Catalytic and Physical Properties Study on NiO

and Pr203-NiO Based Catalyst for CO2/H2

Methanation
R. M. Hasmizam", H. B. Senin®, B. N. Aziah* and W. A. B. W. Azelee*

Department of Chemical Sciences, ^Department of Physical Sciences, Faculty of Science and

Technology, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia.
*Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 Skudai UTM,
Johor, Malaysia.

Abstract. The catalytic behaviour of undoped NiO and doped Pr203-NiO catalysts toward
CO2/H2 methanation reaction has been performed. The result showed 100% conversion of CO2
to CH4 in the presence of H2 for doped 60Ni-40Pr at 300°C, while for undoped NiO, there was
only 40% of CO2/H2 methanation at the same temperature. The result corresponds to the
presence of higher specific surface area of 60Ni-40Pr compared to undoped NiO catalyst. The
XRD analysis showed that this catalyst has some degree of amorphous properties and the
existence of individual phases of cubic NiO and cubic Pr203, which serves more active site for
CO2/H2 methanation. In addition, complimentary results obtained from SEM showed the present
of homogeneous smaller particle size, which support the good performance of 60Ni-40Pr
catalyst towards CO2/H2 methanation.
Keywords: Nickel Oxide, Catalyst, Methanation
PACS: 81.16.Hc

INTRODUCTION

Nickel oxide based catalyst is active for many kinds of catalytic reaction, including
methanation of CO2/H2 [1], but its efficiency is still low. Recently, it was found that
the addition of rare earth elements can increase the performance of the catalyst [2]. In
general, rare earth elements are used in the form of oxide in catalyst formations
(although they can be introduced in the catalyst in several forms) and it do not act
alone but always in combination with other elements. Their role is, therefore, that
being catalyst promoters (structural and electronic or stabilizers and to improve the
activity or increase the thermal stability of true catalyst) [3]. Praseodymium, is a one
of the promising element among the rare earth elements which have been widely used
in the last decade in catalyst formulations for variety of process in the area both
chemical (refining petrochemical products) and environments especially dedicated to
treatment of exhaust gases from mobile sources. There are also several emerging
apphcations or processes for which rare earth oxides are currently being actively
investigated. More specifically rare earth oxide in mixed oxide formulation is key
components in the catalyst materials for reforming and partial oxidation of methane
and water gas shift reaction for "on board" hydrogen production [4]. In this paper,

CP1017, Current Issues of Physics inMalaysia, edited by H. B. Senin, G. Carini, J. Abdullah, and D. A. Bradley
© 2008 American Institute of Physics 978-0-7354-0538-7/08/$23.00
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influence in the addition of the praseodymium on activity and stability of nickel oxide
based catalysts with respect to the CO2/H2 methanation were reported.

EXPERIMENTAL
Catalyst Preparation

Catalyst was prepared by dissolving nickel salt with minimum amount of distilled
water and stirred. At the same time, praseodymium salt solution was added and
continuously stirred. The mixture was then transferred into an evaporating disc and
aged in an oven at 70°C for 72 hours. A greenish solid gel was formed and calcined at
400°C for 17 hours.

Catalytic Testing

The catalytic activities have been performed in a home-built fixed bed micro
reactor of 10mm inner diameter under the atmospheric pressure. The reaction gas
mixture of CO2 and H2 (1:4 volume ratio) was passed continuously over the catalyst.
Before undergo catalytic measurement, the catalyst was preheated at 300°C for 1 hour
and silica powder was used as dilution agent. The catalytic testing was carried out at
operation temperature of 25 up to 500°C.

Catalyst Characterization

Structured investigation catalyst has been determined by X-ray diffraction with Cu-
Ka (X=1.54A) radiation. Scans were performed in step mode of 0.27second and 0.4
seconds/step. The data was collected over the range of 29 from 10 up to 70°. The
particle size of the catalysts was determined according to the Scherrer equation using
the value of full-width at half-maximum (FWHM). Nitrogen gas adsorption was
carried out at 77K via Micrometrics ASAP 2010 to determine the specific surface area
and morphology of the catalyst was observed using SEM, model Philips XL 40 with
the energy of 15.0 kV.

RESULTS AND DISCUSSION

Catalytic Activities

Figure 1 shows the methanation of CO2 in the presence of H2 by prepared catalyst

for undoped NiO and 60Ni-40Pr catalyst. The additions of praseodymium are effective
to enhancing the catalytic activities. The low performance of the undoped NiO catalyst
is probably due to the carbon deposition during the reaction at higher temperature. It is
well known that the CO2/H2 methanation reaction leading to the carbon deposit on the
catalyst is related to the deactivation of NiO catalyst [5]. Otherwise, the performance
of praseodymium doped catalyst in increases till achieve 100% CO2/H2 methanation
even at higher temperature indicate that the present of dopants can minimize the
coking process, thus show a good catalytic activity even at higher temperature.

306
 100 -1

80 -

60 -

40 -

o 20 -
o

100 200 300 400 500

Temperature, °C
Undoped NiO 60Ni-40Pr
FIGURE 1: The plot of CO2/H2 methanation over undoped NiO and
doped 60Ni-40Pr calcined at 400°C for 17 hours.

Catalyst Characterization

To highlight the role of dopant. X-ray diffraction analysis was carried out for the
prepared catalyst. For the undoped nickel oxide based catalyst, three peaks due to NiO
cubic phase detected are shaper and narrower, which revealed higher degree of
crytalhnity (Fig. 2a). However, for 60Ni-40Pr catalyst, the diffractogram comprises
three broad peaks, assigned to cubic phase NiO which is more amorphous. In addition
peaks due to the presence of cubic Pr203 is also detected (Fig. 2b). The broadening of
peaks was contributed by some degree of amorphous property in the catalyst. The
diffractogram also revealed that the phase structure of NiO and Pr203 exist in their
individual phases, whereby solid-state reaction was not occurring [6]. Table 1 shows
that the BET surface area increase upon the addition of praseodymium into nickel
oxide based catalyst, indicates that the 60Ni-40Pr has a small particle size compared to
the undoped NiO. This result agrees well with the particle size of 60Ni-40Pr derived
from XRD using Scherrer equation (Table 1).

307
 (a)UndopedNiO

^
I
(b) 60Ni-40Pr

^A\yM;#^/i'^Siw^

' ' I I r

10 20 30 40 50 60 70
2 Theta Scale, degree
• NiO (cubic) A PrjOj (cubic)

FIGURE 2: X-ray diffractogram patterns of undoped NiO and 60Ni-40Pr catalysts

calcined at 400°C for 17 hours.

TABLE 1: Average particle size and BET surface area of prepared catalyst

Sample "Average particle size (nm) ""BET surface area (mVg)

Undoped NiO 24.70 5.60
60Ni-40Pr 13.80 75.58
a = derived from XRD using Scherrer equation
b = obtain from nitrogen adsorption

The SEM was used to investigate the surface morphology of the catalysts. The
SEM analysis for undoped NiO showed the formation of bulk NiO with larger particle
size and less disperse on the surface on the catalyst [Fig. 3a]. Figure 3b reveals that the
morphology of the 60Ni-40Pr catalyst gave homogeneous smaller particle size with
uniformly distributed on the surface indicating this catalyst had more amorphous
character.

308
 FIGURE 3: SEM micrograph of (a) undoped NiO (b) 60Ni-40Pr after calcinations
400°C with magnification of lOOOX and scale bar: 10 jim

CONCLUSIONS
The 60Ni-40Pr catalyst revealed good catalytic activity with 100% methanation at
300°C. The XRD analysis of 60Ni-40Pr catalyst shows the existence of individual
phases of NiO cubic phase and Pr203 cubic phase, which serve as active sites for
CO2/H2 methanation reaction. The higher BET surface area of 60Ni-40Pr catalyst
contributes better performance. Meanwhile the SEM analyses have shown that the
60Ni-40Pr formed homogeneous smaller size particle which support the good
performance of the 60Ni-40Pr towards CO2/H2 methanation.

ACKNOWLEDGMENTS
The authors are grateful to Ministry of Science, Technology and Innovation
(MOSTI) of Malaysia for financial support vote 74178.

REFERENCES

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