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Graphite crystals in blast furnace coke

Stanislav S. Gornostayev
*
, Jouko J. Harkki
Laboratory of Process Metallurgy, University of Oulu, P.O. Box 4300, 90014 Oulu, Finland
Received 15 November 2006; accepted 26 February 2007
Available online 4 March 2007
Abstract
Graphite was found at several spots on the porous surface of a sample of blast furnace (BF) coke in association with droplets of Si-
bearing iron and other inorganic compounds. It occurred in foliated intergrowths and rose-like aggregates of euhedral to subhedral crys-
tals of various size (10 lm0.7 mm) and morphologies, the generic forms that can be seen in the crystals being basal pinacoid, hexagonal
prism and hexagonal dipyramid. The largest crystals have a ake-like habit and are represented by a combination of a basal pinacoid and
a hexagonal prism. Graphite crystals that have an ideal hexagonal prism in their cross-section are rarer than distorted forms. There are
twins on the dypiramidal composition planes and twins produced by rotation on [0001]. The major deformations in the crystals, i.e.
detaching, bending and rolling of (0001) planes, may be referred to exfoliation phenomena caused by potassium and sodium from cir-
culating BF gases and enforced by the BF gas ows. The formation of graphite crystals on a surface of BF coke, especially those of ake-
like morphology with an undeveloped hexagonal prism, possibly decreases its reactivity and can be accompanied by the generation of
nes. The graphitic coating on a surface of BF coke can act as a lubricant to facilitate coke pieces sliding over each other thus aecting
the mechanical stability of the coke cone in a BF.
2007 Elsevier Ltd. All rights reserved.
1. Introduction
Coke is a key material for blast furnace (BF) operation,
acting as (1) a fuel; (2) a reductant, to generate reducing
gases, including CO; (3) a carburisation agent for the hot
metal, to give it the required properties, and (4) a structural
support to provide permeability for liquid phase drainage
and upward ow of the blast furnace gases [1]. It is charged
into the BF along with the iron ores and various uxes.
Metallurgical coke is made from a mix of several coals,
preferably of low inorganic content, by heating the mix
to 1100 C in coke batteries (ovens) that consist of two
heated walls spaced about 4045 cm apart. Reactivity and
strength are the most important parameters that character-
ize the quality of the coke, and these are in turn dependent
on the amounts and properties of organic (maceral-
derived) carbon-based components [14] and inorganic
matter (minerals) [59] inherited from the primary coals
and serve to determine the behaviour of the coke in the
BF. The evolution of the carbon structure of coke at tem-
peratures comparable to those in the upper parts of a BF
have been discussed recently based on the results of exper-
iments carried out in a horizontal laboratory-scale tube
furnace [10].
The conditions of formation and subsequent degrada-
tion and deformation of graphite crystals can be reected
in their size and morphology, as documented in a number
of studies of natural [1120] and synthetic [2123] graphite.
It is mentioned that well formed natural and laboratory-
grown graphite crystals are uncommon and that they rarely
exceed a few millimetres in size [24]. Conventional graphite
forms hexagonal (dihexagonaldipyramidal class 6/m2/
m2/m) crystals, with weak bonding between the graphite
layers. The hexagonal nature of the crystal arises because
graphite exists as a stack of sheets of carbon atoms par-
allel to {0001}, each sheet having a hexagonal arrange-
ment of atoms. Graphite crystals in the natural
environment usually possess a scaly (ake-like), platy, tab-
ular or columnar habit [1120]. In addition to its unique
0008-6223/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2007.02.033
*
Corresponding author. Fax: +358 8 553 2339.
E-mail address: ssg@cc.oulu. (S.S. Gornostayev).
www.elsevier.com/locate/carbon
Carbon 45 (2007) 11451151
technological properties, graphite is also known as one of
the few single-mineral geothermometers [25], a feature that
could make it useful for temperature estimations in systems
and processes where direct measurements are not possible.
Growing energy demands and shortage of resources
require new approaches and methods for production of
highly eective cokes. The latest is impossible without an
understanding of fundamentals of coking and coke con-
sumption processes, which includes detailed observation,
documentation and careful interpretations of various phe-
nomena that occur in materials taken from dierent stages
of these processes and comparable laboratory-scale exper-
iments. Very little is known as yet about carbon behaviour
in a coke after it is charged into a BF (such coke is often
referred to as BF coke), where it exposed to high tempera-
ture and takes part in various solid-to-solid, solid-to-melt
and solid-to-gas reactions that occur inside the BF. The
scarcity of data on BF coke in general and on the appear-
ance of graphite in it in particular [26], is mostly due to the
obvious diculties encountered in obtaining samples from
inside a working BF. This paper represents the description
of the mode of occurrence and morphological features of
graphite crystals in sample of coke taken from inside a
working BF, from the tuyere zone, where air ows into
the BF and where temperature exceeds 2000 C.
2. Materials and methods
The sample was selected from a drill core obtained from the tuyere
zone of an operating BF at the Ruukki Steel Works in Raahe, Finland,
using a mobile tuyere rig. The original location of the piece of BF coke
was 35 cm from the tuyere level. The details of the tuyere drilling were sim-
ilar to those reported by Kerkkonen [27]. A piece about 30 mm long,
23 mm wide and 57 mm thick was cut from the sample under dry condi-
tions (no cooling water was used in sawing), preserving one original sur-
face. The piece was then xed to a glass plate of 28 48 mm that ts
into the specimen holder of a scanning electron microscope (SEM). A
few particles were also selected from the sample surface for the prepara-
tion of polished sections. The dry-cut section and the polished sections
were examined preliminarily under a stereo microscope and optical micro-
scope and then with a JEOL JSM-6400 SEM equipped with an energy dis-
persive spectrometer (EDS) and operated with the INCA and SemAfore
analytical and image processing software packages.
3. Results and discussion
Investigations of the dry-cut section with a stereomicro-
scope have shown that the porous surface of the sample
hosts numerous particles of dierent size, shape and optical
properties (Figs. 14). There are relatively large segrega-
tions of slag phases (qualitative EDS data), which were
met in a few locations (Fig. 1C). The most abundant parti-
cles, which can be observed by stereomicroscope, are of
0.10.4 mm in diameter (Fig. 1A). They have a rounded
or drop-like shape and possess a dull metallic luster. The
particles often have a sharp contact with the coke matrix
and look submersed into the matrix (Fig. 1A). The sur-
face of these particles has geometric facets bounded by
ridges of triangular cross section (Fig. 1B). These carbon
(EDS-data) facets look similar to the graphitic shells syn-
thesized on top of millimeter-sized spherical transition
metal cores in high vacuum [28]. Some of these particles
also carry occasional graphite crystals on their surface.
In order to investigate the composition of such particles,
a few of them (35 mm in size) were detached from the
sample and used for the preparation of polished sections.
EDS analyses (Table 1) have shown that they are com-
posed of Si-bearing (4.017.30 wt.%) iron with traces of
Mn, V and P. So, these rounded particles seem to be drops
Fig. 1. Appearance, size and morphology of various particles on the
surface of the BF coke. A and C stereomicroscope; B SEM Jeol JSM-
6400. See text for details.
1146 S.S. Gornostayev, J.J. Ha rkki / Carbon 45 (2007) 11451151
of molten iron descending from the cohesive zone of the BF
and they are external in respect of BF coke.
There are larger particles (25 mm) surrounded by a
contact zone (0.51.5 mm), which is full of graphite crys-
tals. Such particles were observed in several separate places
(spots) located a few millimetres apart in dierent parts of
the sample. Two of them (Fig. 2A and B) located 910 mm
apart are discussed below. These particles have no geomet-
ric facets, but their surface in many places is covered by the
inorganic shells containing Ca, Al and Si (qualitative EDS
data on an unpolished surface). A clear oxygen peak was
also detected in the EDS spectrum. The particles also look
submersed into the coke matrix and host occasional graph-
ite crystals on their surface (Fig. 2A and B).
The graphite in the contact zone occurs in foliated
(Fig. 3C) intergrowths and rose-like aggregates (Fig. 2A
and B) of euhedral to subhedral crystals of varying size
and morphology (Fig. 2CK). The crystals themselves were
found on the coke matrix in close association with various
inorganic compounds, which were located in interstices
between the crystals (Fig. 5). X-ray mapping (Fig. 5) has
revealed that the interstitial phase can be presented either
by Fe (Fig. 5A) or by a complex CaFeSiO phase
(Fig. 5B). The later also contains traces of Al and K (qual-
Fig. 2. Appearance, size and morphology of graphite crystals. SEM Jeol JSM-6400. See text for details.
S.S. Gornostayev, J.J. Ha rkki / Carbon 45 (2007) 11451151 1147
itative EDS data). One of the EDS analyses on an unpol-
ished surface on the top of one particle (Fig. 2B) gave
the following concentrations (wt.%, normalized, carbon
was not measured): Fe 97.07, Ca 0.24, Si 0.15, O
2.53. So, the particles surrounded by the reaction zone
composed of graphite crystals, seem to be also droplets
of molten iron, but they were probably mixed with (cov-
ered by) the spatially associated mineral compounds from
the coke matrix.
There are also other small particles, which were
observed attached to the coke surface and to the graphite
crystals. These particles can be seen under high magnica-
tions with a SEM (Figs. 2CK, 3 and 4). Qualitative EDS
analyses has indicated that they composed of aluminosili-
cate (Ca, K and Na) phases. The nature and the compo-
sition of various inorganic compounds in the BF coke and
on its surface have been also discussed in our earlier studies
[69].
The generic forms that can be clearly seen in the crystals
from the contact zone are basal pinacoid {0001} (Fig. 2C
K; Fig. 3, Fig. 4A and B), hexagonal prism f10

10g
Fig. 3. Twinning in graphite crystals. Fig. 4. Deformations in graphite crystals.
Table 1
EDS analysis of some particles from the BF coke surface
a
Si P V Mn Fe Sum
1 4.74 0.56 0.81 94.55 100.66
2 7.30 0.32 1.24 0.58 89.79 99.22
3 4.01 0.35 0.70 94.81 99.88
a
Note: JEOL JSM-6400. Particle index: 1 30424109-35b2; 2
30424109-35b3; 3 30424109-35b4.
1148 S.S. Gornostayev, J.J. Ha rkki / Carbon 45 (2007) 11451151
(Fig. 2FK) and hexagonal dipyramid f10

11g. The dipyr-


amid can be seen in a twinned crystal (Fig. 3A), which is
discussed below. The combination of basal pinacoid and
hexagonal prism (Figs. 2C and 4A) seems to be more fre-
quent than any other combination and it was observed in
crystals of varying size (from 10 lm to 0.7 mm), although
the hexagonal prism in many crystals is not well developed
(Fig. 2C). The crystals which combine basal pinacoid and
hexagonal prism have a ake-like (Fig. 2C), platy
(Fig. 4A) or tabular habit. The ake-like crystals, which
are about 0.50.7 mm in their greatest dimension, along
the basal pinacoid, greatly exceed all the other forms in
size. The combination of basal pinacoid and hexagonal
dipyramid (Fig. 2D and E) is present in crystals which mea-
sure about 5070 lm along the (0001) plane. They have a
platy (Fig. 2D) or in rare cases an elongated-columnar
habit (Fig. 2E), which has been observed to be a rare mor-
phology in natural graphite [13,16]. The combination of
basal pinacoid, hexagonal prism and hexagonal dipyramid
is found in crystals with a platy (Fig. 2F and G) or tabular
(Fig. 2IK) habit, while graphite crystals that have an equi-
dimensional hexagonal prism in their cross-section
(Fig. 2FH) are much rarer than the distorted forms
(Fig. 2C,E and IK). In the latest forms some faces are sub-
ordinate or even missing, reecting less-than-ideal growth
conditions.
It seems likely that the crystals of ake-like morphology
with undeveloped hexagonal prism (Fig. 2C) and their foli-
ated intergrowths (Fig. 3C), which have larger surface area
than the columnar crystals (Fig. 2E), can form graphitic
cover (shield) on a surface of BF coke. The fact that
The carbon structure of coke. . . have a signicant inu-
ence on the coke behavior in a BF such that highly ordered
coke displayed lower reactivity. . . [10] combined with
these data may suggest, that in the case of favourable con-
ditions for graphite crystallization, the graphitic shield can
cover larger area of surface of BF coke (Fig. 6) thus pre-
venting it from reactions with gases circulating in a BF.
Fig. 5. X-ray maps for Fe (A: no elements other than Fe were detected) and Ca, Fe and Si (B) of two separate areas in graphite-bearing spots. SEM Jeol
JSM-6400. Scale bars: A 40 lm; B 100 lm.
Fig. 6. Generalized scheme for occurrence of graphitic coating on a
surface of BF coke (cross-section). (1) A rounded particles of Si-bearing
iron covered by graphitic shells; B particles of Si-bearing iron
surrounded by zones of graphite crystals; (2) graphite crystals and their
aggregates; (3) segregations of slag phases; (4) Internal pores (white) in a
coke matrix (black).
S.S. Gornostayev, J.J. Ha rkki / Carbon 45 (2007) 11451151 1149
One consequence of the symmetry of the internal struc-
ture of crystals is the possibility of formation of twins.
Twinned crystals have two or more parts, in which the
crystal lattice of one part is dierently but symmetrically
oriented to that of the next. The mechanisms by which
twinned crystals can be formed include growth (for pene-
tration and contact twins), transformation and deforma-
tion [29]. The following types of twins have been
identied in the graphite-bearing spots studied here: one
formed on fh0

hlg dypiramidal composition planes


(Fig. 3A and B), yielding twinned crystals (contact twins)
of size about 100 lm and 1520 lm, respectively, and the
other related to rotation on [0001] (Fig. 3C), producing
contact twins, as observed in large ake-like or plate-like
crystals.
It should be mentioned, that the intensity of coke graph-
itization with temperature was found to depend on iron
content of a coke [10]. The assessment of the mechanism
for the graphite crystallization in the BF coke based on
the experiments with the feed coke and almost 100% pure
iron was made by Wang et al. [26] including data of other
investigators [30,31] on the molten iron and vanadium car-
bide catalyzed graphitization process. It was summarized
that The iron melt at rst penetrates the surrounding car-
bon matrix through carbon dissolutionprecipitation
sequences leaving behind the well ordered graphitic car-
bons. As the penetration front moves further into the car-
bon the coke sample transforms into well ordered graphitic
carbon. Since the penetration of iron melt follows the
graphitization front, the precipitated small graphite crys-
tals would be transformed in later recrystallization steps
into large akes [26]. The last referred paper contains
no details on the graphite morphology and has no discus-
sion on possible inuence of graphite on the processes in
the BF, but among many other interesting data it reports
that the synthetic graphite has been formed in the feed coke
samples at temperatures ca. 1500 C that is well below nor-
mal graphitization temperatures due to the catalytic eect
of molten iron.
It seems, that the model proposed for the graphite crys-
tallization in the experiment [26], can be applied, at least
partly (Fig. 5A, iron-catalyzed graphite crystallization),
to the sample from the real process discussed in this study.
Nevertheless, further research will be needed in order to
explain the reason for the graphite appearance near certain
particles of molten iron and lack of it around the others as
well as the graphite association with the CaFeSiO phase
(Fig. 5B). We suggest, that one of the possible explanations
could be related to the properties of the coke matrix them-
selves, i.e. various maceral-derived components inherited
from the coking coal may have reacted dierently with
the iron droplets and other inorganic compounds. The rea-
son for the graphite appearance near the CaFeSiO
phase (Fig. 5B) can be explained by the presence of Fe in
the phase and, probably, by the impurities of other metals,
i.e., Ni and Mn, which also have catalytic eect for graph-
ite crystallization [32]. These metals (Ni and Mn) were not
detected by the X-ray mapping (Fig. 5B) probably due to
low sensitivity of the method, but they are common constit-
uents of the mineral phases of the BF coke samples from
the tuyere drillings at Ruukki Steel Works analyzed by
CAMECA SX-50 electron microprobe (WDS-method)
[33].
Graphite has low modulus of elasticity, but its high
lubricity [34] allows easy sliding of the graphene layers
across one another. For that reason, the graphitic coating
on a surface of BF coke can act as a lubricant to facilitate
the coke pieces sliding over each other thus aecting
mechanical stability of the coke cone in a BF. Further-
more, crystallization of graphite in a tuyere level can be
accompanied by the generation of coke-related nes in this
area. This suggestion can be supported by data from exper-
iments on coke annealing carried out in a horizontal labo-
ratory-scale tube furnace, which established that a higher
ordered carbon structure provided a greater amount of
nes. . . [10], where the coke nes are attributed to the par-
ticles (fractions from 63 to +450 lm were discussed) origi-
nated from coke, which were found in the BF exhaust dust.
The major deformations found in the crystals are
detaching, bending and rolling of the (0001) planes
(Fig. 4AC). Such deformations in graphite may be attrib-
uted to exfoliation, and are considered to be the result of a
phase transition involving vaporization of the intercalate in
the graphite [19,20]. The major intercalates in the BF
graphite were probably potassium and sodium, which are
abundant in BF gases. The process of exfoliation has prob-
ably caused the dismembering of the crystals to micro and
nanosheets [20] and, then, the fragile graphite crystals may
have been deformed by the BF gas ows. In some of the
crystals this concerns only tiny, submicron-thick sheets
(Fig. 4A and B), as noted elsewhere [20], while in others
a whole graphite crystal can be dismembered into several
parts (yielding a stack of sheets) and then they can be bent
(Fig. 4C). The dismembering of the crystals can be behind
the generation of the smallest fraction (comparable to the
crystal size) of nes, when particles of graphite, especially
those of ake-like morphology detached from the larger
crystals, can be easy captured by the circulating BF gas
ows thus contributing the total amount of the BF-gener-
ated dust.
4. Concluding remarks
The BF coke on tuyere level contains graphite crystals of
various size and morphologies. They occur in randomly
distributed spots and are associated with droplets of iron
with varying Si content and other inorganic compounds.
Alkali, which circulate in a BF gases, may have causes sub-
sequent exfoliation of the crystals enforced by the BF gas
ows. The formation of graphite crystals on a surface of
BF coke, especially those of ake-like morphology with
undeveloped hexagonal prism probably decreases its reac-
tivity and can be accompanied by nes generation in a
tuyere level. The graphitic cover on a surface of BF coke
1150 S.S. Gornostayev, J.J. Ha rkki / Carbon 45 (2007) 11451151
can act as a lubricant to facilitate the coke pieces to slide
along each other and thus aect mechanical stability of
coke cone in a BF.
The data presented in this study can be useful for assess-
ing coke behaviour in a BF. It will be essential to perform
further detailed investigations on graphite formation and
its evolution in a coke as well as on the nature and behav-
iour of associated inorganic compounds. This is needed for
better understanding of major reactions in a BF and for
revealing typomorphic features of graphite crystals that
can serve as an indicator of particular coke composition
and BF environment.
Acknowledgements
This research was funded by the Academy of Finland. Mr.
T. Kokkonen is thanked for the samples preparation. Anon-
ymous referees have provided valuable comments which
greatly improved clarity and quality of the manuscript.
References
[1] Andriopoulos N, Loo CE, Dukino R, McGuire SJ. Micro-properties
of Australian coking coals. ISIJ Int 2003;3:152837.
[2] Yamaoka H, Suyama S. Prediction model of coke strength after
gasication reaction. ISIJ Int 2003;43:33847.
[3] Kawakami M, Karato T, Takenaka T, Yokoyama S. Structure
analysis of coke, wood charcoal and bamboo charcoal by Raman
spectroscopy and their reaction rate with CO
2
. ISIJ Int
2005;45:102734.
[4] Sharma R, Dash PS, Banerjee PK, Kumar D. Eect of coke micro-
textural and coal petrographic properties on coke strength charac-
teristics. ISIJ Int 2005;45:18207.
[5] Todoschuk TW, Price JP, Gransden JF. Development of coke
strength after reaction (CSR) at Dofasco. Iron Steel Technol
2004;March:7384.
[6] Gornostayev S, Harkki J. Spinel crystals in tuyere coke. Metall Mater
Trans 2005;36B-2:3035.
[7] Gornostayev S, Harkki J. Mineral matter crystallization and crack
formation in tuyere coke. Fuel 2006;85:104751.
[8] Gornostayev SS, Kerkkonen O, Harkki JJ. Importance of mineral-
ogical data for inuencing properties of coke: a reference on SiO
2
polymorphs. Steel Res Int 2006;77:7703.
[9] Gornostayev S, Harkki J. Mechanism of physical transformations of
mineral matter in the blast furnace coke with reference to its reactivity
and strength. Energy Fuels 2006;20:26325.
[10] Gupta S, Sahajwalla V, Burgo J, Chaubal P, Youmans T. Carbon
structure of coke at high temperatures and its inuence on coke nes
in blast furnace dust. Metall Mater Trans 2005;36B:38594.
[11] Palache C. Graphite. Am Miner 1941;26:70917.
[12] Freise EJ, Kelly A. Twinning in graphite. Proc R Soc London
1961;64-A:26976.
[13] Jaszczak JA. Famous graphite crystals from Sterling Hill, New Jersey.
The Picking Table 1994;35:611.
[14] Jaszczak JA. Unusual graphite crystals from the lime crest quarry,
Sparta New Jersey. Rocks Miner 1997;72:3304.
[15] Luque FJ, Pasteris JD, Wopenka B, Rodas M, Barrenechea JF.
Natural uid-deposited graphite: mineralogical characteristics and
mechanisms of formation. Am J Sci 1998;298:47198.
[16] Kvasnitsa VN, Yatsenko VG, Jaszczak JA. Disclinations in unusual
graphite crystals from anorthosites of Ukraine. Can Mineral
1999;37:95160.
[17] Rakovan J, Jaszczak JA. Multiple length scale growth spirals on
metamorphic graphite {001} surfaces studied by atomic force
microscopy. Am Miner 2002;87:1724.
[18] Jaszczak JA, Robinson GW, Dimovski S, Gogotsi Y. Naturally
occurring graphite cones. Carbon 2003;41:208592.
[19] Anderson SH, Chung DDL. Exfoliation of intercalated graphite.
Carbon 1984;22:25363.
[20] Chen G, Wu D, Weng W, Wu C. Exfoliation of graphite ake and its
nanocomposites. Carbon 2003;41:579625.
[21] Gogotsi Y, Dimovski S, Libera JA. Conical crystals of graphite.
Carbon 2002;40:22637.
[22] Dimovski S, Nikitin A, Ye H, Gogotsi Y. Synthesis of graphite by
chlorination of iron carbide at moderate temperatures. J Mater Chem
2004;14:23843.
[23] Okuno H, Palnichenko A, Despres J-F, Issi J-P, Charlier J-C.
Synthesis of graphite polyhedral crystals using a combustion ame
method. Carbon 2005;43:6927.
[24] Rotkin S, Gogotsi Y. Analysis of non-planar graphitic structures:
from arched edge planes of graphite crystals to nanotubes. Mat Res
Innov 2002;5:191200.
[25] Luque FJ, Barrenechea JF, Rodas M. Graphite geothermometry in
low and high temperature regimes; two case studies. Geol Mag
1993;130:50111.
[26] Wang W, Thomas KM, Poultney RM, Willmers RR. Iron catalysed
graphitisation in the blast furnace. Carbon 1995;33:152535.
[27] Kerkkonen O. Tuyere Drilling Coke Sample Data from Rau-
taruukkis Blast Furnaces No. 1 and 2. AISTech 2004; Iron & Steel
Technology Conference Proceedings, Nashville, TN, USA, September
1517, 2004;I:46981.
[28] Winder SM, Liu D, Bender JW. Synthesis and characterization of
compound-curved graphite. Carbon 2006;44:303742.
[29] Nesse WD. Introduction to mineralogy. New York: Oxford Univer-
sity Press; 2000. p. 442.
[30] Fitzer E, Kegel B. The reaction of vanadium carbide melt with
ordered and disordered carbon. Carbon 1968;6:4336.
[31] Weisweiler W, Subramanian N, Terwiesch B. Catalytic inuence of
metal melts on the graphitization of monolithic glasslike carbon.
Carbon 1971;9:7558.
[32] Sevilla M, Fuertes AB. Catalytic graphitization of templated meso-
porous carbons. Carbon 2006;44:46874.
[33] Gornostayev S, Kerkkonen O, Harkki J. Occurrence and composition
of some mineral phases in the tuyere coke. ISIJ Int 2005;45:17.
[34] Dienwiebel M, Verhoeven GS, Pradeep N, Frenken JWM, Heimberg
JA, Zandbergen HW. Superlubricity of graphite. Phys Rev Lett
2004;92:126101-14.
S.S. Gornostayev, J.J. Ha rkki / Carbon 45 (2007) 11451151 1151