Li2016 Article EffectOfHeatTreatmentOnStructu
Li2016 Article EffectOfHeatTreatmentOnStructu
Li2016 Article EffectOfHeatTreatmentOnStructu
DOI 10.1007/s40789-016-0109-2
Received: 8 July 2015 / Revised: 31 August 2015 / Accepted: 1 September 2015 / Published online: 1 March 2016
Ó The Author(s) 2016. This article is published with open access at Springerlink.com
Abstract Petroleum coke was thermally treated on a fixed bed reactor in a temperature range of 1173–1673 K. The
changes of the elemental composition and crystalline structure of petroleum coke, with heat treatments as well as the
gasification reactivity of the heat-treated petroleum cokes were investigated. The results showed that the petroleum coke
was carbonized and graphitized to a higher degree with increasing heating temperature, while the gasification reactivity
decreased. The treatment at temperatures of 1173 and 1473 K significantly enlarged the specific surface area and the pore
volume of petroleum coke. Both the specific surface area and the pore volume decreased at 1673 K. An empirical normal
distribution function model (NDFM) was found to fit the gasification rates of petroleum coke well. The correlation
coefficient of petroleum coke by normal distribution function model at different heat treatment temperatures is between
0.93 and 0.95.
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54 C. Li et al.
the structure and gasification reactivity of petroleum coke desired temperature, and proceeded isothermally until no
with high-temperature treatments. mass loss occurred. The mass conversion (x) is calculated
according to the following equation:
m0 m
x¼ 100 % ð1Þ
2 Experimental m0 mash
where m0 is the sample weights on a dry basis at the initial
2.1 Petroleum coke samples
time, g; m is the sample weights on a dry basis at time t, g;
mash is the weight of ash in the sample, g.
Two samples of petroleum coke, a Chinese petroleum coke
(P1) and an America petroleum coke (P2), were supplied
2.4 Analysis methods
by Jinling Refinery Plant in Nanjing (China), and Valero
Energy Corporation Refining (USA), respectively. The
The scanning electron microscopy (SEM) analysis was
samples were sieved to within a size range of 83–165 lm.
performed on a JSM-6360LV electron microscope. The
Their proximate analysis and ultimate analysis are listed in
specific surface area and pore volume analysis was con-
Table 1. Due to the low ash content of petroleum coke P1,
ducted on the pore structure analyzer (ASAP 2020) using
it is hard to analyze the ash compositions. The ash com-
N2 adsorption. X-ray diffraction analysis was performed on
positions of petroleum coke P2 are listed in Table 2.
a JSM-6360 LV XRD device using Cu Ka radiation. The
characteristic parameters (d002 and Lc) of the crystalline
2.2 Heat treatment
structure of coke sample were calculated according to the
following equations (Short and Walker 2003):
The coke samples (7–8 mg) were held in a horizontal tube
furnace, alumina crucible, and then heat-treated in a hori- k
d002 ¼ ð2Þ
zontal tube electric furnace under a nitrogen atmosphere. 2 sin h002
The heating rate was 10 K/min. The heat treatment was 0:94k
kept at the final temperatures of 1223, 1473 and 1673 K for Lc ¼ ð3Þ
b002 cosðh0 Þ0
a certain period of time (30 min).
where d002 and Lc are, respectively, the interplanar spacing
2.3 Gasification reactivity and the stacking height of the carbon crystal, k is the
wavelength of the X-ray radiation, h002 is the position of
The measurement of the gasification reactivity of coke was the peak (002), and b002 is the angular width at half-
carried out on a Thermo-Cahn Thermax 500 thermo maximum intensity of the peak (002).
gravimetric analyzer (TGA). In each experiment, a 7–8 mg
sample of coke was used. A nitrogen gas of high purity
(99.99 %) was purged at a flow rate of 1000 mL/min when 3 Results and discussions
the sample was heated up at a heating rate of 25 K/min
until the temperature reached 1273 K. The gasification 3.1 SEM observations
started by switching nitrogen to carbon dioxide at the
Figure 1 shows the typical SEM images of two original
petroleum cokes and their samples treated at different
Table 1 Properties of petroleum coke
temperatures. P1 is the most layered structure and dense in
P1 P2 texture, somewhat regular in arrangement.
Proximate analysis (air dried basis, %) After heat-treated, P1 was more smooth, and the layered
Moisture 1.80 0.30 structure disappeared. In contrast, the surfaces of the
Ash 0.26 3.04
original (P2) cokes were smooth and dense in texture, with
Volatile matter 9.34 10.32
a barely porous structure. However, the surfaces of the
Fixed carbon 88.60 86.34
heat-treated petroleum cokes were more rough with more
fold structure and some porous structure.
Ultimate analysis (dry basis, %)
Carbon 89.15 85.81
3.2 Compositions of petroleum cokes
Hydrogen 3.72 3.68
Nitrogen 0.75 0.35
Table 3 shows the properties of petroleum coke obtained
Sulphur 2.08 6.10
by heat treatments. It was seen that the contents of moisture
Oxygen (by difference) 4.04 1.01
and volatile decreased with increasing heating temperature,
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Effect of heat treatment on structure and gasification reactivity of petroleum coke 55
34.87 31.51 15.08 8.46 3.31 1.79 1.74 1.25 0.87 0.40 0.33 0.15
Fig. 1 SEM images of petroleum coke samples at different heat treatment temperatures. a P1, untreated; b P1, Th= 1173 K; c P1, Th = 1473 K;
d P1, Th = 1673 K; e P2, untreated; f P2, Th = 1173 K; g P2, Th = 1473 K; h P2, Th = 1673 K
P1 1173 2.08 0.23 6.33 91.38 88.91 0.85 1.45 3.58 104.110
1323 0.87 0.24 3.63 95.27 91.99 0.85 1.41 3.76 107.969
1473 0.44 0.23 2.68 96.57 94.84 0.85 1.36 3.62 111.178
1673 0.16 0.26 2.00 97.62 95.87 0.86 0.78 3.87 111.471
1773 0.10 0.24 2.52 97.15 97.51 0.86 0.52 3.44 113.444
P2 1173 2.22 2.88 8.13 86.78 84.45 0.96 1.51 4.56 88.101
1323 2.85 3.11 7.54 88.10 83.91 0.93 1.16 5.63 90.713
1473 1.31 3.37 5.29 90.04 89.09 0.97 0.88 5.60 95.182
1673 0.27 4.19 3.83 91.72 90.48 0.91 0.52 6.38 99.872
1773 0.46 4.53 4.91 90.10 90.52 0.86 0.81 5.06 105.686
whereas the fixed carbon increased. The molar ratio of 3.3 Graphitization of petroleum coke
m(C)/m(H) increased with the increasing heating temper-
ature, implying the progressed aromaticity or carbonization Figure 2 shows the XRD patterns of the petroleum cokes.
of coke with preferential release of hydrogen (Xie 2002). In As the heating temperature was elevated, the peak (002)
addition, the content of nitrogen decreased, suggesting the reflection became sharp and gradually close to that of
preferential release of nitrogen upon heat treatment. graphite (26.6°) in the diffraction angle (Senneca and
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56 C. Li et al.
Sa St
Xa ¼ ; Xt ¼ ð4Þ
Sa þ St Sa þ St
where Sa and St are the peak area of (002) peak of amor-
phous carbon and turbostratic carbon, and Xa and Xt are the
ratio of peak area of peak (002) of amorphous carbon and
turbostratic carbon. The average microcrystalline structure
parameters of petroleum cokes (d002 and Lc) were obtained
from the following equations:
d002 ¼ Xa d002;a þ Xt d002;t ð5Þ
Lc ¼ Xa Lc;a þ Xt Lc;t ð6Þ
Table 5 shows that heat treatment enables more amor-
phous carbon to be converted to turbotratic components,
with the average interplanar spacing decreasing and the
average stacking height of crystal increasing. It was evident
that the polycondensation of petroleum coke was pro-
gressed with the temperature increasing, gradually forming
compact and graphite-like carbon structure. It was reported
that the petroleum coke was thoroughly converted to gra-
phite at a much higher temperature of 2273 K (Sun and
Shen 2004).
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Effect of heat treatment on structure and gasification reactivity of petroleum coke 57
Fig. 3 Gauss fitting curves for 002 peak of petroleum coke samples. (1) Untreated; (2) Th = 1173 K; (3) Th = 1473 K; (4) Th = 1673 K
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58 C. Li et al.
Table 4 Scatting angles (2h) of peak (002) of petroleum coke Table 6 BET surface area and pore volume of petroleum coke
samples
Sample Th (K) SBET (m2/g) Vp (cm2/g)
Sample Th (K) 2h (°)
P1 Untreated 1.1824 0.00595
P1 Untreated 25.32 1173 15.6229 0.01346
1173 25.22 1473 28.5293 0.01782
1473 25.40 1673 3.0254 0.00851
1673 25.50
P2 Untreated 1.9261 0.00443
P2 Untreated 25.22 1173 11.0113 0.01604
1173 25.28 1473 35.1096 0.03336
1473 25.30 1673 7.2068 0.01950
1673 25.36
Table 5 Crystal structure parameters of the petroleum coke obtained at different heating temperatures
Samples Th (K) d002,a (Å) Lc,a (Å) d002,t (Å) Lc,t (Å) Xa Xt d002,a (Å) Lc,a (Å)
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Effect of heat treatment on structure and gasification reactivity of petroleum coke 59
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60 C. Li et al.
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Effect of heat treatment on structure and gasification reactivity of petroleum coke 61
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Basic Research Development Program of China (973 Program, 2010 petroleum coke during the course of carbonization analyzed by
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