experiments. This mechanism suggests that the catalytic
action of alkali metals primarily involves their oxidation–reduction
cycle, in which both metals and metal salts facilitate oxygen transfer
through their oxides and peroxides, allowing reactive oxygen atoms to
Fig. 18. Schematic diagram of alkali metal circulation in a BF [110].
13
Fuel 366 (2024) 131277
engage with carbon. The theory of interlayer compounds posits that
graphitic interlayer compounds form during reactions between alkali
metal carbonates and CO2. The electrochemical mechanism indicates
that metal ions alter their electronic structure upon contact with the
carbon surface and act as electron donors, providing electrons to the
carbon surface. This process speeds up specific reactions, thus enhancing
the overall reaction rate. “Electron transfer” bears close resemblance to
the oxygen transfer mechanism. In the absence of electron transfer
during the catalytic process of gasification reactions, O2 is required for
the transfer, similar to the oxygen transfer mechanism [113].
3.3.2. Effect of zinc on coke properties
The primary source of Zn in BF is ore, with a small portion origi­
nating from coke [114,115]. It enters the charge pores through Zn va­
pors oxidized to gaseous oxides in the gas stream to form fine oxide
particles or condenses on the surface of the charge to form a thin film of
metal or oxide of Zn that accumulates in the furnace. The practice has
shown that the Zn content present in the charge is higher in the range of
(1000 to 1200) ◦ C in the BF, so Zn has a significant effect on the gasi­
fication reaction of coke; the larger the Zn content adsorbed by coke, the
worse its thermal state performance.
Experimental studies showed that the best adsorption effect of Zn
was achieved at 1000 ◦ C; Zn played a positive catalytic role in the
dissolution reaction of coke, and with the increase of Zn adsorption, the
reactivity of coke was subsequently enhanced [116]. ZnO and Zn have
no direct catalytic effect on coke, and only under a CO2 atmosphere do
both of them catalyze the coke solvation reaction, leading to poor per­
formance of coke in the thermal state [117]. The coke adsorption of Zn
produced more cracks on the substrate, which accelerated the coke
gasification reaction, and the Zn content at the edges of the cracks
increased [118].
3.4. Graphitization of coke in the BF
Coke, a porous carbonaceous material, begins to undergo significant
changes upon entering the cohesive zone of the BF. As it descends, coke
is exposed to high temperatures, causing its microcrystalline structure to
grow gradually. This process eliminates aberrations and defects in the
microcrystals, leading to a transformation into graphitized carbon. The
physical phase transformation of ash minerals within the coke and melt
migration further facilitates this graphitization. The direct interaction
between coke and the liquid slag iron in the BF’s lower region can also
influence graphitization [119]. It is crucial to understand the factors that
W. Niu et al.
affect coke graphitization in the BF and the implications of high
graphitization on its structure and strength. This knowledge contributes
to the BF’s smooth operation and supports the goals of green and low-
carbon production.
3.4.1. Influencing factors of graphitization
Temperature is a pivotal factor influencing the degree of graphiti­
zation in coke [48,120]. A plethora of experimental data indicates that a
gradual heating regime enhances the final graphitization quality; higher
temperatures improve graphitization and reduce the time needed to
achieve equilibrium. As a result, coke graphitization escalates markedly,
transitioning its structure towards an orderly, regular graphite form
[120]. With every 100 ◦ C rise in temperature, the graphitization degree
deepens approximately 1.8-fold, the d002 value shows a reduction of
about 2 %, the La value sees an approximate 3 % increase, and the Lc
value escalates by around 15 % [121]. The temperature-dependent
graphitization of various coke types is depicted in Fig. 19. Notably,
the Lc value escalates substantially between 1500 and 1700 ◦ C, under­
scoring the profound impact of temperature on graphitization across the
entire coke mass.
Certain substances in coke ash can act as catalysts for graphitization,
enabling coke to graphitize at lower temperatures or to achieve higher
graphitization at the same temperature. The ash of coke, which is the
solid residue after ashing, typically contains various oxides and has a
mass fraction generally less than 15 %. As Fig. 20(a) illustrates, the stack
height (Lc) of coke microcrystals incrementally increases with the heat
treatment temperature. This increase becomes more pronounced at
temperatures ranging from (1600 to 1800) ◦ C. Additionally, prolonging
the heat treatment time at constant temperatures enhances the final
graphitization degree of coke [122]. As shown in Fig. 20(b), the
graphitization degree of coke rapidly escalates between 1200 and
1300 ◦ C [120]. The XRD patterns reveal that coke’s ash content trans­
forms at temperatures above 1573 K, evidenced by the gradual dimin­
ishing of quartz peaks [123].
Numerous scholars[85,123–126] have indicated that slag iron cata­
lyzes coke’s graphitization with a mechanism akin to graphite forma­
tion. The catalytic component in slag iron utilizes the free energy
disparity between ordered and disordered carbon arrangements to
dissolve carbon and subsequently crystallize it through deposition. In
the BF’s lower cohesive zone, liquid slag iron forms and, while
descending, traverses the dripping zone and combustion belt before
finally reaching the furnace hearth. Throughout this journey, it remains
Fig. 19. Variation of graphitization with temperature for different coke after
heat treatment [82].
14
Fuel 366 (2024) 131277
in constant contact with coke in various forms, undergoing diverse re­
actions [85]. XRD and Raman spectroscopy reveal that both iron and
slag catalyze coke graphitization, with iron’s effect being more pro­
nounced. Metallic iron catalyzes the transformation of SP3 to SP2 carbon
bonds in coke, promoting graphitization. Thermogravimetric analysis
indicates that coke analogs containing metallic iron react more swiftly
with CO2.
3.4.2. Effect of graphitization on coke properties
The graphitization of coke significantly impacts its particle size, pore
structure, strength, and microcrystalline architecture. Gornostayev et al.
[127], Gupta et al. [83] and Li et al. [86] have shown that coke’s
graphitization in high-temperature regions commences at the surface,
leading to the formation of coke fines. As graphitization intensifies, the
spacing (d002) between the levels of the coke’s microcrystalline structure
diminishes, augmenting the interatomic forces within the same layer
and stabilizing the crystal structure [128,129]. This stabilization man­
ifests as a decrease in the CRI and an elevation in CSR. Additionally, the
reduced reactivity of graphitized coke and its heightened post-reaction
strength suggest enhanced structural stability during graphitization
[121]. The smaller the particle size of tuyere coke, the higher the degree
of graphitization. Therefore, the graphitization of coke leads to the
flaking of its surface and the formation of fine powdery particles, so the
pulverization rate is elevated [85,86]. Moreover, the coke’s surface
pores undergo changes: large pores shrink to small or micropores, the
pore walls become thinner, and numerous pits form. These alterations
could result from the transformation of isotropic substances to aniso­
tropic ones within the coke during heat treatment, coupled with an in­
crease in the coarse-grained mosaic structure on the surface [121].
4. Coke quality requirements and evaluation for modernized BF
Addressing the quality of coke entails defining and measuring its
properties to meet the requirements of the BF process. This involves
setting production targets for coke based on its property determination.
The preceding analysis consolidates the role of coke in the BF, its
degradation mechanisms, and the requisite quality standards, as out­
lined in Table 5.
In various regions of the BF, coke encounters diverse conditions such
as pressure, abrasion, gasification, exposure to alkali metals, combus­
tion, graphitization, and carburization. Consequently, coke must serve
as a structural support, facilitating gas and liquid permeability. Specific
quality indices are essential to mitigate coke degradation and ensure
optimal BF performance. From the lumpy zone to the hearth, coke
should possess strong crushing strength, high abrasion resistance, and
robustness against varying atmospheric conditions, alkali metals, and
other chemical assaults. Additionally, it should maintain effective
carburization with the iron melt.
Highly reactive coke in BFs is advocated to lower the thermal reserve
zone temperature, thereby enhancing the gas utilization factor. This
suggests that the ore properties possess potent reducing capabilities
[130]. Increasing coke’s reactivity can improve the permeability of the
stock column and the high-temperature efficacy of the iron-bearing
charge, reducing the reductant rate and consumption [131]. There­
fore, employing highly reactive coke is recommended for achieving
efficient, low-reductant rate BF operations [132].
Coke performance indexes include microscopic parameters and
macroscopic performance, the former is fundamental to the evolution of
the latter. Microscopic parameters determines macroscopic perfor­
mance, and macroscopic performance is the external expression of
microscopic parameters. Through the discussion in the previous chap­
ters, taking the coke macroscopic performance as the target and coke
microscopic parameters as the variables, the main relevant laws are
obtained, as shown in Fig. 21. In order to pursue high strength and low
fine rate, it is necessary to ensure firstly that the coke matrix structure is
strong enough, secondly that the coke pore structure is uniformly
W. Niu et al. Fuel 366 (2024) 131277

Fig. 20. Variation of graphitization degree of coke under different heat treatment conditions [120,122].

influenced by its structure and composition. In BF production, the crit­

Table 5
ical factors impacting coke’s cold strength (M40 and M10) and hot
Coke function, degradation mechanism and quality requirements.
strength (CRI and CSR) include its pore structure, matrix structure,
Position Functions Degradation Quality microcrystalline structure, and mineral composition. Metallurgical
mechanisms requirements
coke, or graphitized carbon, demonstrates decreasing reactivity with
Lumpy Air permeability Alkali deposits, Size, stability, increased Lc and La values. Coke, characterized by highly rounded pores
zone mechanical stress, mechanical strength, and substantial pore wall thickness, exhibits greater strength. The pore
abrasion abrasion resistance
Cohesive Strut, air Gasification reaction, Low carbon dioxide
structure has been analyzed using methods such as drainage, micro­
zone permeability, abrasion reaction, high CRS scopic image analysis, mercury pressure, and gas physisorption,
slag-iron revealing that cokes with a higher proportion of anisotropic structures
discharge tend to be less reactive. The microcrystalline structure of coke has been
Dripping Strut, air Gasification reaction, Size distribution,
characterized through XRD, TEM, HRTEM, XPS, Raman, and FTIR; the
zone permeability, abrasion, alkali metal low carbon dioxide
slag-iron erosion, ash reactions reaction, abrasion mineral composition and distribution within the coke and the detection
discharge resistance methods were also described.
Raceway Production of CO Combustion, Resistant to thermal The evolution of coke within a BF is a progressive and continuous
graphitization, shock, mechanical process, experiencing varying degrees of degradation in different zones.
stress, abrasion stress and abrasion
Hearth Strut, slag-iron Graphitization, Mechanical and
In the BF’s upper region, where temperatures are lower, coke deterio­
discharge, mechanical stress, abrasion strength, ration is mainly physical, attributed to friction, extrusion, and charge
carburization carburization carbon dissolution expansion. Conversely, rapid degradation occurs in the lower high-
temperature zone due to coke’s involvement in multiphase reactions.
As the charge descends, coke reaches the hearth, eventually dissipating
distributed, and lastly that it has appropriate reactivity.
under the influence of slag iron and thermal stress. The cyclical
enrichment of alkali metals and zinc in the BF significantly impacts
5. Conclusions and outlook
coke’s performance. Alkali metals can lower the activation energy
needed for gasification reactions, disrupt the carbon matrix structure,
This paper comprehensively reviews the structure and composition
weaken the carbon boundary connections in graphite microcrystals, and
of coke, its various characterization methods, and summarizes coke’s
catalyze coke reactions. Increased adsorbed Zn content results in
behavior in the BF. The metallurgical properties of coke are primarily
heightened coke reactivity, reduced post-reaction strength, and an
amplified pulverization rate. The increasing heating temperature grad­
ually enhances graphitization as coke moves from top to bottom in the
furnace. This results in a decrease in CRI, an increase in CSR, and a
significant reduction in both gas and liquid permeabilities within the
furnace.
Since the onset of the 21st century, the advancement of large-scale
and intelligent BF has significantly propelled ironmaking technology.
However, challenges such as energy supply constraints and environ­
mental protection requirements have imposed greater developmental
hurdles on the BF ironmaking process, necessitating higher quality
standards for coke. The emergence of new ironmaking technologies, like
hydrogen-rich and oxygen-rich BFs, has led to a notable decrease in the
coke ratio used in BFs, edging closer to the theoretical limit of coke
usage.
Researchers have explored alternatives to coke in BFs in pursuit of
Fig. 21. Relationship between coke microscopic parameters and macro­
green and low-carbon development. Despite these efforts, coke’s role as
scopic properties.

15
W. Niu et al.
a structural support for the material column remains indispensable. It
ensures the smooth flow of BF gases and effective penetration of liquid
slag and iron melt, a function yet to be replicated by other materials.
Research on coke must evolve to foster cleaner production in the steel
industry. New techniques should be developed to elucidate the coke
microstructure, building upon traditional kinetic methods for studying
its macroscopic properties. This approach will enable a comprehensive
systematization of findings related to coke structure and its behavior
inside the furnace.
Furthermore, the introduction of a coke-quality evaluation system is
imperative. This system should define quality evaluation indices for
various types of coke tailored to modernized BF ironmaking processes.
These indices would regulate coke allocation, ensuring that the most
suitable types of coke are used in specific processes. This strategic
approach will provide vital guidance for achieving efficient and low-
consumption BF ironmaking, aligning with the industry’s broader sus­
tainability goals.
CRediT authorship contribution statement
Wenquan Niu: Writing – original draft, Methodology, Investigation,
Formal analysis, Conceptualization. Yan Li: Writing – review & editing,
Investigation. Qiang Li: Resources, Methodology. Jingsong Wang:
Supervision, Resources, Formal analysis, Conceptualization. Guang
Wang: Supervision, Investigation. Haibin Zuo: Methodology, Formal
analysis. Xuefeng She: Methodology, Investigation. Qingguo Xue:
Funding acquisition.
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.
Data availability
Data will be made available on request.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (grant number U1960205), China Baowu Low Carbon Metal­
lurgy Innovation Foundation (grant number BWLCF202101 and
BWLCF202104) and China Minmetals Science and Technology Special
Plan Foudation (grant number 2020ZXA01).
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