Int J Coal Sci Technol (2019) 6(4):611–620

https://doi.org/10.1007/s40789-019-00279-y

Experimental investigation of process parameters

during graphitization of catalytic coke
Kobra Pourabdollah1 • Masoud Samadian Zakaria2 •
Seyed Mohammad Mir Najafizadeh2 • Fatemeh Motaghedi1

Received: 3 June 2019 / Revised: 29 August 2019 / Accepted: 14 October 2019 / Published online: 11 November 2019
Ó The Author(s) 2019

Abstract The aim of this project is studying the effect of thermal operation parameters on the graphitization of self-
diffused ethane-based catalytic coke. The novelty of this study refers to self-diffused metals that had given unique
properties to the catalytic coke and had improved the graphitization degree at low temperatures. The main feature of this
research is presenting a remarkable energy saving approach that uses low-cost installations for production of graphitized
carbon. The experiments were performed in two steps including preparation of self-diffused ethane-based catalytic coke
and then low-temperature graphitization of coke samples below 1500 °C. Characteristic tests were performed by deter-
mination of electrical resistivity and XRD pattern of graphitized samples including graphitization degree, aromaticity, coke
rank, number of carbon rings, graphene thickness and length. The results revealed that the blanket atmosphere, final
temperature and exposure time had the greatest impact on the aforementioned criteria, while the role of thermal ramp and
sulfur content of catalytic coke was negligible. The electrical resistivity tests on the graphitized sample showed how the
electrical resistivity of graphitized samples is a function of graphitization degree.

Keywords Graphite  Catalytic coke  Self-diffusion  Desulfurization

1 Introduction Catalytic graphitization of coal and hydrocarbons by

transition metals has been used for encapsulation, forma-
Solid carbons, cokes and chars consist of randomly arran- tion of fibers and carbon nanotubes (De Jong and Geus
ged crystalline-phases that are imperfect and distributed in 2000; Bokhonov and Korchagin 2002; Helveg et al. 2004).
the solid matrix (Wissler 2006). Synthetic cokes (Pourab- When the solid carbon is produced from a gas phase, the
dollah 2018a) exhibit the properties of metals including catalytic graphitization can intensify the reaction by
electrical and thermal conductivity and of non-metals forming a thin film of amorphous carbon on the catalyst
including lubricity, high thermal resistance and inertness particles (Anton 2005, 2008). Using nickel (Anton 2009)
(Feng et al. 2003) and are used in cathodic wells and oil and iron (Bokhonov and Korchagin 2002) catalyzers, the
wells (Pourabdollah 2017a, 2018b), batteries (Pourabdollah graphitization was conducted with encapsulation of metal
2017b) and furnaces. particles by graphite layers.
Interaction of metallic catalyzers (such as La, Ce and Pr)
with coal, coke and graphite materials is based upon the
chemical addition of fine powders of metals followed by
& Kobra Pourabdollah heating and proceeding the reaction (Wang et al. 2016). On
[email protected]
the other hand, the diffusion of some elements in the gra-
1
Chemistry and Chemical Engineering Research Center of phite matrix has been investigated and it was revealed that
Iran, Tehran, Iran boron (Hennig 1965), argon and helium (SHIGENO et al.
2
Department of Research and Technology, Tehran Province 1988), uranium (Loch et al. 1956), cesium (Carter et al.
Gas Company, Tehran, Iran 2015) and iron (Stoneham 1979) diffuse in the coke matrix

123
612 K. Pourabdollah1 et al.

at elevated temperature, leading to the catalysis of the 2.1 Preparation of the catalytic coke
graphitization reaction.
Feng et al. (2003) investigated the crystallite structure of A cylindrical self-diffused catalytic coke was prepared
several coke samples during CO2 and air gasification. The inside a tubular reactor located in the hot section of gas-
thermal annealing of several coke samples were applied cracker furnace. The reactor was heated by a gas fuel
and followed by studying the evolution of carbon structure stream from bottom (1175 °C) to top (157 °C) sections of
in the coke matrix and the results revealed a linear corre- furnace. In order to improve the thermal stability of tubular
lation between the annealing temperature and the stack reactor, their optimum chemical composition was Fe, Ni,
height (L002) of carbon crystallite (Gupta et al. 2005). The Cr and Nb (37 : 35 : 25 : 3 wt%), respectively. At the
carbon structure in the coke matrix, which has a non-gra- initial stage of the cracking process, a sulfidation stage is
phitic and turbostratic scaffold, can capture inorganic performed in order to cover the inside surfaces of tubular
impurities such as metals. The dimensions of graphitic- reactor and decrease the adhesion tendency of the catalytic
crystallite in the coke matrix is characterized by the coke. Therefore, dimethyl disulfide (DMDS) was injected
interlayer spacing (c/2 = half the hexagonal lattice c-axis), into the stream of dilution steam for sulfidation at 1 h and
the thickness of hexagonal packing (Lc = crystallite 101 kPa. During the sulfidation, DMDS concentration in
dimension in the c-axis direction) (Feret 1998; Lu et al. dilution steam was set to be 100–1000 ppm. Just after
2001; Sonibare et al. 2010; Mollick et al. 2015), the spread sulfidation, the coils temperature was optimized to be
of carbon basal plane (La = crystallite dimension in the 825–836 °C and the steam flow was co-injected.
a-axis direction) (Sonibare et al. 2010; Mollick et al. 2015), Ethane feed along with dilution water steam and DMDS
aromaticity (Sonibare et al. 2010; Odeh 2015), coke rank was injected into the tubular reactor leading to gradual
(Yoshizawa et al. 2001; Sonibare et al. 2010), graphitation formation of catalytic coke layer on the inside surface of
degree (Mollick et al. 2015) and number of carbon rings the tubes. In the cracking temperature (800–820 °C), the
(Belenkov 2001) and grapheme layers (Mollick et al. transition metals are self-diffused into the produced coke.
2015), which are determined from X-ray diffraction (XRD) The behavior of catalytic coke shows that a filamentous
patterns. Not only the bond strengths are not fixed along the morphology and Fe, Ni and Cr from the metal matrix of the
crystallographic directions, but also a variety of voids, reactor walls diffuse into the filaments coke matrix (Rey-
defects and cross-links are present in the coke matrix. niers et al. 1994). For the consideration of energy saving,
Therefore, various reaction rates in the coke matrix show the cooling water was directed to a steam boiler as boiler
an anisotropic character and have a directional nature (Li feed water (BFW) for production of dilution steam. After
et al. 2014). increasing the coke thickness and reducing the interior
The first aim of this study is to produce a catalytic coke diameter of tubular reactor, the furnace was switched to the
from ethane feed at temperature 850 °C range along with decoking stage, at which the cylindrical catalytic coke was
the self-diffusion of some transition metals (Fe, Ni and Cr) separated from the tubular reactor by steam and air injec-
as catalyzers of the upcoming reaction. The second aim is tion at hot temperatures (810–850 °C). Figure 1 shows a
to optimize the low-temperature (850–1470 °C) catalytic schematic of ethane cracker furnaces, their flow diagrams
graphitization reaction based upon the aforementioned self- and the tubular reactor direction.
diffused catalyzers. The third aim is to characterize the
self-diffused catalytic graphitization of coke by XRD 2.2 Graphitization of the catalytic coke
algorithms. The micro-texture terminology and the classi-
fication of graphite samples vary in different countries; The cylindrical samples of catalytic coke were milled and
hence, a reference method was developed for characteri- sieved in the particle range of 0.1–1.0 mm. The calcination
zation of graphite scaffolds and measurement of their of coke breeze was performed in a reactor embedded in box
electrical resistance. furnace (REBF) under controlled atmosphere, temperature
and time. The calcination of catalytic coke breeze were
carried out in different conditions including N2, water
2 Experimental methods steam, air and CO2 atmospheres, the temperatures of
850 °C, 1050 °C, 1350 °C and 1470 °C, temperature
The experiments have been conducted in two sections ramps of 5, 10, 15 and 20 °C/min, the range of sulfur
including preparation of the catalytic coke from ethane content 0% – 1.0%, 1.0% – 2.0%, 2.0% – 3.0% and
feed in a gas cracker furnace and graphitization of the 3.0% – 4.0% wt. and the heating times of 1, 30, 60 and
catalytic coke in a calcination kiln. 120 min. The REBF was filled by ceramic balls (3 mm and
10 mm in diameter) as the supporting material and the
catalytic coke breeze was filled and packed as presented in

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Experimental investigation of process parameters during graphitization of catalytic coke 613

Fig. 2. The controlled atmosphere was flowed and degree (g) and the number of carbon rings per lamella (N),
exhausted from the sides of REBF. The ceramic balls not respectively.
only improved the gas flow distribution but also prevented
the choking tendency of fine particles in the exhaust line. 2.3 Determination of electrical resistivity
The calcination was designed by Taguchi algorithm and
the above-mentioned parameters (five items), each of them The electrical resistivity was evaluated using a micro-
at four different levels, were optimized. Table 1 shows the ohmmeter and the four-point soil box adopted for this
examined parameters and the relevant levels. The application. The electrical current was applied between the
agglomeration runs were designed according to design of outer-pins while the voltage was monitored between the
experiments (DoE) methodology, based upon 6 terms of inner-pins. The electrical resistance was determined by the
aromaticity (f), coke rank (CR), La, Lc, graphitization appropriate values of electrical current and the voltage-
drop was measured between the inner-pins.

Fig. 1 Schematic representation of ethane cracker furnace for production of self-diffused catalytic coke

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614 K. Pourabdollah1 et al.

Table 1 The controlled parameters in L16 orthogonal-array at different levels

Parameters Symbols L1 L2 L3 L4

Atmosphere P1 N2 Water steam Air CO2

Temperature (°C) P2 850 1050 1350 1470
Temperature ramp (°C/min) P3 5 10 15 20
Sulfur content (wt%) P4 0–1.0 1.0–2.0 2.0–3.0 3.0–4.0
Heating time (min) P5 1 30 60 120

3 Results and discussions Car A002

f ¼ ¼ ð1Þ
Car þ Cal A002 þ Ac
The investigated parameters on the graphite samples
I26
include f-value, CR, La, Lc, g and N, which were deter- CR ¼ ð2Þ
I20
mined by pattern recognition of XRD signals (Fig. 3). The
signals include c (17°), 002 (26°), 100 (42°), 101 (43°), 004 1:84k
La ¼ ð3Þ
(53°), 103 (59°) and 110 (78°) in the range of 2h = 5° – Ba cos ua
80°. By improving the graphitization degree, the shape and 0:89k
the situation of XRD signals are varied leading to orien- Lc ¼ ð4Þ
Bc cos uc
tation of the carbon scaffold. The step size and scanning
rate of XRD tests were fixed to be 0.02 degrees 2-theta and nk
d002 ¼ ð5Þ
10°/min, respectively. sin uc
The strength of signals (I), the area behind them (A), the 3:44  d002
full width at half maximum (FWHM, B) and the angle of g¼ ð6Þ
0:086
signal (u) are the key elements to formulate the graphiti-
Lc þ d002
zation process of cracked cokes. The subscripts a and c are N¼ ð7Þ
d002
corresponded to (100) and (002) peaks, respectively.
Table 2 shows the above-listed parameters for two distinct where in Eq. 1, Car and Cal show the number of aromatic
signals that have been obtained during the pre-designed and aliphatic carbons (Lu et al. 2001; Odeh 2015),
experiments. Figure 4 shows the XRD patterns of all the respectively. Likewise, A002 and Ac represent the integrated
samples. area under the corresponding peaks 002 (2h = 26.7°) and c
ASTM D5187 covers the determination of the mean (2h = 17°–20°), respectively. On the other hand, in Eq. 2,
crystallite thickness of coke samples by XRD patterns that I26 and I20 reveal the peaks intensity at positions 2h = 20°
are obtained by conventional X-ray scanning instruments. and 2h = 26°, respectively. In Eqs. 3 and 4, B and u show
The XRD pattern was obtained in the range of 5°–85°2h the half width of peaks (2h, radians) and the corresponding
´
using Cu tube (k = 1.54Å) and R1-6 are determined by
Eq. 1 to Eq. 7.

Fig. 2 Graphical implementation of REBF filled by ceramic balls

and catalytic coke Fig. 3 XRD pattern of un-graphitized coke

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Experimental investigation of process parameters during graphitization of catalytic coke 615

Table 2 The results of XRD readouts for the designed experiments

Run A002 (counts-2h) Ac (counts-2h) I26 (counts) I20 (counts) Ba (rad) Bc (rad) ua (°) uc (°)

1 40100 479 8020 652 0.0065 0.0045 20.95 13.20

2 39800 502 7990 652 0.0065 0.0043 20.9 13.20
3 50150 489 10010 713 0.0063 0.0034 20.95 13.25
4 45000 491 9020 719 0.005 0.0041 20.9 13.24
5 4800 520 990 688 0.0174 0.0175 20.5 12.94
6 10100 492 2030 689 0.0162 0.0172 20.5 12.96
7 9980 490 2000 700 0.0154 0.0155 20.55 12.97
8 14400 492 2890 650 0.0128 0.0148 20.65 13.00
9 29950 478 5980 702 0.0109 0.0093 20.75 13.09
10 30100 520 6050 699 0.0108 0.0091 20.8 13.11
11 41000 552 8100 629 0.0085 0.0065 20.85 13.18
12 36000 551 7210 791 0.0092 0.0081 20.85 13.16
13 14400 539 2890 681 0.0133 0.0139 20.6 13.01
14 20500 589 4120 680 0.0119 0.0107 20.7 13.06
15 24400 522 4900 640 0.0101 0.0095 20.7 13.08
16 30300 520 6070 641 0.0101 0.0087 20.75 13.10

Fig. 4 XRD patterns of all the samples

scattering angles (h, degree), respectively. The subscript interlayer spacing, in which n is a positive integer and k is
´
signs a and c are corresponded to (100) and (002) peaks, the wavelength of the incident wave (Cu, 1.54Å).
respectively. d002 in bragg’s equation (Eq. 5) exhibits the Therefore, all of 6 responses (R1 to R6) are controlled by
eight readouts obtained from the XRD patterns of

123
616 K. Pourabdollah1 et al.

individual coke and graphite samples that were produced

from run 1 to run 16. According to Eqs. 1–6, these readouts
are including A002, Ac, I26, I20, Ba, Bc, ua and uc. The next
section reveals the results of XRD experiments represent-
ing the above-listed readouts.
In Table 3, the terms of R1-6 reveal the responses
obtained by XRD patterns of graphitized coke samples,
which has been used for the determination of coke crys-
tallinity including f-value, CR, La, Lc, g and N.
The results of Taguchi algorithm revealed that among
five parameters, the atmosphere composition strongly
affected the graphitization efficiency. Increasing the max- Fig. 5 Schematic illustration of Taguchi response for graphite-
imum temperature from 850 to 1470 °C as well as the optimization of catalytic coke
exposure time of thermal operation from 0 to 120 h led to
polycyclic planes of catalytic coke. This damage is the
the improvement of the graphitization of catalytic coke.
main cause of micro-fractures in the body of deposited
Likewise, the temperature ramp of 15 °C/min and sulfur
coke used in decoking operation of gas crackers of
content range of 1%–2% wt. revealed the other optimum
refineries. At high temperatures, the thermal decomposition
conditions. Figure 5 shows the graphical implementation
of water steam on the carbon surfaces helped form active
of Taguchi response by five parameters and four levels.
hydrogen atoms that are responsible for ring opening of
polycyclic aromatic scaffolds of coke matrix and the
3.1 Effect of graphitization atmosphere
decreasing of the graphite properties. On the other hand,
CO2 atmosphere limits the graphitization phenomena of
As presented in Fig. 5, the gasification (water–gas shift)
catalytic coke because of the enhancement of the gasifi-
reaction by water steam and CO2 (Chianese et al. 2015) has
cation process.
decreased the graphitization efficiency of ethane-based
It was demonstrated that aforementioned Cr (Chianese
catalytic coke. The experimental results revealed that water
et al. 2015), Ni (Zhao et al. 2014; Guo et al. 2015) and Fe
steam decreases the graphitization efficiency of ethane-
(Chianese et al. 2015) dopants preset in the matrix of
based catalytic coke. Water steam loses the coke structure,
catalytic coke catalyze the gasification reactions under
leading to the increasing of the structural damage of
water steam and CO2 atmospheres. The unique

Table 3 The run test characteristics

Run Parameters Responses
P1 P2 P3 P4 P5 R1 R2 R3 R4 R5 R6

1 N2 850 5 0–1.0 1 0.99 12.3 467 313 0.79 94

2 N2 1050 10 1.0–2.0 30 0.99 12.3 467 327 0.79 98
3 N2 1350 15 2.0–3.0 60 0.99 14.0 482 414 0.94 124
4 N2 1470 20 3.0–4.0 120 0.99 12.5 607 343 0.91 103
5 Water steam 850 10 2.0–3.0 120 0.90 1.4 174 80 0.02 24
6 Water steam 1050 5 3.0–4.0 60 0.95 2.9 187 82 0.08 25
7 Water steam 1350 20 0–1.0 30 0.95 2.9 197 91 0.11 27
8 Water steam 1470 15 1.0–2.0 1 0.97 4.4 237 95 0.20 29
9 Air 850 15 3.0–4.0 30 0.98 8.5 278 151 0.47 46
10 Air 1050 20 2.0–3.0 1 0.98 8.7 281 155 0.53 47
11 Air 1350 5 1.0–2.0 120 0.99 12.9 357 217 0.73 65
12 Air 1470 10 0–1.0 60 0.98 9.1 330 174 0.67 52
13 CO2 850 20 1.0–2.0 60 0.96 4.2 228 101 0.23 31
14 CO2 1050 15 0–1.0 120 0.97 6.1 255 131 0.38 40
15 CO2 1350 10 3.0–4.0 1 0.98 7.7 300 148 0.44 45
16 CO2 1470 5 2.0–3.0 30 0.98 9.5 300 162 0.50 49

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Experimental investigation of process parameters during graphitization of catalytic coke 617

thermophysical properties of H2O and CO2 are responsible 1050 °C the broad signal was split into three segments
for distinct reactions of catalytic coke under gasification having signal centers at 23°2h, 26°2h and at 31°2h. The
process (Hwang et al. 2011; Zhu and Wachs 2015) as middle signal was sharp (FWHM = 3.43°) at 2h value
Eqs. 8–10 explain: closer to the anticipated 002 signal of graphite. Upon fur-
CO2 ðgÞ þ C ðsÞ ! 2COðgÞ ð8Þ ther increase in temperature to 1350 °C, this signal was
further narrowed (FWHM = 2.43°). Reduction of signal
H2 OðgÞ þ C ðsÞ ! COðgÞ þ H2 ðgÞ ð9Þ width was continued when the temperature was increased
H2 OðgÞ þ COðgÞ ! CO2 ðgÞ þ H2 ðgÞ ð10Þ to 1470 °C. The middle signal at 26°2h was further nar-
rowed (FWHM = 2.03°). Decreasing of signal width along
In air atmosphere, the burning process of catalytic coke with increasing the graphitization temperature reveals the
was carried out, activating rings opening of polycyclic increasing of sp2-bonded content in the coke matrices.
aromatics and losing the graphite planes at annealing When the metal-impregnated catalytic coke is heat-
conditions, while under nitrogen atmosphere none of the treated under nitrogen atmosphere, the metallic species are
gasification and burning reactions was carried out to reduced from the metal oxide to the elemental metal (e.g.
improve the graphitization process at the temperatures of Fe and Ni). At temperatures higher than 800 °C, the self-
interest. diffused metallic particle contained within the coke media
acted as catalyst for the conversion of amorphous-carbon to
3.2 Effect of graphitization temperature more ordered graphitic-carbon. The type of doped metal
has a great role in the graphitization of coke samples. In
While some carbon-substrates attain ordered orientation at this regard, Sevilla and Fuertes (Sevilla and Fuertes 2006)
temperatures below 2000 °C, the other carbonaceous studied the effect of three metals on the graphitization
materials do not exhibit such ordered scaffold even above degree and they proposed the following order:
3000 °C. Therefore, the graphitization reactions also Ni [ Mn [ Fe.
depend on the scaffold of the materials being graphitized
(Gupta et al. 2017). On the other hand, carbon graphiti- 3.3 Effect of temperature ramp and sulfur content
zation at relatively low temperatures (below 1500 °C) has
been assessed by low dosage injection of some transition The samples of petroleum coke were normally calcined up
metals (such as Fe, Ni and Mn) (Sevilla and Fuertes 2006; to 1400 °C and desulfurization was carried out to a sig-
Barbera et al. 2014) as the scope of the present study. nificant degree within this temperature range. However, the
The effect of graphitization temperature was assessed in desulfurization efficiency was not only dependent on the
the range of 850–1470 °C and the results showed that the applied temperature, but also was affected by other
graphitization was enhanced at high temperatures up to parameters including the heating ramp, residence time, gas
1470 °C, at which the structural modifications of poly- blanket atmosphere and the concentration of catalytic
cyclic scaffolds were occurred and more desulfidation was metals. Thermal desulfurization of catalytic coke was
performed. High temperature desulfurization is discussed conducted along with the graphitization reaction, simulta-
in the next section. Figure 6 shows the effect of maximum neously and it is divided into four phases as the following
temperature on the graphitization degree of catalytic coke, (Al-Haj-Ibrahim and Morsi 1992).
schematically.
The coke samples were graphitized at 850 °C showing a (1) Initial phase of desulfurization (850 °C)
broad signal at 26°2h (002) along with a shoulder at 42°2h
(100). By increasing the temperature of graphitization to

Fig. 6 Graphical implementation of graphitization degree versus heating temperature

123
618 K. Pourabdollah1 et al.

The sulfur bounds on the surfaces or in the matrix pores are

broken and simultaneously the side chains of aromatic
molecules are cracked. The maximum amounts of sulfur
removed in this phase are reported to be less than 25%
since no reaction takes place between sulfur and metals and
no variation is observed in desulfurization degree of cat-
alytic cokes with self-diffused metals.
(2) Second phase of desulfurization (1050 °C)
In this phase, little or no desulfurization is performed as it
is significantly depressed by the self-diffused metals (e.g.
Ni) that react with dissociated-sulfurs to form refractory-
sulfur. Ash and self-diffused metals seem to have no effect
on desulfurization up to this temperature, while at tem-
peratures greater than or equal to 1050 °C desulfurization
is further inhibited by forming a thermally stable metal-
sulfide.
(3) Third phase of desulfurization (1350 °C)
Fig. 7 Linear dependency of g vs. q for the graphitized samples of
Upon further increase in temperature of catalytic coke to
ethane-based coke
1350 °C, the available energy is enough high for the
decomposition of sulfur-hydrocarbon compounds such as 3.5 Electrical resistivity
thiophenes. In this phase it is not possible to eliminate total
sulfur from the coke matrix since the desulfurization The success of catalytic graphitization can be assessed by a
degree is significantly related to total sulfur content of the notable improvement in the electrical resistivity (q)
coke. (Sevilla and Fuertes 2006). The electrical resistivity of
(4) Third phase of desulfurization (1470 °C) graphitized coke samples depends mainly on the atmo-
Further increase in temperature cannot lead to more sphere, the exposure time and the temperature employed.
desulfurization, since it depends mainly on the nature of Figure 7 shows the linear dependency of q to g, repre-
coke. In this phase, the apparent density of catalytic coke senting a threshold point at g = 10% and q = 65X.cm.
was increased from 1.3(± 0.1) to 1.8(± 0.2). In this tem-
perature range, the density change depends on the initial 3.6 Determination of transition metals
sulfur-content. In the presence of high sulfur-content cokes,
the coke density was decreased; and with coke samples of Coke formation in tubular reactors is a steady state process,
low sulfur-content, the density was increased. The decrease which takes place in long periods of time, in the range of
of apparent density at 1470 °C, which is called the puffing several days. At enough high temperatures, iron and nickel
phenomenon, is the result of porosity development when elements diffuse into the coke matrix along with chromium
the sulfur-species get out from the coke media. migration leading to formation of a ferromagnetic coke.
Distribution of the above-mentioned elements in the coke
3.4 Effect of heating time matrix was studied by EDX–mapping (Tsuneta et al. 2002;
Allen et al. 2012) and the results revealed that the con-
Abdul Abas et al. (Abas et al. 2006) studied the centration of the diffused elements is reduced from the
graphitization of blast furnace coke and they reported exterior surface to the inner surface of coke layer. On the
that the graphitization degree is independent from time. other hand, the concentration of sulfur-containing com-
However the results of the present study revealed that the pounds was studied along the thickness of the coke layer by
graphitization criteria of catalytic coke are declined by EDX–mapping and the results revealed that sulfur con-
increasing the exposure time. This may be due to the centration is increased from the outer to the inner surface.
high surface energy of the coke, which intensifies the Figure 8 shows a schematic representation of metal and
time-dependent puffing phenomena at elevated temper- sulfur distribution in the coke matrix.
atures. The porosity development of the aged samples of
heat-treated coke leads to decreasing the graphitization
criteria.

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Experimental investigation of process parameters during graphitization of catalytic coke 619

Fig. 8 EDX-mapping of the deposited coke on the inner surfaces of tubular reactor

4 Conclusions link to the Creative Commons license, and indicate if changes were
made.

(1) Self-diffusion of some structural metals into the coke

matrix varies their reactivity and their responses in
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