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Radiation Physics and Chemistry 71 (2004) 10951101

Effect of electron beam irradiation on CO2 reforming of


methane over Ni/Al2O3 catalysts
Jin Juna,*, Jo-Chun Kimb, Joong-Hyeok Shina, Ki-Wan Leea, Young Soon Baekc
a
Department of Environmental Engineering, Dongshin University, 252 Daeho-Dong, Naju, 520-714, South Korea
Department of Environmental Engineering, Konkuk University, 1 Hwayang-Dong, Gwangjin-Gu, Seoul 143-701, South Korea
c
LNG Technology Research Center, Korea Gas Corporation, 973 Dongchun-Dong, Yeonsu-Gu, Incheon, 406-130, South Korea
b

Received 20 February 2003; accepted 18 July 2003

Abstract
The effect of electron beam irradiation on the CO2 reforming of methane over Ni/Al2O3 was investigated. The
conversion rate of CO2 and CH4 forming H2 and CO using various catalysts irradiated with an absorbed dose greater
than 2 MGy was 510% higher than when using an untreated catalyst. The Ni/O ratio on the catalyst surface increased
after treatment with an electron beam, and was more prominent for catalysts with a higher Ni content. As such, based
on XRD and XPS measurements, electron beam treatment was found to result in either the desorption of oxygen from
NiO or the removal of OH groups from the outermost surface layer of the catalyst. In addition, the concentration of
active sites, such as Ni2+ and NiO, or surface defects was also found to increase with the absorbed radiation dose,
thereby increasing the conversion rate.
r 2003 Elsevier Ltd. All rights reserved.
Keywords: CO2 reforming of methane; Electron beam; Reforming catalyst; Ni/Al2O3 catalyst; Synthetic gas

1. Introduction
Recently, there has been an increased interest in the
application of radiation technologies, as they are more
efcient and offer new possibilities for solving environmental problems. For example, it has been reported that
the performance of the electron beam (EB) technique is
equivalent to that of commercially available state-of-theart approaches for water or air pollution control (Getoff,
1999; Matzing et al., 1996). The free radicals produced in
media under the inuence of radiation can initiate
efcient processes, especially in relation to degrading
pollutants or synthesizing new compounds, etc. (Woods
and Pikaev, 1994). In addition to environmental
applications, the effectiveness of radiation technology
has also been demonstrated in the modication of solid
*Corresponding author. Tel.: +82-613303157; fax: +81613303160.
E-mail address: jinjun@dsu.ac.kr (J. Jun).

materials, especially solid catalysts, where g-ray irradiation of a CuOAl2O3 catalyst was found to cause
signicant changes in the surface and catalytic properties
(Youssef et al., 1992; El-Shobaky et al., 1988). As such,
EB technology would appear to be an alternative method
for improving catalysis. The reforming reaction of CH4
with CO2 over various catalysts has already been actively
studied in the context of solving both the greenhouse
effect and energy resourcing (Wang and Lu, 1999; Kim
et al., 2000). Several other methods for improving the
CO2 reforming of methane have also been suggested,
including controlling the size of the catalyst particles to
be nanosized (Kim et al., 2000) and adding alkali metal
oxides or transition metals to the catalyst (Hei et al.,
1998; Choi et al., 1998). Accordingly, the current study
investigated the application of EB technology to improve
the reforming reaction. The conversion rate of CO2 and
CH4 over both pure and EB-treated Ni/gAl2O3 catalysts
was investigated, and the effect of EB irradiation on the
catalytic properties discussed.

0969-806X/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2003.07.006

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J. Jun et al. / Radiation Physics and Chemistry 71 (2004) 10951101

2. Materials and methods


The current study used a Ni/g-Al2O3 catalyst and the
effect of electron beam treatment on the catalyst was
evaluated by comparing the conversion rates of methane
and carbon dioxide when using untreated and
EB-treated catalysts. The results were obtained by
analyzing the surface state change using various
analytical instruments.
2.1. Catalyst synthesis and analysis
Alumina-supported 5 and 20 wt% Ni catalysts were
prepared by impregnating commercial g-Al2O3 (Sterm
Chemicals, 98%) with an aqueous solution of nickel
nitrate (Junsei Chemicals, Japan, Reagent grade). After
evaporation, the catalysts were dried at 110 C for 24 h
and calcined at 500 C for 6 h in air. The surface area
and pore size distribution of the catalysts were measured
using the BET method. To observe the effect of EB
irradiation on the surface properties of the catalysts,
XRD (Rigaku, Geiger), EDX (KEVEX Sigma Gold),
and XPS (ESCALAB220, VG) analyses were carried
out.

controlled using a thermocouple (T-type) positioned on


a tray inside the vessel. A tray, 55 mm in diameter and
2 mm in height, was installed inside the reactor to
maximize the effect of the treatment by layering the
catalyst in a powder phase and enabling the EB
radiation to affect all parts of the catalyst equally.
2.3. Electron beam accelerator and dosimetry
An electron beam accelerator (1 MeV, maximum
power 40 kW, ELV4 Type) was used for the electron
beam irradiation. The absorbed dose was measured
using a cellulose triacetate lm (CTA, FTR=125 Fuji,
Japan). The absorption change in the CTA lms located
above and below the powder catalyst spread thinly on
the reactor tray was measured and the average of both
values considered as the absorbed irradiated dose. The
powder catalyst was re-mixed before the catalytic
reactions and surface analyses were carried out. The
irradiation treatment of the catalyst was performed
under a He atmosphere at room temperature, and the
range of the absorbed dose was 2.54000 kGy. The
catalysts used in the current study were denoted
according to their Ni content and absorbed dose of
irradiation, as given in Table 1.

2.2. Reactor
2.4. Catalytic reaction
To conduct all types of reaction with the same
reaction vessel, a specially designed reactor was constructed, as shown in Fig. 1. An aluminum cylindrical
reactor vessel was constructed with three taper-sealed
access ports on the cylindrical surface, which were used
for the sample inlet/outlet and thermocouple installation. The vessel cover included a titanium foil window to
minimize any electron beam scattering. The volume of
the vessel was 420 cm3. Heating cartridges were immersed into the body of the vessel and the temperature

The effect of EB treatment was evaluated by comparing the conversion rates of CH4 and CO2 between
untreated catalysts and N5 and N20 catalysts treated
with doses of 2.5, 120, 320, 2000, and 4000 kGy. Before
admitting the reactants, the catalysts were pretreated
with 100 ml/min of He at 500 C for 3 h. The catalytic
reforming reaction was carried out under atmospheric
pressure in a ow system and the ow rates controlled
using a mass ow controller (MFC, Bronkhorst,

Fig. 1. Block diagram of experimental apparatus: (A) titanium foil, (B) catalyst, (C) tray with heater and thermocouple, (D) electron
beam window, (E) mass ow controller and (F) mixer.

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Table 1
Notation of catalysts
Ni wt% on g-Al2O3

Absorbed dose (kGy)

Catalysts

Ni wt% on g-Al2O3

Absorbed dose (kGy)

Catalysts

5
5
5
5
5

0
2.5
320
2000
4000

N5
N5-E5
N5-E250
N5-E2000
N5-E4000

20
20
20
20
20

0
2.5
320
2000
4000

N20
N20-E5
N20-E250
N20-E2000
N20-E4000

Netherlands). The molar ratio of the reactant gas


mixture was CO2/CH4/He=1:1:3 with a gas hourly
space velocity (GHSV) of 12,000 cm3 h 1 g 1. The
conversion rates of the reactant gases and products
(H2 and CO) were analyzed by gas chromatography (HP
5890) using TCD and FID.

40

CH4 Conversion
35
30
E
25
20

The conversion rates of the reactants over the N5 and


N20 catalysts irradiated with EB within a range of 2.5
4000 kGy are presented in Figs. 2 and 3, respectively.
The conversion rate of CH4 was 2035% for all the
catalysts concerned, while that of CO2 was 3040%. In
addition, the conversion rate of CH4 was consistently
higher than that of CO2 under the same conditions, and
higher for N20 with a higher Ni content than for N5.
The conversion rates between CO2 and CH4 relative to
the absorbed radiation dose did not exhibit any
signicant differences for the catalysts irradiated with
a low dose of less than 500 kGy, yet the conversion rates
increased for the catalysts irradiated with a dose greater
than 2 MGy.
Youssef et al. (1992) investigated the effect of gamma
rays on the conversion rates of isopropanol as a function
of the absorbed dose within a range of 0.21.6 MGy
over a CuOAl2O3 catalyst. In their study, the conversion rates decreased with the absorbed dose, and
reached a minimum value at 0.4 MGy. However, the
conversion rate was increased with g-ray irradiation at a
higher dose, plus the conversion rates after g-ray
irradiation were slightly higher than those before the
treatment. The explanation given for the increase in the
conversion rates over the catalysts irradiated with a
higher energy was based on an increase in the number of
CuO sites due to the removal of many OH groups on the
catalyst surface. Furthermore, it was also assumed that
the increased activity was due to a change in the
magnetic property of the catalyst.
El-Shobaky et al. (1988) also reported a considerable
increase in activity after g-ray irradiation of a CuO

Conversion (%)

3. Results and discussion


3.1. Conversion rate relative to Ni content and absorbed
dose

D
A,B
C

15
10

CO2 Conversion
35
E
30

D
A,B
C

25
20
15
10
0

30

60

90

120

150

180

Time (min)
Fig. 2. (I) CH4 and (II) CO2 catalytic conversion using N5
series catalyst at 500 C, where applied catalysts were: (A) N5
(), (B) N5-E5 (X), (C) N5-E250 (), (D) N5-E2000 (}) and
(E) N5-E4000 (m).

Al2O3 catalyst. The authors attributed this effect to an


increase in the concentration of active sites and Cu2+
cations along with the desorption of strongly bound
chemisorbed oxygen and removal of OH groups from
the outermost surface layers of the catalyst as a result of
absorption by the g-ray dose.
The present study observed an increase in the
conversion rates of CH4 and CO2 after EB treatment.
This effect was explained by the production of more
active sites on the catalyst surface and by a change in the
oxidation state of the metal. Various instrumental
analyses, such as EDX, XRD, and XPS, were used to
support these explanations.

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Table 2
Effect of EB irradiation on surface area and surface element
composition

40

CH4 Conversion
35
30
25

B
A,C

20

Conversion (%)

Catalysts

Surface
Element composition
area (m2/g)
Al (wt%) O (wt%) Ni (wt%)

g-Al2O3
g-Al2O3-E4000a
N5
N5-E250
N5-E2000
N5-E4000
N20
N20-E250
N20-E2000
N20-E4000

197
193
170
173
198
173
144
136
144
128

E
D

15
10

CO2 Conversion
35

E
D

30

C
A,B

82.05
96.93
64.64
63.66
67.40
65.41
54.48
53.21
49.74
47.53

17.95
3.07
28.21
27.47
20.30
19.28
21.60
21.63
13.48
12.87

7.15
8.87
11.76
14.65
23.93
25.16
36.28
38.24

g-Al2O3 treated with 4 MGy of EB.

25
20

10
0

30

60

90

120

150

180

Time (min)
Fig. 3. (I) CH4 and (II) CO2 catalytic conversion using N20
series catalyst at 500 C, where applied catalysts were: (A) N20
(), (B) N20-E5 (X), (C) N20-E250 (), (D) N20-E2000 (})
and (E) N20-E4000 (m).

wt% ratio (Ni/O)

15

N20
2

N5
0
0

3.2. Variations in surface area and surface composition


after electron beam treatment
The BET surface area and element composition of
each catalyst based on an EDX analysis are presented in
Table 2. The data clearly shows that the surface area of
the catalyst decreased with an increase in the Ni content.
However, an increase in the electron beam dose did not
cause a variation in the surface area of the catalyst.
The oxygen content decreased with an increase in the
absorbed dose, yet at the same time the Ni content was
greatly increased. This phenomenon was more evident
with the catalysts treated with a high dose, greater than
2 MGy, plus it was also found that the oxygen content
on the surface of the pure alumina greatly decreased
after a dose of 4 MGy.
The change in the weight ratio of nickel and oxygen as
a function of the absorbed dose is shown for catalysts
N5 and N20 in Fig. 4. In both cases, the Ni/O ratio
increased linearly with the absorbed dose. The N20
catalyst, containing more Ni, exhibited a much greater
increase in the Ni/O ratio relative to the absorbed dose
than the N5 catalyst.

1000

2000

3000

4000

Irradiated dose (kGy)


Fig. 4. Variation of Ni weight percent ratio (Ni/O) as function
of absorbed radiation dose for catalysts N5 and N20.

To observe the effect of EB irradiation on the catalyst


structure, the XRD patterns were studied as a function
of the dose for the g-Al2O3, N5, and N20 groups, as
shown in Fig. 5.
The N5 and N20 catalysts exhibited the typical shape
of amorphous g-Al2O3, plus the crystallization of the
alumina improved as the absorbed dose was increased.
The N5 group with a small Ni content did not show any
peaks related to Ni support, whereas the N20 group with
a relatively high Ni content revealed manifest peaks
(2y=43.3, 62.9) considered as NiO. In addition, it was
found that the peak intensity increased with the
absorbed dose. As such, these observations support the
fact that the oxygen content was greatly reduced by the
electron beam treatment of g-Al2O3 and that the Ni/O
ratio increased as the dose increased for the N5 and N20
catalysts. In addition, these results indicate that oxygen

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Intensity

N20-E4000
N20-E2000
N20-E250
N20-E5
N20
N5-E4000
N5-E2000
N5-E250
N5-E5
N5
-Al2O3-E4000
-Al2O3-E250
250
-Al2O3
10

20

30

40

50

60

70

2
Fig. 5. XRD patterns of g-Al2O3, N5, and N20 series catalysts exposed to different doses of electron beam irradiation.

I) N5

Ni 2p3/2
B
A

a
b
c
d

Intensity (a.u.)

was removed from NiO, hence the Ni/O ratio was


increased and a variation in the Ni oxidation state
occurred when the initial state of Ni on the fresh catalyst
was NiO. Furthermore, the results also suggest that the
concentration of Ni or surface defects known as active
sites was increased when the treatment caused the
removal of OH groups from the outermost surface
layers of the catalyst. It was found that this effect was
greater for catalysts with a higher metal content. The
variation in the surface after electron beam treatment
was similar to that caused by g-rays (El-Shobaky et al.,
1988; Youssef et al., 1992).
Several researchers have suggested Ni, C, and NiO as
active sites (Ruckenstein and Hu, 1996; Lemonidou
et al., 1998), while Ruckenstein and Hu (1996) proposed
that new active sites of Ni and C are produced during
the reforming reaction of CH4 with CO2 over Ni/gAl2O3. It has also been reported that catalytic activity is
greatly inuenced by the amount of NiO, according to
Lemonidou et al. (1998) who studied the reforming
reaction of CO2 by a nickel calcium aluminate catalyst,
plus Ni2+ exists as NiO rather than in a spinel structure
with an increasing calcination temperature. This is
coincident with the effect that the Ni content on the
surface increases with the calcination temperature, and
matches the results of the current EDX analysis, where
the Ni content increased when increasing the dose of EB
for the N5 and N20 catalysts. Therefore, the enhanced
conversion rates for catalysts treated with a high
radiation dose were attributed to an increase in the
concentration of active sites on the surface, which was
also conrmed by the results of the XPS analysis for the
N5 and N20 catalysts, as shown in Fig. 6.
According to Fig. 6, the intensity of Ni 2p3/2 peak
(binding energy of NiO: 854.3 eV, Ni2O3: 857.3 eV)
decreased with increasing doses of EB over the N5 and

II) N20
B

Ni 2p3/2

a
b
c
d
e

868

864

860

856

852

Binding Energy (eV)

Fig. 6. XPS spectra of Ni 2p for (I) N5 and (II) N20 series


catalysts exposed to different doses of electron beam irradiation:
(a) untreated, (b) 2.5 kGy, (c) 320 kGy, (d) 2 MGy and (e) 4 MGy.

N20 catalysts. It is generally accepted that peak intensity


of XPS increases with decreasing particle size (Delannay, 1984). Therefore, the decrease in peak intensity

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J. Jun et al. / Radiation Physics and Chemistry 71 (2004) 10951101

Table 3
B/A ratio for XPS peak area in Fig 6
Catalysts
Peak area B/A ratio
Catalysts
Peak area B/A ratio

N5
1.11
N20
1.14

N5-E5
1.13
N20-E5
1.24

after irradiation is possibly explained by the fact that EB


irradiation might cause the sintering of Ni on the
surface. The ratio between the two peaks area (A: high
binding energy; B: low binding energy) around 856 eV in
Fig. 6 was evaluated, as seen in Table 3, to investigate
the variation in the oxidation state of Ni with EB
treatment. It was observed that the peak area with the
lower binding energy relatively increased as the
absorbed dose increased for both the N5 and N20
groups, and this effect was more evident for the N20
group catalysts, where the oxidation state of Ni became
lower as the absorbed dose increased. This suggests that
Ni tended to be exposed on the surface after EB
treatment rather than positioned in a Ni2O3 or alumina
site, which also agreed with the EDX and XRD pattern
ouputs.
The output from the EDX measurements clearly
indicated that the oxygen content was seriously reduced,
yet the Ni content on the catalyst surface was
signicantly increased in the N5 and N20 groups as
the absorbed dose increased (Table 2). The XRD results
(Fig. 5) showed that the peak of NiO became larger for
the N20 group as the absorbed dose was increased.
Meanwhile, the outcome from the XPS data (Table 3)
indicated an increase in the NiO concentration as the
absorbed dose was increased. All the results were
consistent with each other. As such, a high dose of EB
treatment was found to produce a change in the
oxidation state of the metal and create surface defects
as active sites, and the greatest effect was exhibited by
N20 with a higher Ni content. Consequently, the effect
of an electron beam was determined to be more
favorable to a catalyst with a higher metal content, as
the active reaction sites were strongly related to the Ni
content.

4. Conclusions
The conversion rate of CH4 and CO2 after EB
treatment of various catalysts at an absorbed dose of
2 MGy was 510% higher compared to that of untreated
catalysts.
Catalytic activity can be increased by EB treatment. It
would appear that the concentration of NiO or surface
defects, known as active sites, is increased if the
treatment causes a change in the oxidation state of the

N5-E250
1.27
N20-E250
1.24

N5-E2000
1.23
N20-E2000
1.40

N5-E4000
1.31
N20-E4000
1.44

metal or removal of OH groups from the outermost


surface layers of the catalyst.
The relative content of Ni on the catalyst surface was
increased by EB treatment, and this effect was more
evident for a catalyst with a greater metal content.

Acknowledgements
The authors thank Dr. H.J. Jung, Dongshin University, for his advice. This study is supported by Korea
Gas Corporation and Biology Research Center for
Industrial Accelerators in Dongshin University that is
assigned by Korea Science Foundation.

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