Applied Thermal Engineering 23 (2003) 22292239

www.elsevier.com/locate/apthermeng

Catalytic cracking of tar component from

high-temperature fuel gas
Binlin Dou
a

a,*

, Jinsheng Gao b, Xingzhong Sha b, Seung Wook Baek

Division of Aerospace Engineering, Department of Mechanical Engineering, Korea Advanced Institute of Science
and Technology, 373-1 Kusong-dong, Yusong-gu, Taejon 305-701, South Korea
b
Department of Energy Chemical Engineering, East China University of Science and Technology,
Meilong Rd. 130 #, 200237 Shanghai, China
Received 19 January 2003; accepted 1 June 2003

Abstract
The cracking removal of tar component in high-temperature fuel gas cleanup is one of the most crucial
problems in developing cleanest advanced power technology. Five catalysts were evaluated to tar component removal from high-temperature fuel gas in a xed-bed reactor. 1-Methylnaphthalene was chosen as
a model of tar component. The Y-zeolite and NiMo catalysts were found to be the most eective catalysts.
Two catalysts almost removed 100% tar component at 550
C. The process variables, temperature and
space velocity, have very signicant eects on tar component removal with catalysts. The long-term durability shows that two catalysts maintain more than 95% removal conversion at 550
C in 168 h. The
combustion study of coke deposited on catalysts by thermal gravimetric analysis technology shows that
very small amount buildup of coke appears on two catalysts surface. Using a rst-order kinetic model, the
apparent energies of activation and pre-exponential factors for tar component removal reaction and coke
combustion on catalysts were obtained for the most active catalysts.
 2003 Elsevier Ltd. All rights reserved.
Keywords: Tar component; 1-Methylnaphthalene; Catalytic cracking; High-temperature fuel gas

1. Introduction
The integrated gasication combined cycle (IGCC) involves the total gasication of coal,
mostly with oxygen and steam, to produce a high heating value, high-temperature fuel gas for

Corresponding author. Tel.: +86-42-869-3754/3710; fax: +86-42-869-3710/5754.

E-mail addresses: bldou@sjtu.edu.cn, bldou@hotmail.com (B. Dou), .

1359-4311/$ - see front matter  2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S1359-4311(03)00185-6

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B. Dou et al. / Applied Thermal Engineering 23 (2003) 22292239

combustion in a gas turbine. The high-temperature molten carbonate fuel cells (MCFC) based on
coal-derived gases is highly ecient in power generation. Aerosol tars are not readily removed
from fuel gas in these processes by conventional means and, as a consequence, often result in
plugged lters or fouled fuel cells, turbines, or sorbents. In addition, fuel gases are often laden
with tars which contain sulfur. High-temperature gas desulfurization processes are not eective
for destruction of tars or removal of the sulfur in the tars. Catalytic cracking of tars to smaller
molecular compounds would prevent these problems [1].
The literature survey indicated that several types of catalysts have potential for cracking tars
generated from coal-derived gases [27]. Nickel catalysts of various types have been found to be
very eective catalysts for tar and as well as for simultaneous ammonia removal in coal or biomass gasication. Two main lines and/or processes are nowadays emerging for cleaning of tars.
One is the use of calcined dolomites or limestones which are active for tars elimination at temperature above 850
C. The other one is the use of hydrocracking or steam-reforming catalysts of
nickel based, which are the most studied in the world [812]. They seem to be the most promising
ones for future commercial applications. In some studies it has been demonstrated that almost
complete tar conversion can been achieved with synthetic catalysts at above 900
C. However, the
catalysts are relatively expensive, and coke deposition on the catalysts is also very serious. In
addition, very high temperatures are required for decomposition of tars. The coal-derived fuel gas
cleanup in IGCC process operates at a low temperature about 500600
C. Consequently using
cheap catalytic materials and eective decomposition of tars with catalysts in low temperatures
become attractive. In this study, the primary objective was to determine the eectiveness in
cracking tar component over various catalysts. The coke buildup on the catalysts was also investigated.
Fixed-bed gasication that uses coal as fuel generates tars which consists mainly of aromatic
ring compounds such as 1-methylnaphthalene (1-MN), naphthalene, benzene and other poly-cycle
hydrocarbons. The main components of poly-aromatic hydrocarbons (tars) in the product gas of
biomass uidized-bed gasication are naphthalene and benzene [13]. There has not been agreement concerning tar model compound. Simell et al. conducted a number of studies on catalytic
cracking of tars with benzene as the model compound [3], but there are some tar components easy
to convert, which consist of multi-aromatic ring compounds. We used 1-MN as a model compound of tar component in this work.

2. Experimental section
2.1. Catalyst preparation
Five catalytic materials, including Y-zeolite, NiMo catalyst, silica, alumina and lime, were used
to remove 1-MN in this study. Among these materials, silica and lime are the naturally occurring
minerals, and Y-zeolite and alumina obtained from the catalyst corporation are commercial
catalysts, NiMo catalyst was prepared by impregnation procedure using a nitrate aqueous solution as a precursor. Surface areas of ve catalytic materials were determined with BET method
using a Micrometric Acusorb 2100E apparatus. All catalysts were calcined at 550
C for 4 h prior

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2231

Table 1
The properties of ve fresh catalysts
Catalyst

Composition (wt%)

Surface area (m2 /g)

Alumina
Lime
Silica
Y-zeolite
NiMo

98.2% Al2 O3 , 2.0% SiO2

77.2% CaO, 7.8% CaCO3 , 6.5% MgO, 8.5% SiO2
12.0% Al2 O3 , 88.0% SiO2
34.1% Al2 O3 , 44.5% SiO2 , 14.5% CaO, 6.9% Na2 O
4.0% NiO, 14.3% MoO3 , 82.7% Al2 O3

258.3
17.8
56.9
585.0
323.3

to use, which were in the form of 0.450.90 mm size in all experiments. Table 1 shows the
compositions of fresh catalyst and results of specic surface area measurement.
2.2. Catalytic activity tests
The experiments for catalytic cracking tar component were carried out by using a xed-bed
reactor. A schematic diagram of the experimental setup is shown in Fig. 1. The details of experimental setup were also previously described [14]. The setup consists of three sections. The rst
section is for preparing a fuel gas with a controlled composition and ow rate. The second section
is the reactor system including the xed-bed reactor and temperature control device. The tube in
the center of xed-bed reactor, which has a diameter of 10 mm and length of 500 mm, is made of
quartz. The tube was placed in an oven which can be operated at temperature between 20 and
1000
C. The sample temperature was indirectly measured by a thermocouple placed at sample
height in between the quartz tube and the inner wall of oven. A test had shown that the dierence
between the temperature at this location and the temperature of sample was not more than 2
C.
The third section is analysis system, which includes some continuous titration systems. The
gaseous euent from the xed-bed reactor is analyzed for 1-MN content by dissolving in a solution of trinitrophenol and titration of the solvent [15]. In a typical experiment, the catalyst
sample of 5 g was supported by quartz wool in the center of tube. The fuel gas which is mixed with
contaminant mainly consisted of 70% N2 and 30% H2 , all experiments were achieved at 101.3 kPa.
Catalytic activity of various catalysts is evaluated by the conversion of 1-MN (x), which is
based on the amount of feeding and the amount of residual 1-MN analyzed from the outlet gases
during the test. Thus, x was calculated by following equation:

Fig. 1. Schematic diagram of experimental apparatus: 1, mass ow controller; 2, mixer; 3, reactor system; 4, temperature control; 5, analysis system; 6, wetmeter.

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B. Dou et al. / Applied Thermal Engineering 23 (2003) 22292239

x Cin
Cout =Cin  100%

Cin and Cout represent the inlet and outlet 1-MN concentrations of the gas (mg/m3 ), respectively.
2.3. The measurement of coke deposited on catalyst
The primary source of deactivation for a catalyst may be the formation of coke deposit on the
catalyst. Thus, an important aspect to consider is the coke yield, which is dened as the grams of
coke divided by the grams of tar converted. The measurement of coke deposited on catalysts by
combustion was investigated using a thermo-gravimetric analyzer (model SDT 2960 and thermal
analyst 2000, TA instruments). Temperature and sample weight were recorded at 10 s intervals.
The sample was heated from 30 to 780
C at a heating rates of 10 K min
1 in a owing air in the
thermo-gravimetric analyzer.

3. Results and discussion

3.1. The catalytic activity for ve catalysts

Conversion(%)

Fig. 2 shows the curves of 1-MN conversions vs time with ve catalysts under the conditions of
550
C, space velocity of 3000 h
1 and inlet 1-MN concentration of 3000 mg/m3 . Fig. 3 gives the
average conversion of 1-MN for 10 h test time. The quartz material was used as inert bed material

100
90
80
70
60
50
0

Y-zeolite
NiMo
lime
alumina
silica

10

time(h)

Average conversion(%)

Fig. 2. Conversion of 1-MN vs time for ve catalysts for 10 h test runs.

100
95
90
85
80
75

Y-zeolite NiMo

Lime Alumina Silica

Catalyst

Fig. 3. Average conversion of 1-MN with ve catalysts for 10 h test time.

Average conversion(%)

B. Dou et al. / Applied Thermal Engineering 23 (2003) 22292239

2233

100
80
Y-zeolite
NiMo

60
40

250

350

450

550

650

Temperature( C)

Average conversion(%)

Fig. 4. Average conversion of 1-MN vs temperature at the space velocity of 3000 h
1 .

100
90
Y-zeolite
NiMo

80
70
0

3000

6000

9000

12000

-1

Space velocity(h )

Fig. 5. Average conversion of 1-MN vs space velocity at 550
C.

to determine the eectiveness of thermal cracking 1-MN, and was also tested at the same conditions. The quartz material cracked 18.3% of 1-MN. Fig. 2 shows Y-zeolite and NiMo catalyst to
be most eective catalysts. Over 10 h test period, two catalysts almost removed 100% of 1-MN,
and deactivations of two catalysts were not yet observed. With other catalysts, deactivation was
rapid. For example, the activity of alumina dropped from nearly 100% of 1-MN conversion
initially to less than 80% after 9 h. The silica appears to be much less catalytic activity than other
catalysts for cracking 1-MN.
Figs. 4 and 5 show the eect of process variables, temperature and the space velocity, on average conversion of 1-MN with two most eective catalysts in test time of 10 h per temperature
and space velocity, respectively. The eect of temperature on conversion was carried out under the
conditions of the space velocity of 3000 h
1 and inlet 1-MN concentration of 3000 mg/m3 . With
various space velocities, the catalytic activities of two catalysts were tested at 550
C, inlet 1-MN
concentration of 3000 mg/m3 . There was a clear eect of process variables on the catalyst activity
in this study. The activities of two catalysts show signicant improvement at the higher temperature. 1-MN average conversion of higher than 90% on two catalysts were achieved above 500

C. Actually, at low temperature the coke formation rate would be higher than the coke removal
one, but catalysts may reduce it by changing the course of catalytic reaction and extend the
lifetime before regeneration is required. Thus with suitable catalysts, the very high temperature
may be not required for catalytic removal of tars from a fuel gas in IGCC and MCFC processes.
Fig. 5 shows that 1-MN average conversion are nearly 100% with two catalysts at space velocity
of 10004500 h
1 , but they dramatically decrease when the space velocity is increased to above
7000 h
1 . It is deduced that the catalysts cannot be eectively used at the high space velocity. The

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B. Dou et al. / Applied Thermal Engineering 23 (2003) 22292239

space velocity, which demonstrates production capacity of the reactor, should be as high as
possible. Therefore, it is necessary to choose the optimum space velocity for eective removal tar
components. It appears that the process conditions play a very important role in tar component
removal with catalytic cracking.
3.2. Catalytic cracking kinetics
The mathematical model used to describe the kinetics of catalytic cracking system undergoing
chemical change is usually expressed in the form:
dx
f xkT
dt

As 1-MN catalytic removal are often chain reactions, f x represents the net result of a series of
elementary steps, each of which has its own activation energy, with the corresponding response to
temperature change. The rate constant k changes with absolute temperature according to the
Arrhenius equation. This model is used almost universally to express the temperature dependence
of the rate constant of the reaction and is dened as:


E
3
kT k0 exp

RT
Fiynns isoconversional method is the most widely used and was adopted in the present study
[9], assuming a rate law of the type:


dx
E
4
k0 exp

1
xn
dt
RT
where x represents 1-MN removal conversion; k0 is the pre-exponential factor for overall removal
reaction; E is the apparent activation energy; T is the temperature; R is the universal gas constant,
n is the reaction progression. The assumption of n 1 might be revised in the future. Nevertheless, n 1 was selected in this work. This is due to most studies in catalytic hot gas have agreed
upon n 1 [16], which also simplify data processing. Such a model was previously described,
which uses the following single rst-order (for tar) kinetic equation [4,12]. Thus, the kinetic
constants for 1-MN removal can be calculated by:


ln1
x
E
ln k0

5
ln

t
RT
The plot of ln
ln1
x=t vs 1=T is a straight line with slop equal to
E=R and an intercept equal to ln k0 .
The average removal rate as function of the temperature is presented in Fig. 6. The plot of
ln
ln1
x=t vs 1=T are presented in Fig. 7. It indicates apparent activation energies around
66.6 and 37.2 kJ/mol for NiMo and Y-zeolite, respectively. The intercepts of the straight line in
Fig. 7 yield the k0 of the removal reaction as 0.000312 and 0.0000568 s
1 for NiMo and Y-zeolite,
respectively. It is found the lower value E of Y-zeolite than one of NiMo catalyst, which indicated
that Y-zeolite is more active than NiMo catalyst for 1-MN removal reaction. There may be due to
a combination of necessary amount of reactive component and favorable structure for Y-zeolite,

Removal rate(mg/g.h)

B. Dou et al. / Applied Thermal Engineering 23 (2003) 22292239

2235

1.8
1.6
1.4

(1) Y-zeolite
(2) NiMo

(1)

1.2
1
0.8
200

(2)

300

400
500
Temperature( oC)

600

700

Fig. 6. 1-MN average removal rate at dierent temperature with two catalysts.

ln[-(ln(1-x)/t)]

-0.6
Y-zeolite
NiMo

-1.2
-1.8
-2.4
0.0012

0.0014

0.0016

0.0018

0.002

1/T(K -1 )

Fig. 7. ln
ln1
x=tas a linear function of the 1=T for two catalysts.

which is crystalline aluminosilicates with a tetrahedral framework structure enclosing cavities

occupied by cations and water molecules. However, the variations in reactivity between two
catalysts were minor. The calculated apparent activation energies reported for tar component
cracking in literature varied over a wide range. Azner et al. [11] found energies between 30 and 97
kJ/mol for dierent catalysts with a rst-order reaction rate, while Narvaez et al. [12] obtained 72
97 kJ/mol also with a rst-order rate.
3.3. The long-term durability of the catalysts
The discussion above suggests the superior catalytic cracking activities of Y-zeolite and NiMo
catalysts under the condition of 500650
C and space velocity of 10004500 h
1 . To conrm the
practical applicability of two promising catalysts, Y-zeolite and NiMo catalyst, long-term durability test was conducted using conditions of 550
C, space velocity of 3000 h
1 and inlet 1-MN
concentration of 1000 mg/m3 in several days, to get data on the catalysts activity vs time which is
shown in Fig. 8. It is shown that two catalysts maintain more than 95% of 1-MN removal conversion for more than 168 h at 550
C. Besides, the conversion shows no tendency to decrease in
these times. Of course, long-term (more than 200 h, at least) tests are needed to check the feasibility of catalysts at a commercial scale.
3.4. Combustion of coke deposited on the catalysts
The primary products of cracking tar component in a fuel gas are coke and gas. The majority of
the sulfur from tar cracking with catalysts is in the gas primarily as H2 S, which can be easily

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B. Dou et al. / Applied Thermal Engineering 23 (2003) 22292239

Conversion(%)

100
80
60
NiMo
Y-zeolite

40
20
0
0

20 40 60 80 100 120 140 160 180

Time(h)

Fig. 8. Durability of two catalysts at 550
C.

removed. The gas produced consisted primarily of propylene, methane, ethylene, ethane, butane,
and so on. The tars contain insucient hydrogen and oxygen to convert all of tars to gases by
cracking, unless hydrogen or oxygen is added from an outside source, while the production of
coke is inevitable. The amount of gases produced from the 1-MN removal conversion is very small
compared to the total simulated fuel gas, and therefore dicult to analyze accurately. But all
catalysts will lose activity with time due to coke build up. The literature agrees that coke mainly
consists of polyaromatic moieties [17]. In the present work on the catalytic cracking of tar model
(1-MN), coke perhaps consists of ve or more aromatic rings. Dierent techniques have been used
to obtain quantitative information regarding the deposition of coke [18]. Among these techniques,
the thermal gravimetric analysis (TGA) is a very simple method using air combustion to convert
coke into gas by calculating weight loss. The value of the error for this technique can be estimated
less than 5% due to the instrumentation sensitivity limited. Coke combustion curves for two
catalysts after durability test by TGA are shown in Fig. 9, and the data of plots are given in Table
2.

Weight(wt%)

100
(1) Y-zeolite
(2) NiMo

(1)

96

(2)

92
88
0

100 200 300 400 500 600 700 800

Temperature( o C)

Fig. 9. TG curves of two samples.

Table 2
The results of TG for two catalyst samples
Catalyst

NiMo
Y-zeolite
a

Sample
(mg)
26.49
19.92

Dehydration
(mg)
2.38
1.24

Coke combustion
temperature

Coke amount

(original/
C)

(end/
C)

(mg)

(%)a

Rate for coke

combustion
(mg/min mg) 10
3

350
400

685
675

1.02
0.41

5.68
4.26

1.15
0.74

g of coke/g of tar component(1-MN) converted.

B. Dou et al. / Applied Thermal Engineering 23 (2003) 22292239

2237

ln(z/T )

-16.8

NiMo
Y-zeolite

-17.4
-18
-18.6
-19.2

0.00126 0.00132 0.00138 0.00144 0.0015

-1

1/T(K )

Fig. 10. Relationship between lnz=T 2 and 1=T .

As expected, a very small amount buildup of coke appears on the catalyst surface (Table 2).
Actually, hydrogen partial pressure in catalytic cracking tar component may be very signicant,
particularly without a hydrogenation catalyst present. Hydrogen in fuel gas may hydrogenate
olens, aromatics and other coke precursors and reduce coke formation. These results show Yzeolite and NiMo are the most promising catalysts for practical application in tar component
removal, having a good anti-coking ability. The conversion of TGA data into the kinetic parameters of coke combustion was based on the classical laws of kinetics. Detailed descriptions of
method for evaluating the kinetic parameters from the TGA data have been given by Coats and
Redfem [19]. The kinetics of coke combustion on the catalysts can be obtained by using following
equation:
dz
0
Af ze
E =RT
dt

where z represents coke combustion conversion; A is coke combustion rate coecient; E0 is apparent activation energy of coke combustion; f z 1
zn , n is coke combustion reaction
progression.
Finally, the following equation can be obtained to calculate kinetic parameters of coke combustion:



 z 
AR
2RT
E0
7
1

ln
ln
T2
bE0
E0
RT
where b is heating rates of temperature on coke combustion:
b

dT
dt

The linearity of lnz=T 2 as a function of 1=T is shown Fig. 10. The result also shows that the
model is good enough for coke combustion. The obtained apparent activation energies for coke
combustion are 54.7 and 60.1 kJ/mol for NiMo and Y-zeolite, respectively.

4. Conclusion
1-MN was chosen as a model of tar component. Five catalysts were evaluated to tar component
removal from high-temperature fuel gas in a xed-bed reactor. The Y-zeolite and NiMo catalysts

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B. Dou et al. / Applied Thermal Engineering 23 (2003) 22292239

were found to be the most eective catalysts. Two catalysts almost removed 100% tar component
at 550
C. However, the temperature and space velocity had signicant eects on the tar component removal conversion with catalysts. The long-term durability shows that two catalysts
maintain more than 95% removal conversion at 550
C, and the conversion shows no tendency to
decrease in several days. The combustion study of coke deposited on catalysts by TGA technology
shows that very small amount buildup of coke appears on two catalysts surface. Using a simple
kinetic model for tar component decomposition and coke combustion, apparent energies of activation and pre-exponential factors were obtained for the Y-zeolite and NiMo catalysts.

Acknowledgement
This work is sponsored by the National Natural Science Foundation of China (No. 59776017).

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