ARTICLE IN PRESS

Catalysis Communications 5 (2004) 209–213

www.elsevier.com/locate/catcom

Preparation of egg-shell type Ni-loaded catalyst by adopting

‘‘Memory Effect’’ of Mg–Al hydrotalcite and its application
for CH4 reforming
Katsuomi Takehira a,*, Tetsuya Shishido b, Daisuke Shoro c, Kazuhiro Murakami a,
Masahide Honda c, Tomonori Kawabata a, Ken Takaki a
a
Department of Chemistry and Chemical Engineering, Graduate School of Engineering, Hiroshima University,
1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527, Japan
b
Department of Chemistry, Tokyo Gakugei University, Nukui-kita 4-1-1, Koganei, Tokyo 184-8501, Japan
c
Hiroshima Prefectural Institute of Industrial Science and Technology, 3-10-32 Kagamiyama, Higashi-Hiroshima 739-0046, Japan
Received 14 November 2003; accepted 10 February 2004
Published online:

Abstract

Ni-loaded catalyst in egg-shell type was successfully prepared by adopting ‘‘Memory Effect’’ of Mg–Al hydrotalcite-like com-
pounds. Mg–Al mixed oxide particles were prepared by calcination of Mg–Al hydrotalcite and dipped in Ni(II) nitrate aqueous
solution. Upon dipping, Mg–Al hydrotalcite was reconstituted in the surface layer of the particle and a part of the Mg sites was
replaced by Ni. Finally egg-shell type loaded Ni catalyst was obtained after the calcination followed by the reduction of the particles.
The catalyst showed a high and stable activity for autothermal CH4 reforming due to highly dispersed and stable Ni metal particles
concentrated in the catalyst surface layer.
Ó 2004 Elsevier B.V. All rights reserved.

Keywords: Supported Ni catalyst; Egg-shell type loading; Autothermal reforming of CH4 ; Mg–Al hydrotalcite

1. Introduction Supported metal catalysts for the hydrocarbon re-

Hydrogen production for polymer electrolyte fuel cell
(PEFC) is current topics in the world. Steam reforming
of hydrocarbons, especially of methane, is the largest
and generally the most economical way to make H2 [1–
3]. However, the catalyst for the H2 production to PEFC
requires high efficiency and stability taking account that
the reformer should be compact in the FC system not
only on-board of vehicle but also in the stationary FC
system and, moreover, the reformer would be frequently
started up and shut down during the domestic uses and
an air-contamination in the fuel gas could not be avoi-
ded. These restrictions inevitably require a new concept
of the catalyst preparation and also of its use in the
reformer.
*
Corresponding author. Tel./fax: +81-824-24-7744.
E-mail address: takehira@hiroshima-u.ac.jp (K. Takehira).
forming are conventionally prepared by wet impregnation
of different supports. Use of the precursors containing
metal ions in the crystal structure, which on further cal-
cination and reduction, may result in the formation of
highly dispersed and stable metal particles on the surface.
The authors have applied this method for the preparation
of stable and highly dispersed metal-supported catalyst as
‘‘solid phase crystallization’’ (spc) method from perov-
skite [4,5] or hydrotalcite [4,6–15] as precursor.
Hydrotalcite is anionic clays, layered mixed hydrox-
ides containing exchangeable anions and affords the
oxide by calcination that shows interesting properties,
such as high surface area, ‘‘Memory Effect,’’ and basic
character [16]. Preparation of heterogeneous catalyst
from Mg–Al hydrotalcite-type precursors and its utili-
zation in the CH4 reforming have been reported [17–20].
We have recently reported that spc-Ni/MgAl catalysts
were prepared starting from Mg–Al hydrotalcite

1566-7367/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2004.02.004
 ARTICLE IN PRESS
210 K. Takehira et al. / Catalysis Communications 5 (2004) 209–213
containing Ni at the Mg sites as the precursors, and were
successfully applied in the reforming reactions of CH4
[14,15]. Spc-Ni/MgAl precursor uniformly contains Ni
species from the catalyst surface to the bulk by forming
Mg–Ni–O solid solutions. As a result, a considerable
amount of Ni included in the catalyst bulk becomes ir-
reducible and therefore ineffective for catalysts. It is
desirable to prepare supported metal catalysts loaded in
egg-shell type, i.e., active metal species are concentrated
in the surface layer of the catalyst particles where the
gas-phase reaction preferentially proceeds in the micro-
and meso-porous space. We have developed an ad-
vanced method of the preparation of Ni catalysts loaded
in egg-shell type by applying ‘‘Memory effect’’ in which
Mg(Ni)–Al hydrotalcite structure is reconstituted on the
catalyst surface during the preparation. The details of
novel preparation of egg-shell type loaded Ni catalyst
are reported in the present paper.
2. Experimental
Spc-Ni/MgAl catalysts were prepared by spc-method
as previously reported [14,15]; Mg–Al(3/1) hydrotalcite
precursors based on [Mg6 Al2 (OH)16 CO3 ] 4H2 O, in
which a part of Mg(II) was replaced by Ni(II), were
prepared by co-precipitation of nitrates of Mg(II), Ni(II)
and Al(III). An aqueous solution containing the nitrates
was added slowly with vigorous stirring into an aqueous
solution of sodium carbonate. By adjusting pH of the
solution to 10 with an aqueous solution of sodium hy-
droxide, heavy slurry precipitated, followed by the crys-
tal growth by aging the solution at 333 K for 12 h. After
the solution was cooled to room temperature, the pre-
cipitate was washed with de-ionized water and dried in air
at 378 K. The hydrotalcite, [Mg(Ni)6 Al2 (OH)16 CO3 ]
4H2 O, thus obtained was calcined in a muffle furnace in a
static air atmosphere by increasing the temperature from
ambient temperature to 1173 K at a rate of 5 K min
1
followed by keeping at 1173 K for 5 h. The catalyst, spc-
Ni/MgAl, was pressed at 70 MPa, crushed and sieved to
particles of the size of 0.36–0.60 mmu.
Egg-shell type loaded Ni catalysts were prepared by
adopting ‘‘Memory Effect,’’ i.e., the reconstitution of
Mg–Al hydrotalcite structure from Mg–Al mixed oxide
[16]. Mg–Al(3/1) hydrotalcite was prepared by the co-
precipitation from the nitrates of Mg(II) and Al(III),
dried in air at 378 K, and calcined at 1123 K for 1 h to form
Mg–Al(3/1) mixed oxide. The mixed oxide was pressed at
70 MPa, crushed and sieved to particles of the size of 0.36–
0.60 mmu. The particles were immersed in an aqueous
solution of 1.0 M Ni(II) nitrate by controlling pH at
ambient temperature for 15–60 min, dried in air at 378 K
and calcined at 1173 K for 5 h. Thus, spc-preparation was
applied just on the surface layer of Mg–Al(3/1) mixed
oxide particle; Mg–Al(3/1) hydrotalcite structure, a part
of the Mg(II) sites were replaced by Ni(II), was reconsti-
tuted in the surface layer upon immersing the particles in
aqueous solution of Ni(II) nitrate. The egg-shell type
loaded Ni catalysts are denoted as s-spc-Ni/MgAl cata-
lysts, in which s-spc-means surface-spc-method.
Imp-Ni/Mg3 Al catalysts were prepared by impregna-
tion, i.e., incipient wetness method, using Mg–Al(3/1)
mixed oxide particles of the size of 0.36–0.60 mmu as the
carrier in aqueous or acetone solution of Ni(II) nitrate
and denoted as imp-Ni/Mg3 Al-aq or imp-Ni/Mg3 Al-ac,
respectively. Mg–Al(3/1) mixed oxide was prepared by
calcining Mg–Al(3/1) hydrotalcite obtained by co-pre-
cipitation at 1173 K for 5 h in air. The loading amount of
Ni was fixed around 8.3 or 16.3 wt% on all catalysts.
The structures of the catalysts were studied by XRD,
BET, SEM, TEM, and a H2 -adsorption method. X-ray
diffraction was measured by using a Rigaku RINT
2550VHF diffractometer with Cu Ka radiation. BET
measurement was conducted using N2 at 77 K with a
Bell Japan BELSORP18 instrument. Scanning electron
micrograph (SEM) was recorded on a JEOL JSM-6340F
instrument equipped with a Link SATW EDS. Trans-
mission electron micrograph (TEM) was obtained on a
JEOL JEM3000F instrument equipped with a Hitachi/
Kevex H-8100/DeltaIV EDS. The Ni dispersion was
determined by static equilibrium adsorption of H2 at
ambient temperature using the pulse method on a 20 mg
of the catalyst reduced at 1073 K in H2 /N2 (5/20
ml min
1 ) flow for 30 min. The composition of metals
was determined by ICP analysis for both spc- and s-spc-
catalysts after the reduction at 1073 K, while the value
was calculated for imp-catalysts from the amount of raw
materials used.
Autothermal reforming of CH4 was conducted using
a fixed-bed flow reactor in a mixed gas flow of CH4 /
H2 O/O2 ¼ 2/2/1 at 1073 K. N2 gas was added and used
as an internal standard. A U-shaped quartz reactor was
used, with the catalyst bed near the bottom. The catalyst
was calcined by increasing the temperature at a rate of
10 K min
1 from ambient temperature to 773 K, fol-
lowed by at a rate of 2 K min
1 from 773 to 1173 K, and
finally by keeping at 1173 K for 0.5 h. Before the reac-
tion, the catalyst was pre-reduced in a gas flow of 20
vol% H2 /N2 at 1073 K for 1 h. The reaction temperature
was controlled by a thermocouple placed at the center of
the catalyst bed. Product gases were analyzed by online
TCD-gas chromatography. The catalytic activity was
also tested by changing the space velocity from 6000 to
30,000 ml h
1 g-cat
1 with the catalyst particles of the
size 0.36–0.60 mmu dispersed in quartz sand.
3. Results and discussion
Typical XRD patterns of s-spc-catalyst during the
preparation are shown in Fig. 1. Mg–Al hydrotalcite
 ARTICLE IN PRESS
K. Takehira et al. / Catalysis Communications 5 (2004) 209–213
10 kcps
e
Intensity / cps
c
b the calcination was fixed on a sample holder with epoxy
a trated, while Mg was diluted, on going to the surface
0 20 40 60 80
2θ / degree
Fig. 1. XRD patterns during the preparation of s-spc-Ni0:50 /Mg2:63 Al
catalyst (
Hydrotalcite; j Mg–Ni–O; d Ni metal; N MgAl2 O4 ): (a)
after the co-precipitation; (b) after the calcination at 1123 K; (c) after
dipping the sample (b) in Ni(II) nitrate aqueous solution for 15 min; (c)
after the dipping in Ni(II) nitrate aqueous solution for 45 min; (d) after
calcining the sample (c) at 1173 K; (e) after the reduction at 1073 K.
(Mg/Al ¼ 3/1) was formed by the co-precipitation from
the nitrates of Mg(II) and Al(III) (Fig. 1(a)), and con-
verted to Mg–Al(3/1) mixed oxide by the calcination at
1123 K. This mixed oxide was composed of MgO and
MgAl2 O4 spinel (Fig. 1(b)). When the Mg–Al(3/1)
mixed oxide was pressed, crushed and sieved to the
particles and dipped in an aqueous solution of Ni(II)
nitrate (1 M, pH ¼ 3.0) at ambient temperature for 15
min, the reconstitution of Mg–Al hydrotalcite structure
was clearly observed (Fig. 1(c)). Increase in the dipping
time for 45 min (Fig. 1(d)) resulted in no significant
change in the XRD pattern, suggesting that the recon-
stitution proceeded rapidly and almost completed in a
short time within 15 min. By ICP analyses, the con-
centration of Ni in the sample increased, while that of
Mg decreased, after the dipping for 15 min, suggesting
that Ni replaced the Mg site during the reconstruction of
hydrotalcite. No considerable change was observed in
the concentration of Al. When the dipped sample was
again calcined at 1173 K, Mg–Ni–O solid solutions were
formed (Fig. 1(e)) and finally reduced to form Ni metal
after the reduction with H2 as s-spc-Ni0:50 /Mg2:63 Al
catalyst (Fig. 1(f)). The number in the catalyst symbol
shows the content of the corresponding metal obtained
by ICP analyses.
The results of SEM/EDS analyses of s-spc-Ni0:50 /
Mg2:63 Al catalyst are shown in Fig. 2. The sample after
211
Fig. 2. SEM/EDS analyses of cross section of s-spc-Ni0:50 /Mg2:63 Al
catalyst particle.
resin, then polished and analyzed by using Mg Ka and
Ni Ka lines. It is clearly shown that Ni was concen-
layer from the center of the catalyst particle. Both Al
and O showed no observable change over cross-section
of the particle. These again suggest that a part of Mg(II)
sites in hydrotalcite, formed by reconstitution, were se-
lectively replaced by Ni(II) during the dipping. The re-
constitution of hydrotalcite from Mg–Al mixed oxide
may be explained by dissolution-recrystallization
mechanism, i.e., Mg(II) in the mixed oxide tend to dis-
solve in acidic solution, while Mg(II) in solution tend to
form hydrotalcite structure probably due to self-orga-
nization as the motive force, just like as observed in co-
precipitation. Co-presence of Ni(II) reasonably resulted
in the incorporation of Ni(II) at the Mg(II) site.
Interestingly, BET surface area of the Mg–Al(3/1)
mixed oxide particle drastically decreased (from 150 to
0 m2 g
1 ) after the dipping treatment, indicating that
the surface was covered by dense layer. This dense layer
is probably composed of Mg(Ni)–Al hydrotalcite which
covered the particle surface and hindered the further
penetration of Ni(II) nitrate aqueous solution. It is likely
that a balance between the reconstitution rate of
Mg(Ni)–Al hydrotalcite and the penetration rate of
Ni(II) nitrate aqueous solution decides the egg-shell type
Ni loading or not. Egg-shell type Ni loading was
achieved when the surface layer covering by the recon-
stitution of Mg(Ni)–Al hydrotalcite took place rapidly
on the Mg–Al(3/1) mixed oxide particle. A low heating
rate, a low calcination temperature and a short time of
calcination of Mg–Al(3/1) hydrotalcite were preferable
for the egg-shell type Ni loading by accelerating the
reconstitution to form the dense layer of Mg(Ni)–Al
hydrotalcite.
Autothermal reforming of CH4 was carried out at
1073 K over the supported Ni catalysts. The activities of
s-spc-Ni0:50 /Mg2:63 Al and s-spc-Ni0:22 /Mg2:82 Al catalysts
are shown by both CH4 conversion and rate of H2
production with increasing the space velocity in Fig. 3
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212 K. Takehira et al. / Catalysis Communications 5 (2004) 209–213

100 by H2 adsorption well coincided with the order of the

size of Ni metal particles as follows: s-spc-Ni0:50 /

-1
Mg2:63 Al (14.8%)  spc-Ni0:5 /Mg2:5 Al (14.7%) > imp-

Rate of H2 production / mol h g-cat

10
16.3 wt%Ni/Mg3 Al-aq (7.5%) > imp-16.3 wt%Ni/

-1
Mg3 Al-ac (2.7%). Imp-16.3 wt%Ni/Mg3 Al-ac showed a
CH4 Conversion / %

large size of Ni metal particles, since no detectable re-

constitution of Mg–Al hydrotalcite took place in ace-
95 tone solution. Even though imp-16.3 wt%Ni/Mg3 Al-aq
5 induced reconstitution of hydrotalcite during the dip-
ping in aqueous solution, its activity was lower than s-
spc-Ni0:50 /Mg2:63 Al and still lower even compared with
s-spc-Ni0:22 /Mg2:82 Al of small Ni loading of 8.3 wt%
(Fig. 3). Careful treatment in s-spc-preparation induced
90 0
the formation of highly dispersed Ni metal particles in
the surface layer of the catalyst particle, while no sig-
0 100000 200000 300000
nificant effect was expected even in impregnation in
-1 -1
Space velocity/ml h g-cat aqueous solution. The amount of Ni and the depth of Ni
layer could be well controlled by changing the calcina-
Fig. 3. Autothermal steam reforming of CH4 over supported Ni
catalysts. Reaction temperature, 1073 K; CH4 /H2 O/O2 ¼ 2/2/1; d tion procedure of Mg–Al(3/1) mixed oxide, the dipping
s-spc-Ni0:50 /Mg2:63 Al; j s-spc-Ni0:22 /Mg2:82 Al; N spc-Ni0:5 /Mg2:5 Al; s time and the concentration of Ni solution.
imp-16.3 wt%Ni/Mg3 Al-aq;
imp-16.3 wt%Ni/Mg3 Al-ac; — CH4
Conversion; - - - Rate of H2 production.

Acknowledgements

together with those of spc-Ni0:5 /Mg2:5 Al, imp-16.3 The authors sincerely thank the financial support by
wt%Ni/Mg3 Al-aq and imp-16.3 wt%Ni/Mg3 Al-ac as a the Hiroshima Industrial Technology Organization.
comparison. S-spc-Ni0:50 /Mg2:63 Al and s-spc-Ni0:22 / Also the authors sincerely thank the valuable advice of
Mg2:82 Al catalysts were loaded in 16.3 and 8.3 wt% of Professor T. Takahashi of Kagoshima University for
Ni, respectively, after the reduction treatment. Products evaluating the effectiveness factor of the catalyst parti-
distribution always followed the thermodynamic equi- cles.
librium of the reaction as follows: H2 and CO as the
major products together with small amount of CO2 and
H2 O. Among these catalysts, s-spc-Ni0:50 /Mg2:63 Al cat- References
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