Fuel 190 (2017) 245–252

Contents lists available at ScienceDirect

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

Full Length Article

Co-gasification reactivity of petcoke and coal at high temperature

Liwei Ren a,b, Ruidi Wei a,⇑, Yuhong Gao a
a
Department of Chemistry, Chemical Engineering and Material, Handan University, Handan, Hebei 056005, PR China
b
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, PR China

h i g h l i g h t s

Co-gasification reactivity of petcoke with coal was studied at high temperature.

The reactivity of petcoke can be improved greatly by co-gasifying with coal.

The synergistic effect is closely related to the minerals in coal but not coal rank.

The Ca-/Fe-components is beneficial for gasification of petcoke even at 1400 °C.

a r t i c l e i n f o a b s t r a c t

Article history: Petcoke, as a byproduct of petroleum refinery process, can be used as feedstock of gasifiers due to its high
Received 2 August 2016 carbon content and high calorific value. However, its low gasification reactivity and low ash content
Received in revised form 17 September restrict its application to some gasifiers. In this work, experimental study on co-gasification reactivity
2016
of petcoke with coal under CO2 atmosphere was investigated in a drop-in-fixed-bed reactor in the tem-
Accepted 3 November 2016
Available online 10 November 2016
perature range of 1200–1400 °C. Produced CO was monitored continually using an online mass spectrom-
etry to calculate the carbon conversion and gasification rate. The experimental results reveal that the
gasification reactivity of petcoke can be improved greatly by co-gasifying with coals or by loading their
Keywords:
Co-gasification reactivity
ashes, even at temperatures higher than the ash fusion temperature. Both the coal and its ash can
Petcoke improve the gasification reactivity of petcoke. The synergistic effect is closely related to the composition
Coal of minerals in coal but not coal rank. The high content of active components such as Ca- and Fe- in coal or
Mineral matter ash is beneficial for co-gasification. Some coals, however, are lack of these active components and with
Catalytic effect high Si- and Al-components content which may retard the gasification reaction. During co-gasification,
the oldhamite (CaS), anhydrite (CaSO4) and magnetite (Fe3O4) have positive catalytic effect, while mulite
(3Al2O32SiO2) has negative effect on gasification reaction at high temperature.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction Increasing the gasification temperature is one of the most effec-

With the increasing demand of petroleum and the installation
of more petroleum deep conversion process units, the output of
petcoke has increased rapidly [1]. Petcoke has a high carbon con-
tent and calorific value which usually be used as fuel to combust,
inevitably with low efficiency and high pollution especially high-
sulfur petcoke. Fortunately, it is increasingly considered as an
attractive feedstock for gasification to produce hydrogen, power,
and steam in the petroleum industry [2,3]. However, the low reac-
tivity and ash content of petcoke has greatly restricted its applica-
bility for gasification [4–6].
⇑ Corresponding author.
E-mail address: weiruidi0205@163.com (R. Wei).
tive methods to improve the gasification reactivity of petcoke. In
our previous work [7], it was found that the CO2 gasification rate
of petcoke increases 25 times as the temperature increases from
1200 °C to 1600 °C. However, the gasification rate of petcoke was
still several times lower than that of coals even at 1600 °C in both
CO2 and steam atmosphere. In order to achieve a high carbon con-
version, a higher temperature or a larger residence time is neces-
sary. But this will reduce the gasification efficiency and
economics. Moreover, the low ash content of petcoke is not suit-
able for entrained-flow slagging gasifiers with a cooled membrane
wall.
On the other hand, it is known that coal is the most common
feedstock used for gasification. The reactivity of coal often varies
with its rank, which decreases from low rank coal to high rank coal.
The low rank coal usually has a high reactivity as its high content of

http://dx.doi.org/10.1016/j.fuel.2016.11.020
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
246 L. Ren et al. / Fuel 190 (2017) 245–252

volatile and mineral matter [8]. However, it is not often used as
feedstock in most entrained-flow gasifiers, which is because of
its high moisture, low calorific value and low concentration in
coal-water slurry [9,10]. How to utilize the large deposits of low
rank coal remains a serious problem, especially in China.
Considering the characteristics of petcoke and low rank coal,
co-gasification will be a better method to improve the low
reactivity of petcoke and also offer a suitable way to utilize the
large amount of low rank coal. Understanding the co-gasification
behavior and reaction mechanism of petcoke and coal is essential
for the development of co-gasification technology. Up to now,
there are a number of studies concerning on co-gasification of coal
and petcoke. It is important to note that some synergetic effects
may occur during co-gasification of petcoke with coal or other
materials [11–13]. Due to the synergy effect, the gasification
reactivity, carbon conversion, syngas heating value and cold gas
efficiency of petcoke can be improved by co-gasifying with coal
or other materials [14–16].
However, it should be noted that although the studies in the lit-
eratures are valuable for understanding the co-gasification behav-
ior of petcoke with coal, there is still some insufficiency especially
for co-gasification reaction mechanism at high temperature. As the
complicated properties of petcoke and coal, the detail reasons of
synergetic effect during co-gasification is not very clear. It is worth
to verify which components in coal has positive effect on co-
gasification reaction at high temperature. Moreover, it is necessary
to investigate whether the synergetic effect is existent at temper-
atures higher than the coal ash fusion temperature.
In this work, an attempt was made to understand the co-
gasification behavior of petcoke with coal with respect to CO2 in
the temperature range of 1200–1400 °C. A drop-in-fixed-bed reac-
tor coupled with a mass spectrum (MS) was used to analyze the co-
gasification reactivity. Four different rank coals, including two low
rank coal, one middle rank coal and one high rank coal were chosen
to seek the key factor that influence the co-gasification reactivity.
The effect of coal ash on gasification of petcoke was investigated.
XRD method was used to analysis the major mineral matters in
the residual char.
2. Experimental section
compressed into pellets of about 3 mm in diameter and 60 mg in
weight. The choice of the pellet was to facilitate the feeding of
the samples into the drop-in-fixed-bed reactor. The cylindrical pel-
lets were formed by placing the wetted samples into a mould and
applying a pressure of 0.5 MPa. Under the same preparation condi-
tions, the thickness of the pellets is more or less the same.
2.2. Gasification experiments
The experiments were performed in a drop-in-fixed-bed reactor
which was described in detail in our previous work (Fig. 1) [7]. The
alumina reaction tube is placed vertically with a constant-high-
temperature of about 100 mm. The gas is feed in the reaction tube
from the bottom. The sample is charged from the top by the sample
feeder.
In the experiment, CO2 with atmospheric pressure was used as
gasifying agent. The flow rate of CO2 is 500 mL/min which was
selected to avoid the effect of flow rate on gasification reaction. A
single pellet was placed on the sample feeder. When the reactor
reached to the reaction temperature, the pellet was fed and being
placed on the reaction bed within 0.51 s (estimated by considering
the gravity and gas drag force). The gaseous products were imme-
diately swept into an online Mass Spectrometry by the gas flow
and monitored continuously.
Here it should be mentioned is that the pellet mentioned above
may burst into powder after it dropped into the reaction bed. Fig. 2
shows the change of the particle size for typical test samples before
and after fed into the reaction bed, in which the sample is devola-
tilized in Ar under atmospheric pressure at 1400 °C for 1 min. It
shows that the coal/petcoke pellets are likely burst into power.
2.3. Data processing
The carbon conversion ratio was calculated based on the profile
of CO obtained by transforming the data from the online MS. It can
be assumed that the peak area of the CO profile is proportional to
the amount of CO produced during the reaction. The carbon con-
version ratio can be calculated by Eq. (1).
nt;CO kCO  St;CO St;CO
X¼ ¼ ¼ ð1Þ
ntotal;CO kCO  Stotal;CO Stotal;CO

2.1. Samples
Four coals from different rank (XLT and SL, low rank coal; XCG,
middle rank coal and GP, high rank coal), and two petcokes (YS and
JS) were selected. The samples were pulverized to pass through a
100-mesh screen (0.149 mm) and dried in vacuum oven at
110 °C for 24 h prior to use as the raw sample. The results of the
proximate and ultimate analyses of the raw samples are listed in
Table 1.
The powder petcoke and coal or ash sample were thoroughly
mixed with a certain ratio in a mortar for 5 min. Then, about 10%
of distilled water was added to the blends. Finally, the blends were
where X is carbon conversion ratio; ntotal;CO is the total amount of CO
produced; nt;CO is the amount of CO produced from time 0 to time t;
Stotal;CO is the total peak area of CO profile; St;CO is the peak area of CO
profile from time 0 to time t; and kCO is the corresponding coeffi-
cients for the peak area of CO. The gasification rate, r, is defined
as the differential of the carbon conversion ratio with respect to
time and can be derived from Eq. (1) as:
dX 1 dSt;CO
r¼ ¼  ð2Þ
dt Stotal;CO dt
The data process procedure can be seen in our previous work
[7], where the repeatability of the method was also confirmed.

Table 1
Proximate and ultimate analyses of the samples.

Samples Proximate (wt%) Ultimate (wt%, daf)

Ad Vd FCd C H Oa N St
XLT 10.34 42.86 46.80 77.20 4.81 15.51 1.26 1.22
SL 43.16 27.98 28.86 75.40 4.75 17.43 1.22 1.20
XCG 4.11 34.84 61.05 81.73 4.73 12.06 1.23 0.25
GP 22.84 9.14 68.02 88.06 3.81 6.30 1.36 0.47
YS 0.88 7.99 91.13 88.97 3.12 5.54 1.01 1.36
JS 1.54 9.83 88.63 84.98 1.90 5.79 0.93 6.40

A: ash; V: volatile matter; FC: fixed carbon; d: dry basis; daf: dry ash-free basis.
a
By difference.
 L. Ren et al. / Fuel 190 (2017) 245–252 247

Fig. 1. Schematic diagram of the drop-in-fixed-bed reactor system.

2.4. Sample characterization

The XRD patterns of the residual char samples were examined

by a X-ray diffractometer with Cu Ka radiation (D8-Advance of
Bruker). A step size of 0.02° at the speed of 4° (2h)/min over
10–80° was applied.

3. Results and discussion

3.1. The influence of blending ratio

In order to investigate the effect of blending ratio on the gasifi-

cation process, XLT coal was chosen to mix with YS or JS petcoke.
The blending ratio of XLT coal to petcoke is 100:0, 75:25, 50:50,
Fig. 2. Photographs of the sample particles before and after fed into the reaction
bed.
25:75, and 0:100, respectively. The blends were compressed into
pellets (Section 2.1). The gasification reactivity of these pellets is

100 100
XLT XLT
Carbon conversion ratio, X (%)

Carbon conversion ratio, X (%)

80 80
75%XLT+25%YS
75%XLT+25%JS

60 60 50%XLT+50%JS

50%XLT+50%YS
25%XLT+75%JS
40 40
25%XLT+75%YS

20 YS 20
o JS o
Solid line--Experimental 1200 C Solid line--Experimental 1200 C
Dot line--Calculated Dot line--Calculated
0 0
0 100 200 300 400 500 600 700 800 900 1000 0 250 500 750 1000 1250 1500 1750 2000
Time, t (s) Time, t (s)

Fig. 3. Effect of blending ratio on co-gasification reactivity of petcoke with coal.

248 L. Ren et al. / Fuel 190 (2017) 245–252

presented in Fig. 3. In the figure, the solid line was drawn from the
experimental data, while the dot line was drawn from calculated
data (the weighted average data). The weighted average data can
be calculated based on the Eq. (3).
X c ¼ v 1 X 1t þ v 2 X 2t
where v1 and v2 are the percentage content of coal and petcoke in
the blends, respectively; X1t and X2t are the carbon conversion of
single coal and petcoke at time t, respectively.
From Fig. 3, it was observed that the gasification reactivity of
the two petcokes was improved by co-gasification with XLT coal.
The blending ratio has significant effects on co-gasification reactiv-
ity. The high blending ratio of coal to petcoke is favor to the co-
gasification reactivity. For example, the gasification reaction of
50%XLT  50%YS and 50%XLT  50%JS was completed in about
500 s, while the YS and JS petcoke required more than 1000 s
ð3Þ
and 2000 s, respectively. It should be noted that the experimental
data was obvious higher than that of the calculated data at the
same reaction time in the later gasification stage. Moreover, the
complete time of the co-gasification one is much more shorter than
that of petcoke under the same reaction conditions.

100 100
50%XLT+50%YS 50%XLT+50%JS
Carbon conversion ratio, X (%)

Carbon conversion ratio, X (%)

80 80
50%SL+50%JS
50%XCG+50%YS
60 60
50%SL+50%YS 50%XCG+50%JS

40 50%GP+50%YS 40 50%GP+50%JS
JS
20 YS 20
Solid--Experimental o o
1200 C Solid--Experimental 1200 C
Dot--Calculated Dot--Calculated
0 0
0 100 200 300 400 500 600 700 800 900 1000 0 500 1000 1500 2000 2500
Time, t (s) Time, t (s)

100 100
50%XLT+50%YS 50%XLT+50%JS
Carbon conversion ratio, X (%)

Carbon conversion ratio, X (%)

50%XCG+50%JS
80 80
50%GP+50%YS
50%SL+50%JS
60 60
50%SL+50%YS
50%XCG+50%YS 50%GP+50%JS
40 40
JS
YS

20 20
Solid--Experimental o o
1300 C Solid--Experimental 1300 C
Dot--Calculated Dot--Calculated
0 0
0 100 200 300 400 500 600 700 800 900 1000 0 250 500 750 1000 1250 1500 1750 2000
Time, t (s) Time, t (s)

100 100
50%XLT+50%YS 50%XLT+50%JS
YS
Carbon conversion ratio, X (%)

Carbon conversion ratio, X (%)

80 50%SL+50%YS 50%SL+50%JS
80
50%GP+50%YS
50%XCG+50%JS
60 60
50%XCG+50%YS
50%GP+50%JS

40 40

JS
20 20
Solid--Experimental o o
1400 C Solid--Experimental 1400 C
Dot--Calculated Dot--Calculated
0 0
0 100 200 300 400 500 600 700 800 0 500 1000 1500 2000
Time, t (s) Time, t (s)

Fig. 4. Co-gasification reactivity of coals with petcoke in temperature range of 1200–1400 °C.
 L. Ren et al. / Fuel 190 (2017) 245–252 249

Generally, the gasification reactivity of carbonaceous feedstocks As a low rank coal, the XLT coal can greatly improve the gasifi-
can be affect by mineral matters, especially for low rank coals cation reactivity of petcoke. During co-gasification, the complete
[17,18]. For XLT coal, there are plenty of mineral matters which gasification time was significantly reduced and the gasification
results in a high reactivity to some extent. For petcoke, however, reactivity was distinctly improved than that of pure petcoke. It
it can be seen that the mineral matter content is very low; hence, can be say that distinguished synergy effect to improve the gasifi-
the catalytic effect is limited. The higher co-gasification reactivity cation reactivity was occurred during the co-gasification of XLT
of petcoke with coal than that of pure petcoke may mainly attri- coal and petcoke.
bute to the catalytic effect of mineral matters in coal. When it comes to another low rank coal, SL coal, however, the
co-gasification reactivity of petcoke with SL coal was even lower
3.2. The influence of coal type than that of pure petcoke. It seems that the SL coal has a negative
effect on the gasification reaction of petcoke. For the higher rank
In order to verify the influence of coal type on co-gasification coals, the XCG and GP coal only have a very slightly effect on the
with petcoke, four coals in different ranks and two petcokes were gasification reaction of petcoke.
chosen. The blending ratio is 50:50 for coal and petcoke. Fig. 4 It is interesting to note that the two low rank coals, XLT and SL,
shows the co-gasification reactivity of petcoke with coal in temper- with similar reactivity, but appears opposite effect on co-
ature range of 1200–1400 °C. It can be seen that different coals gasification reactivity with petcoke as mentioned above. This
show different features when co-gasified with petcoke. may be caused by the difference in coal composition, especially
the mineral matters constituent and content. The distinguished
Table 2 synergy effect of XLT coal on co-gasification with petcoke is mainly
Ash fusion temperatures of samples. due to the active components in mineral matters. For the SL coal,
Sample DTa/°C STb/°C HTc/°C FTd/°C
the negative effect on co-gasification with petcoke is probably
due to the inhibition of the inert components in mineral matters,
XLT 1243 1271 1287 1299
which may hinder the proceeding of the co-gasification reaction.
SL 1306 1353 1357 1372
XCG 1180 1206 1224 1318 This hypothesis will be verified and discussed further in the next
GP 1481 >1500 >1500 >1500 section.
a In addition, it is known that the industrial gasifier usually oper-
DT: deformation temperature.
b
ST: sphere temperature. ates at temperatures higher than the ash fusion temperature.
c
HT: hemisphere temperature. Therefore, it is necessary to explore whether the synergetic effect
d
FT: flow temperature. is existent at temperatures higher than the ash fusion temperature
of coal. The ash fusion temperatures of coals are shown in Table 2.
It can be seen that the melting temperatures of XLT and SL coal are
all lower than that of 1400 °C. According to the information of
Fig. 6 and Table 2, it can be concluded that the synergetic effect
is existent even at temperatures higher than the ash fusion tem-
perature for XLT coal.
It is known that the molten coal ash will hinder the char gasifi-
cation reaction and lead to a low reactivity at high temperature.
From Fig. 4, however, it can be seen that the XLT coal ash probably
accelerate the gasification reaction of petcoke when the tempera-
ture is higher than the ash melting temperature. Fig. 5 shows the
photographs of co-gasification residual chars of coal and petcoke.
The residual char was prepared in a typical horizontal tube furnace
with a holding time of 1 min at 1400 °C in CO2. From Fig. 5, it can
be seen that the residual ash on the surface of the coal/petcoke is in
a powdered form. No obvious ash melting phenomena was found
Fig. 5. Photographs of co-gasification residual chars of coal and petcoke at 1400 °C when the carbon was present. It shows that the un-reacted carbon
in CO2. can inhibits the melting of minerals in coal when the temperature

100 100 o
(a) 1400 C
o (a) 1400 C
YS+SL ash JS+XLT ash
Carbon conversion ratio, X (%)

Carbon conversion ratio, X (%)

YS+GP ash
80 80
YS
JS
YS+XCG ash
60 60
YS+XLT ash JS+SL ash
40 40
YS+CLR ash

20 20

0 0
0 100 200 300 400 500 600 0 250 500 750 1000 1250 1500 1750 2000
Time, t (s) Time, t (s)

Fig. 6. Gasification reactivity of petcokes with different ashes.

250 L. Ren et al. / Fuel 190 (2017) 245–252

is higher than the melting temperature of minerals. When the car-
bon reaction is complete, the ash begins to melt and aggregate
(point a in Fig. 5). These together provide the possibility of catalytic
effect of coal ash on petcoke at high temperature.
3.3. The influence of coal ash
As discussed above, the mineral matters may play an important
role on co-gasification. It is necessary to investigate the effect of
ash on co-gasification reactivity for a better understanding of co-
gasification mechanism. Except coal ashes, one coal liquefaction
residue (CLR) ash were also selected for comparison. The ash sam-
ples were prepared at 815 °C according to the Chinese national
standard of GB/T 1574-2001. The gasification behaviors of petcoke
with a loading of 10% ash were compared.
Fig. 6 shows the effect of ashes on the gasification reactivity
of petcokes. As expected, the type of ash has a significant effect
on the gasification reactivity of petcoke. The catalytic effect of
the XLT and CLR ash is much higher than that of SL, XCG and
GP ash. The XLT and CLR ash have the similar catalytic effect
on petcoke gasification, which can reduce the complete gasifica-
tion time from 400 s to 200 s for YS petcoke and 1200 s to 250
for JS petcoke. However, the catalytic effect of XCG and GP ash
on gasification is very limited. Moreover, both GP and SL ash
have a certain restraining effect on the gasification reaction of
petcoke. Take SL ash for example, the restraining effect is very
clear. After loading with 10% SL ash, the complete gasification
time increases from 400 s to 600 s for YS petcoke and 1200 s
to 1800 for JS petcoke. The effect of coal ash on gasification of
petcoke is consistent with the co-gasification behaviors of
petcoke with coals which was shown in Fig. 4. This suggests that
the co-gasification behavior is closed related to the minerals in
coal at high temperatures.
There are many types of mineral matters in coal. It is certain
that different mineral matters has different effect on petcoke gasi-
fication reaction. Table 3 shows the composition of different ashes.
From Table 3, it can be seen that the XLT and CLR ash have a much
higher content of Ca and Fe elements than that of other ashes.
These active components are positive effective catalysts for coal
gasification [19–21]. However, for the ash of SL, XCG and GP, there
are large amounts of inert Si- and Al-compounds but lack of active
elements, which are bound to limit the catalytic effect. In addition,
the Si- and Al-compounds tended to cover the surface of the un-
reacted carbon and suppress the gasification reaction [22]. There-
fore, the existence of inert components limited the catalytic effect
and led to a low gasification reactivity.

Table 3
Composition analyses of the coal ashes.

Samples SiO2 Al2O3 Fe2O3 CaO MgO TiO2 SO3 K2O Na2O P2O5
XLT 33.97 10.88 11.67 27.90 2.80 0.70 9.72 0.43 0.08 0.27
SL 60.82 22.89 3.86 3.82 2.55 1.13 1.40 1.10 1.82 0.13
XCG 61.08 18.10 5.25 7.48 2.12 0.97 2.04 1.76 0.46 0.12
GP 51.22 33.44 3.29 5.04 0.99 1.13 2.03 1.04 0.57 0.23
CLR 12.73 7.59 33.67 17.99 4.11 0.42 21.31 0.23 1.17 0.32

90

80 50 Fe2O3+CaO
SiO2+Al2O3
70 Si+Al Fe+Ca
40
60
Content (%)

Content (%)

50 30

40
20
30

20
10
10

0 0
XLT CLR XCG GP SL XLT CLR XCG GP SL

4.0
(Fe2O3+CaO)/(SiO2+Al2O3)
3.5 (Fe+Ca)/(Si+Al)
The value of ratio (-)

3.0

2.5

2.0

1.5

1.0

0.5

0.0
XLT CLR XCG GP SL

Fig. 7. Comparison of mineral matters in coals.

 L. Ren et al. / Fuel 190 (2017) 245–252
1200
50% XLT + 50% YS
1000 A O
O
Intensity (CPS)
800
600
400 M 200
O O
200
0 0
10 20 30 40 50 60 70
o o
2θ ( )
Fig. 8. XRD patterns of major minerals in residual chars (A, Anhydrite; M, Magnetite; O, Oldhamite; Mu, Mulite).
For a better understanding of the effect of mineral matter, the
content of Ca, Fe, Si and Al compounds were compared in Fig. 7.
It can be seen that the content of Si + Al or SiO2 + Al2O3 in XCG,
GP and SL ash is much higher than that of XLT and CLR ash. On
the other hand, the content of Fe + Ca or Fe2O3 + CaO in XCG, GP
and SL ash is much lower than that of XLT and CLR ash. Conse-
quently, the ratio of (Fe + Ca)/(Si + Al) or (Fe2O3 + CaO)/(SiO2 + Al2O3)
of XLT and CLR ash is much higher than that of XCG, GP and SL ash.
For example, the value of (Fe + Ca)/(Si + Al) of XLT and CLR ash is
around 1.30 and 1.65, however, the XCG, GP and SL ash are all
below 0.25. Clearly, the higher the value of (Fe + Ca)/(Si + Al) in
coal, the higher the co-gasification reactivity is, and vice versa.
It is known that the active components such as Ca- and Fe- will
melt and aggregate at high temperatures, which will limit or even
lose the catalytic effect on gasification reaction. Therefore, it is still
doubt that which components have catalytic effects on gasification
reaction at high temperature. Fig. 8 shows the XRD patterns of
major minerals in residual chars (prepared in a typical horizontal
tube furnace at 1400 °C in CO2). The major minerals in 50%XLT
+ 50%YS residual char are oldhamite (CaS), anhydrite (CaSO4),
and magnetite (Fe3O4). These minerals have catalytic effect on
gasification reaction at high temperature which is confirmed by
Ma et al. [23]. For 50%SL + 50%YS residual char, however, major
mineral is mulite (3Al2O32SiO2). The mulite is inert mineral
on gasification reaction. The large amount of mulite will
cover the surface of the un-reacted carbon and hinder the
gasification reaction.
4. Conclusions
In this work, experimental study on co-gasification reactivity of
petcoke with coal under CO2 atmosphere were investigated in a
drop-in-fixed-bed reactor in the temperature range of 1200–
1400 °C. The effect of coal ashes on gasification of petcoke at high
temperature were also studied. The results reveal that the gasifica-
tion reactivity of petcoke can be improved greatly by co-gasifying
with some coals or by loading their ashes, even at temperatures
higher than the ash fusion temperature. It is interesting that both
the coal and its ash can improve the gasification reactivity of
petcoke at high temperature. The synergistic effect during
co-gasification is closely related to the composition of mineral
matter in coal but not coal rank. The high content of active
components such as Ca- and Fe- components in coal or ash led to
high co-gasification reactivity with petcoke at high temperature.
251
600
Mu 50% SL + 50% YS
500
Intensity (CPS)
400
300 Mu Mu
100
80 10 20 30 40 50 60 70 80
2θ ( )
However, the small amount of active components in coal or ash
limited the catalytic effect. Moreover, the high content of inert
Si- and Al-components also tended to suppress the gasification
reaction. During co-gasification, the oldhamite (CaS), anhydrite
(CaSO4) and magnetite (Fe3O4) have positive catalytic effect, while
mulite (3Al2O32SiO2) has negative effect on gasification reaction at
high temperature. Therefore, it is important to seek coals rich in
active components, such as Ca- and Fe- when co-gasify with low
reactivity of petcoke at high temperature.
Acknowledgements
The authors gratefully acknowledge the financial support from
the Hebei Natural Science Foundation in China (B2015109004), the
National Basic Research Program of China (2010CB227003) and the
Major Scientific Research Program of Handan University (14103).
Prof. Bijiang Zhang, Prof. Jianli Yang, Dr. Muxin Liu and Dr. Shijie
Qu of Institute of Coal Chemistry, Chinese Academy of Sciences,
are acknowledged for their valuable suggestions and help with
experiments.
References
[1] Wang J, Anthony EJ, Abanades JC. Clean and efficient use of petroleum coke for
combustion and power generation. Fuel 2004;83:1341–8.
[2] Murthy BN, Sawarkar AN, Deshmukh NA, Mathew T, Joshi JB. Petroleum coke
gasification: a review. Can J Chem Eng 2013;9999:1–28.
[3] Kandasamy J, Gokalp I. Gasification characteristics of petcoke and coal blended
petcoke using thermogravimetry and mass spectrometry analysis. Appl Therm
Eng 2015;80:10–9.
[4] Li Y, Yang H, Hu J, Wang X, Chen H. Effect of catalysts on the reactivity and
structure evolution of char in petroleum coke steam gasification. Fuel
2014;117:1174–80.
[5] Wu Y, Wang J, Wu S, Huang S, Gao J. Potassium-catalyzed steam gasification of
petroleum coke for H2 production: reactivity, selectivity and gas release. Fuel
Process Technol 2010;92:523–30.
[6] Wu Y, Huang S, Wu S, Gao J. Investigations on CS2-solube fractions and
gasification reactivity of liquid-phase carbonization cokes. Energy Fuels
2010;24:5596–601.
[7] Ren L, Yang J, Gao F, Yan J. Laboratory study on gasification reactivity of coals
and petcokes in CO2/steam at high temperatures. Energy Fuels
2013;27:5054–68.
[8] Li C. Some recent advances in the understanding of the pyrolysis and
gasification behaviour of Victorian brown coal. Fuel 2007;86:1664–83.
[9] Boylu F, Dincer H, Atesßok G. Effect of coal particle size distribution, volume
fraction and rank on the rheology of coal–water slurries. Fuel Process Technol
2004;85:241–50.
[10] Azargohar R, Gerspacher R, Dalai AK, Peng DY. Co-gasification of petroleum
coke with lignite coal using fluidized bed gasifier. Fuel Process Technol
2015;134:310–6.
252 L. Ren et al. / Fuel 190 (2017) 245–252
[11] Edreis EM, Luo G, Li A, Xu C, Yao H. Synergistic effects and kinetics thermal
behaviour of petroleum coke/biomass blends during H2O co-gasification.
Energy Convers Manage 2014;79:355–66.
[12] Shen CH, Chen WH, Hsu HW, Sheu JY, Hsieh TH. Co-gasification performance of
coal and petroleum coke blends in a pilot-scale pressurized entrained-flow
gasifier. Int Energy Res 2012;36:499–508.
[13] Zou J, Yang B, Gong K, Wu S, Zhou Z, Wang F, et al. Effect of mechanochemical
treatment on petroleum coke-CO2 gasification. Fuel 2008;87:622–7.
[14] Zhan X, Jia J, Zhou Z, Wang F. Influence of blending methods on the co-
gasification reactivity of petroleum coke and lignite. Energy Convers Manage
2011;52:1810–4.
[15] Fermoso J, Arias B, Gil MV, Plaza MG, Pevida C, Pis JJ, et al. Co-gasification of
different rank coals with biomass and petroleum coke in a high-pressure
reactor for H2-rich gas production. Bioresour Technol 2010;101:3230–5.
[16] Fermoso J, Arias B, Plaza MG, Pevida C, Rubiera F, Pis JJ, et al. High-pressure co-
gasification of coal with biomass and petroleum coke. Fuel Process Technol
2009;90:926–32.
[17] Skodras G, Sakellaropoulos G. Mineral matter effects in lignite gasification.
Fuel Process Technol 2002;77:151–8.
[18] Bai J, Li W, Bai Z. Effect of mineral matter and coal blending on gasification.
Energy Fuels 2011;25:1127–31.
[19] Miura K, Hashimoto K, Silveston P. Factors affecting the reactivity of coal
chars during gasification, and indices representing reactivity. Fuel 1989;68:
1461–75.
[20] Takarada T, Tamai Y, Tomita A. Reactivity of 34 coals under steam gasification.
Fuel 1985;64:1438–42.
[21] Liu X, Zhou Z, Hu Q, Dai Z, Wang F. Experimental study on co-gasification of
coal liquefaction residue and petroleum coke. Energy Fuels 2011;25:3377–81.
[22] Sekine Y, Ishikawa K, Kikuchi E, Matsukata M, Akimoto A. Reactivity and
structural change of coal char during steam gasification. Fuel 2006;85:122–6.
[23] Ma Z, Bai J, Bai Z, Kong L, Guo Z, Yan J, et al. Mineral transformation in char and
its effect on coal char gasification reactivity at high temperatures, part 2: char
gasification. Energy Fuels 2014;28:1846–53.